Acta mater. 48 (2000) 38573868 www.elsevier.

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COMPLEX HETEROGENEOUS PRECIPITATION IN TITANIUM NIOBIUM MICROALLOYED Al-KILLED HSLA STEELSI. (Ti,Nb)(C,N) PARTICLES
A. J. CRAVEN1, K. HE2, L. A. J. GARVIE1 and T. N. BAKER2
1

Department of Physics and Astronomy, University of Glasgow, Glasgow G12 8QQ, UK and 2Metallurgy and Engineering Materials Group, Department of Mechanical Engineering Materials, University of Strathclyde, Glasgow, UK
( Received 16 November 1999; received in revised form 15 June 2000; accepted 21 June 2000 )

AbstractPrecipitation in TiNb Al-killed microalloyed HSLA steels (Ti/N weight ratio from 4.4 to 1) was investigated in both the as-rolled and the normalised conditions using analytical electron microscopy including parallel electron energy loss spectroscopy (PEELS). An extensive formation of heterogeneously nucleated complex (Ti,Nb)(C,N) particles down to 10 nm in size was observed. The core of such a complex particle is based on TiN and has a spherical, cubic or cruciform shape. The N/(Ti + Nb) atomic ratio in the core is similar to the average value in the steel whereas the Nb/Ti ratio is much smaller than the average value and not proportional to it. Many of the cores have caps in the form of epitaxial overgrowths based on NbC. Their composition changes from Nb(C,N) to (Nb,Ti)C as the N/Ti ratio decreases. The formation of these complex particles and their detailed morphology are controlled by the processing conditions as well as the overall composition. 2000 Acta Metallurgica Inc. Published by Elsevier Science Ltd. All rights reserved. Keywords: Microstructure; Electron energy loss spectroscopy (EELS); analysis(EDX); Microalloyed steels; Carbides/nitrides Energy dispersive X-ray

1. INTRODUCTION

High strength, tough, low carbon plate steels with improved weldability can be achieved by the combination of microalloying and controlled rolling. The improvements in mechanical properties result mainly from the renement of the ferrite grain size together with a controlled amount of dispersion strengthening. One of the benecial effects of Ti additions in Nb high strength low alloy (HSLA) steels is an improvement in the toughness of the heat affected zone (HAZ) resulting from welding, especially after high heat inputs. This is because stable Ti rich carbonitride particles are formed and these can restrict austenite grain growth in the HAZ at high temperature and hence improve HAZ toughness [1, 2]. The presence of Nb(C,N) can effectively retard recovery and recrystallisation during hot rolling, facilitating austenite

To whom all correspondence should be addressed. Tel.: +44-141-330-5892; fax: +44-141-330-4464 E-mail address: a.craven@physics.gla.ac.uk (A.J. Craven) Currently at the Department of Materials Science, University of Leeds, UK. Currently at the Department of Geology, Arizona State University, USA.

and ferrite grain renement. It also contributes to dispersion hardening as ne precipitates ( 10 nm) during and after the austeniteferrite transformation. In practice, multi-microalloying is often adopted by the combination of (Ti + V), (Ti + Nb) or (Ti + Nb + V) micro-additions, with the expectation that the potential of each element can be fully exploited. However, the effect of Ti additions on the mechanical properties is still uncertain and controversial [36]. There is now mounting evidence to show that Ti additions can have unwanted side-effects on the properties of Nb bearing steels. For instance, Crowther and Morrison [3] found that 0.01% Ti additions reduced the yield strength of commercial CMnNb steels in both the as-rolled and normalised conditions by at least 20 MPa on average. This observation was supported by the work by He and Baker [4] on laboratory steels but the loss of strength reported was smaller. On the other hand, it has also been suggested that Ti additions to Nb-bearing HSLA steels enhanced the efciency of Nb strengthening when sufcient Ti was present to combine with all the N in the steel [5, 6]. Because of the importance of multi-microalloying in modifying the microstructure, many attempts have been made to characterise the precipitates in these steels experimentally. There is considerable evidence

1359-6454/00/$20.00 2000 Acta Metallurgica Inc. Published by Elsevier Science Ltd. All rights reserved. PII: S 1 3 5 9 - 6 4 5 4 ( 0 0 ) 0 0 1 9 4 - 4

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that such precipitates have complex structures. Houghton et al. [7] reported precipitates which contained a marked Ti and Nb compositional gradient using energy dispersive X-ray (EDX) microanalysis. Chen et al. [8], also using EDX microanalysis, found a Nb-rich skin with a thickness of about 70 nm surrounding 0.5 m Ti rich cuboids. Grujicic et al. [9] observed a complex of cuboids (>0.1 m) with spherical attachments in a 0.016C0.05Nb0.027Ti 0.075N steel when the specimen was annealed at 1050C for 48 h, then controlled rolled with a nishing temperature of 700C and nally slowly cooled to room temperature. Furthermore, a complex of lath precipitates with a Ti-rich cuboid core was found when the specimen was annealed at 1250C for 1 h and then at 900C for 48 h. On the other hand, no microscopical evidence of such coring effects was obtained in other studies on the growth of TiNb carbonitrides [10] or on the formation, chemistry and stability of carbides and nitrides in TiNb steels [11 13]. However, only the average composition of precipitates in terms of the relative percentages of Ti, Nb and sometimes Al was presented in these publications. This probably reects the difculty of analysing in detail the very small particles ( 20 nm) which are the most effective in dispersion strengthening and grain rening. If the precipitation sequences are not clearly understood, average compositions of the precipitates are of little help in designing multimicroalloyed steels. Apart from these experiments, a number of theoretical models have been developed to predict the precipitation sequence and the micro-chemistry of the precipitates in multi-microalloyed steels [7, 911]. Houghton [14] studied in detail the equilibrium solubility and composition of mixed metal carbonitrides in microalloyed austenite. He treated the problem in the limit of two extreme cases. In the rst, the nitrides and carbides were assumed to undergo complete intermixing of the constituents while, in the second, they were assumed to co-precipitate as two binary compounds. In each case, both the TemkinHillert Staffansson (THS) model and the quasi-regular solution model were used. Houghtons results show that the predictions based on the two extreme cases differed markedly in the temperature range 9001300C, the effective temperature range for solution treatments and thermomechanical processing. However, he found that it was difcult to determine which case best described what is found in practice because there is still a lack of experimental data of sufcient quality. Thus it is still not clear whether the precipitates are a combination of different binary nitrides and carbides, a complete solid solution or somewhere inbetween. The situation is further complicated, in reality, by the effect of Ti additions on the formation of AlN, which results from the Al added to the system to produce austenite grain renement. The objective of the present papers is to survey the precipitate morphologies and compositions found in

a set of controlled-rolled and normalised TiNb microalloyed HSLA steels, to note the effects of the systematic change of the N/Ti ratio and to discuss implications for the properties of the steels. In this paper, we describe the experimental techniques and procedures and concentrate on the results from the (Ti,Nb)(C,N) complex particles. In Part II [15], we deal with the other precipitates observed and the implications for the properties of the steels. Preliminary reports of the work have appeared in References [16, 17].
2. MATERIALS AND EXPERIMENTAL PROCEDURES

Four steels were chosen for investigation. Steels A C underwent the same solidication and thermomechanical treatment. They have Ti/N weight ratios of 1.1, 2.0 and 4.4, respectively, while the value in stoichiometric TiN is 3.4. Thus Steels A and B have insufcient Ti to take up all the N and hence other compounds, such as AlN, would be expected to precipitate. All three steels contain Nb with the aim of forming Nb(C,N) for dispersion strengthening. The fourth steel, labelled A , has a similar composition to Steel A but underwent a different solidication and thermomechanical treatment. The chemical compositions of the steels are given in Table 1. On going from Steel A to Steel B, the N and Nb contents are reduced while maintaining the Ti content and increasing the C content by 20%. On going from Steel B to Steel C, the N and Nb contents are held constant and the Ti content is increased. The levels of the other nitride-forming elements such as Al are maintained at approximately constant levels. These four steels allow both a comparison of the effect of the change of composition with a given treatment and the effect of the treatment for a given composition. Plates of each steel were manufactured by British Steel. Steels A, B and C were vacuum melted at the Swinden Technology Centre, Rotherham while Steel A was a commercial steel. The rolling schedule used provided controlled rolling with a 3:1 reduction below 880C and nishing at 800C. With the exception of Steel A , the nal thickness of the plates was circa 16 mm. The nal thickness of the plate of Steel A was circa 50 mm. Some material, size about 280 mm150 mm16 mm, from Steels B and C was normalised at 910C for 30 min. To study the precipitates, extraction replicas were prepared in a four-step procedure by etching the polished surface in 2% nital, coating the surface with a thin lm of either C or Al, stripping the lm in 5% nital and then cleaning in both distilled water and methanol. The precipitates were examined using imaging techniques, electron diffraction, EDX and parallel electron energy loss spectroscopy (PEELS). For the combined electron diffraction and EDX studies, an Al lm was used. This provided an internal standard for the lattice parameter measurements.

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Table 1. The C, N, Ti and Nb content of the steels in wt%. All steels typically contain the following wt% of other elements: Al (0.036), Mn (1.4), Ni (0.50), P (0.015), S (0.002), Si (0.4). In addition, Steel A contains Cu (0.012) and Steel A contains B (0.0002), Ca (0.0031), Cr (0.027), Mo (0.004) and V (0.003). The Ti/N weight ratio for stoichiometry is 3.42:1 C A A B C 0.060 0.070 0.097 0.081 N 0.0082 0.0079 0.0049 0.0050 Nb 0.023 0.025 0.017 0.016 Ti 0.008 0.009 0.010 0.022 Ti/N (Wt) 1.0 1.1 2.0 4.4

Bright eld (BF) and dark eld (DF) diffraction contrast imaging, electron diffraction and EDX were performed on a Philips EM400T transmission electron microscope (TEM) equipped with a STEM/EDAX 9100-60 system. This system was used for initial inspection of the C replicas in order to select those suitable for more detailed examination in the HB5 system described below. It was also used to obtain selected area diffraction (SAD) data from individual particles on the Al replicas. In these experiments, BF and DF images were used to conrm that the precipitate selected gave rise to the diffraction pattern and EDX analysis was used to measure the mean Ti/(Ti + Nb) atomic fraction from the intensities of the K lines. The cross-sections, uorescence yields and partition functions tabulated by Zaluzec [18] were used to convert the intensity ratio to an atomic ratio. There may be a small systematic error from this process but it remains xed and is smaller than the spread of the compositions observed in the complexes in a given steel. While it is possible to use the Nb L lines instead of the Nb K lines, a degree of caution should be exercised as there are greater uncertainties in the effective L cross-sections. More importantly there are also a number of commercial software packages providing standardless analysis in which there are serious errors when L lines are used. A VG Microscopes HB5 scanning transmission electron microscope (STEM) equipped with a cold eld emission gun operated at 100 keV and postspecimen lenses [19] was used to study a selection of precipitates in more detail. Annular dark eld (ADF) imaging proved very useful for studying the morphology of the precipitate complexes because the various components showed up clearly in the images. The 1 nm diameter probe of the HB5 was used to obtain PEELS and EDX spectra from various points within the complexes so that the compositions of the individual components could be investigated. A probe semi-angle of 8 mrad and a PEELS collection angle of 12.5 mrad were used. To obtain information about the C content of the precipitates, it was essential to reduce, or ideally remove, the C signal from the C replica itself. Thus replicas were prepared with C lms down to a few nanometers in thickness. Numerous holes and cracks formed in these support lms and so, in many cases, it was possible to analyse the parts of the precipitate complex which overhung the

edge of the C lm so removing its C signal altogether. Nominally stoichiometric commercial powders of NbC and NbN and an arc-melted ingot of TiN0.88 were used as standards in the analysis of the PEELS spectra. They were used to determine the atomic ratios and also to provide suitable background shapes under edges when the simple power law form normally assumed was unsuitable. The compositions of the powder standards were conrmed from their lattice parameters, as determined by X-ray diffraction, while that of the TiN0.88 was determined gravimetrically and conrmed using its lattice parameter.
3. RESULTS

3.1. Analysis of the particles Using the HB5 STEM/EDX/PEELS facilities, four distinct phases were identied with nominal chemical compositions of TiN, NbC, AlN and (MnSiN2)(AlN). Many of the precipitates were complexes, i.e. one or more particles of one phase were attached to or surrounded by one or more particles of a second phase. All four phases were found in Steels A and A and these steels also contained the widest range of complex morphologies. Precipitate complexes based on a TiN core with overgrowths based on NbC were the most common precipitate complexes found in all four steels. The results for these (Ti,Nb)(C,N) complexes are considered in detail below. The other phases are considered in Part II [15]. The observed morphologies are described rst. The diffraction and EDX results are then described followed by the detailed PEELS and EDX results. In general, the results for Steels A and A are presented rst, showing the effect of a change in solidication and thermomechanical treatment. The results for Steels B and C are then presented to show the effects of changing composition. Where appropriate, the results presented for the as-rolled condition are supplemented by observations on the normalised condition. In the case where the morphology is common to several of the steels, the best examples of the images and spectra obtained are used whichever steel they are from. 3.2. The morphology of the (Ti,Nb)(C,N) complexes Fig. 1 shows the range of morphologies observed. Fig. 1(a) shows an ADF image of a plate and some cubes on which a single cap is the dominant addition.

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Fig. 1. Images of the (Ti,Nb)(C,N) complexes. (a) An ADF image showing cores in the form of plates or cuboids with predominantly single caps; inset a CTEM dark eld image in the (420) cap reection showing the distribution of the cap phase. (b) An ADF image of cuboid cores with multiple caps; inset is an image showing capping on all faces. (c) An ADF image of small spheroidal cores surrounded by the capping phase. (d) A CTEM bright eld; inset are two ADF images of cruciform complexes.

Inset is a TEM tilted DF image of a similar precipitate taken using the 420 reection from the cap material. This clearly shows the single cap on the left-hand side and may also show additional cap material on either the top or bottom of the core. (There is a well-dened orientation relationship between the caps and the core so that all caps are in contrast together.) Fig. 1(b) shows an ADF image of cuboid cores with several caps. Inset is an example of an ADF image which clearly shows four caps formed on the sides of a cuboid core with the probability that there are also caps on the top and bottom faces. Fig. 1(c) shows an ADF image of smaller spherical particles which often show a marked difference in contrast between the interior and the exterior. This normally indicates a cap in the form of a spherical shell. Fig. 1(d) shows examples of cruciforms. These were conned to Steel A in this study but have also been seen in other related steels [20]. The left-hand side shows a TEM BF image while the right-hand side shows two examples of ADF images of complexes in the shape of a cruciform. Here the precipitates have extended arms along the 001 directions. One of the ADF images shows clearly that all six

possible arms are present and this is true in most cases. Some of the cruciforms look as though there are other phases growing on the arms or around the centre where the arms meet. Because the difference in contrast between the cuboid core and the hemispherical cap is frequently poor in both TEM and STEM BF imaging conditions, the fact that such precipitates are complexes may have been overlooked in some earlier work. However, in the STEM ADF image, the widely different scattering power of the cores and caps gives good contrast between them so that they stand out clearly. Thus the ADF technique is very useful when deciding if the particles are complex, especially when they are below 50 nm in size. It also demonstrates the spatial inhomogeneity of the cap distribution. In some areas of the replica, one or more hemispherical caps are seen on almost every plate or cuboid whereas, in other areas, most cores had no caps. Two size distributions of these core/cap particles were found; one in which the size of both core and cap was the same and in the range of 1550 nm; the other in which the core was a plate with lateral dimensions in the range 501000 nm with a cap with dimensions in the range 4070 nm. In the latter case,

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the cap size appeared to be independent of the size of the plate or cuboid core. However, well developed caps were not observed on the many ne complex particles with dimensions of 20 nm or less. Here, a coating was often revealed by the difference in contrast between the two phases in the ADF image as noted above. In Steel B, the particle size was, in general, larger than in Steel A, while in Steel C, coarser plates and cuboids (size >0.1 m) were found with greater frequency. On average, a higher frequency of caps was formed on the nitride cores in Steel C than in the steels with the higher N/Ti ratios. 3.3. Diffraction and EDX (Ti,Nb)(C,N) complexes analysis of the

Selected area electron diffraction patterns from these complex particles are consistent with a core based on TiN and caps based on NbC with a cube-oncube orientation relationship. Selected area diffraction patterns were taken from a range of individual precipitate complexes and the average value of the Ti/(Ti + Nb) ratio for each complex was measured by EDX spectroscopy using the Philips EM400T TEM system. Data were obtained for Steels A, A , B and C in the as-rolled condition and for Steels B and C in the normalised condition. The complexes were tilted close to a low order zone axis and a particular reection, typically a (420) reection, was set to the exact Bragg condition. Each plate showed both the diffraction pattern from the precipitate complex and the ring pattern from the polycrystalline Al support lm. Thus each plate had its own internal standard, allowing the lattice parameter to be determined from measurements on a single plate and hence eliminating the uncertainty in the camera length. When a reection from one of the phases in the complex was at the Bragg condition, the equivalent reection from the other phase was also very close to the Bragg condition. This is due to the cube-on-cube orientation relationship and the very similar lattice parameters of the two phases. The lattice parameters of the core, acore, and the cap, acap, were determined from this pair of reections. The position of a reection was compared to the position of the nearest ring in the Al pattern to minimise the effect of radial distortion. By making of the order of 10 repeated measurements for each reection and evaluating the mean and the standard error in the mean, a precision of 0.2% could be achieved. There will be residual systematic errors at this level but they should remain the same for all the measurements, allowing the effects of the change of composition to be observed. Some of the diffraction patterns showed spots from only one phase. Tilted dark eld images conrmed that cap material was not present in these cases so that the Ti/(Ti+Nb) ratio represented the metal fraction in the core phase alone. This allows the core lattice parameter to be plotted as a function of the core metal fraction as in Fig. 2. Fig. 2(a) gives the data for as-

Fig. 2. Graphs of lattice parameter versus metal fraction. (a) Steel A : as-rolled; normalised. (b) Steel B: asrolled; normalised. (c) Steel C: as-rolled; normalised. (d) The average values and standard errors in the mean for Steels A, B and C shown on expanded scales: as-rolled; normalised. In each case, the lower dashed line is the data of Duwez and Odell [21] for (Ti,Nb)N and the upper dashed line is the data of Norton and Mowry [22] for (Ti,Nb)C. [NB: in (d) the error bars indicate the precision, the accuracy being limited by residual systematic errors which are the same for all the points.]

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rolled Steels A and A, Fig. 2(b) gives the data for asrolled and normalised Steel B, while Fig. 2(c) gives the same data for Steel C. The error bar shown in each case is typical of that for all points. The dashed lines represent the limits set by the data of Duwez and Odell [21] for (Ti,Nb)N and Norton and Mowry [22] for (Ti,Nb)C. To allow comparisons between the phases in the same steel and in different steels, the means of the core lattice parameters, acore>, the means of the cap lattice parameters, acap>, and the means of the metal fractions of the uncapped cores, Ti/(Ti + Nb)>, are given in Table 2. Also given are the standard errors in the means and the standard deviations of the distributions. Fig. 2(d) shows the mean values and standard errors in the mean for the uncapped cores in Steels A, B and C on an expanded scale. It must be emphasised that while these means are precise and allow inter-comparison, they are not accurate in the sense that residual systematic errors remain at the level of 0.2%. The residual systematic errors are considered further in Section 4.1. 3.4. Detailed PEELS and EDX (Ti,Nb)(C,N) complexes in Steel A analysis of

The 1 nm diameter probe of the HB5 allows the composition within the complexes to be explored in more detail. However, while spectra can be recorded from positions where there is only the cap phase under the beam, it must be assumed that both phases are present at positions where the core phase is under the beam. Given suitable cross-sections or standards, the mean composition at a given position can be found using either the ionisation edges present in the PEELS spectrum or the peaks in the EDX spectrum. However, where the two phases overlie, determining their individual compositions is non-trivial. Even if it is assumed that the composition of each phase is uniform, their relative thicknesses are not known. Fortunately, the situation here is somewhat simpler

than in the general case because the composition of the cap phase can be determined directly. Further, the predictions made by Houghton [14] can then be used as a guide to making the assumptions necessary to obtain a good estimate of the core composition. The analysis below is based on the PEELS data because it gives information on the widest range of elements. The EDX data taken from the same areas is consistent with the PEELS data. In each case, the complexes for which the most complete analysis could be obtained are discussed in detail. The results from similar complexes are then considered. Fig. 3(a) is the PEELS spectrum from point a on the cap of the (Ti,Nb)(C,N) complex shown in the inset image. This complex overhangs the edge of the C lm, which is present in the left-hand part of the image. The background under the Nb M4,5-edge ( 205 eV) has been removed by subtracting a function of the form AE r where E is the energy loss and A and r are constants determined by tting the function to a region of the spectrum prior to the edge [23]. This procedure is followed for all PEELS spectra in subsequent gures. The resulting backgroundsubtracted spectrum shows the Nb M4,5-edges ( 205 eV), the C K-edge ( 282 eV), the Nb M3-edge ( 363 eV), the Nb M2-edge ( 378 eV), the N K-edge ( 397 eV) but no Ti L2,3-edges ( 455 eV) or O K-edge ( 532 eV). The absence of Ti was conrmed by the EDX spectrum from the same point. Fig. 3(b) shows the PEELS spectrum from point b, showing large contributions from Ti and N and smaller ones from Nb and C but no contribution from O. The metal contributions were conrmed by EDX. The simplest way to extract the atomic ratios present in the cap from the spectrum shown in Fig. 3(a) is to compare it to spectra taken from samples of commercial NbC and NbN powders. Such spectra are shown in Fig. 3(a) with the intensities of their Nb M4,5-edges scaled to match that of the spectrum from the cap. Using the spectrum from the NbN powder

Table 2. The mean values of the core lattice parameters, acore>, and metal fractions, Ti/(Ti+Nb)>, for uncapped cores in Steels A , A, B and C in the as-rolled (a-r) and normalised (n) states. The mean values of the lattice parameters of capped cores, acore> and acap>, are also given. The quoted errors are standard errors in the means. The standard deviations of the distributions are in italics. The standard errors in the means show that the means are precise, allowing comparisons between the different phases and steels. However, it must be emphasised that the accuracy is limited by the residual systematic errors, which are estimated to be at a level of 0.2% Uncapped acore> (pm) A (a-r) A (a-r) B (a-r) B (n) C (a-r) C (n) 431.2 1.1 428.2 0.8 427.6 1.2 427.9 1.5 427.4 1.8 428.4 1.3 0.5 0.3 0.4 0.5 0.4 0.4 0.75 0.02 0.04 0.86 0.02 0.04 0.91 0.01 0.03 0.89 0.02 0.05 0.91 0.01 0.03(5) 0.90 0.01 0.02(5) Ti/(Ti+Nb)> 429.2 0.4 0.8 428.0 0.4 0.9 428.0 0.3 0.7 427.4 0.4 0.9 acore> (pm) 445.2 0.2 0.4 444.8 0.4 1.0 445.4 0.5 1.1 440.0 0.5 1.2 Capped acap> (pm)

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Fig. 3. PEELS spectra from the complex in Steel A shown inset: (a) from point a where the cap overhangs the edge of the C support lm, which is present on the left-hand side of the image; (b) from point b where the (core+cap) overhangs the edge of the C support lm.

as a background under the C K-edge, it is clear that the C content of the cap is signicantly less than that of the NbC powder. Similarly, the N content of the cap is very much less than that in the NbN powder. Detailed analysis gives the composition of the cap as Nb(C0.7N0.3). The shapes of the C K-edges in the NbC and the cap are similar but not identical. This change of shape is typical of the effect of the substitution of C by N [24]. However, both shapes are markedly different to that from amorphous C. Altogether, spectra were recorded from caps on a further six capped particles with mean dimensions perpendicular to the beam ranging from 20 to 50 nm. The N/Nb ratios lay in the range 0.250.35 but the underlying carbon lm prevented the C/N ratio from being determined. Turning to the spectrum from point b shown in Fig. 3(b), it is unclear at this stage whether the Nb is in the core or whether it is from overlying cap material. There is also a small amount of C present under the beam. In such a high N steel, Houghtons calculations [14] suggest that the TiN is unlikely to contain signicant C but could contain some Nb. If the C is attributed to amorphous C and not to an overgrowth of the cap phase, then the core has a composition of (Ti0.8Nb0.2)N1.1. If the C signal is attributed to the presence of an overgrowth of the cap phase, the con-

tribution of the overlying phase can be removed by scaling the spectrum in Fig. 3(a) and subtracting it from the (core+cap) spectrum of Fig. 3(b). The scaling factor is chosen so that the C K-edge can no longer be detected. In this case, the core composition is (Ti0.9Nb0.1)N1.1(5). The uncertainties in the Nb/Ti and the N/Ti ratios are 10%. Both values of Ti/(Ti+Nb) are consistent with the distribution of values shown for Steel A in Fig. 2(a). However, N/(Ti+Nb) is most unlikely to exceed unity. Taking into account the estimated errors, the rst composition is consistent with a value of 1. The second composition is only consistent with a value of N/(Ti+Nb) of unity if the error in the N/Ti ratio is underestimated slightly. The spectra from the core regions of the other six complexes examined showed a range of values of the Ti/Nb ratio from 1.8 to 2.2 and of the N/Ti ratio from 1.3 to 1.1. The relatively high amounts of both Nb and N suggest that there is material from the cap phase overlying the core. Unfortunately the signal from C in the underlying amorphous lm dominated that from the C in the cap phase. Hence, it was not possible to make the necessary scaled subtraction to remove the contributions of the cap phase from the (core+cap) spectrum in these cases. Within the errors, the data are consistent with a core composition of (TixNb1 x)N covered by a cap of composition Nb(CuNv). The range of values of x (i.e. Ti/(Ti+Nb)), is consistent with that seen in Fig. 2(a), assuming the range of values of v (i.e. N/Nb) is the same as that noted for the caps above. The ratio of the number of moles of the cap phase to the number of moles of the core phase varied from 0.1 to 0.7, with no apparent dependence on the lateral dimensions of the complex. The cruciform shaped precipitates in Steel A, shown in Fig. 1(d), were also examined. PEELS showed that the main body of the cruciform was (Ti,Nb)N, while EDX showed that the Ti/(Ti+Nb) ratio varied with position in a given cruciform. Values of 0.6, 0.7 and 0.85 were found at three different points on a cruciform which showed no obvious overgrowths. 3.5. Detailed analysis of the (Ti,Nb)(C,N) complexes in Steels B and C Having discussed the complexes in Steels A and A , the morphologically similar features observed in Steels B and C are now considered. The inset to Fig. 4(a) shows an ADF image of a small ( 20 nm) particle in the as-rolled state of Steel B. It consists of a core surrounded by cap material and overhangs the edge of the C support lm, which is present in the top left-hand corner of the image. Fig. 4(a) shows a PEELS spectrum from point a on the cap where it overhangs the edge of the C lm. Only Nb and C edges are present. The absence of Ti was conrmed by EDX. It can be seen that the spectrum shape is a good match to that from NbC powder showing that the cap is close to stoichiometric NbC. Fig. 4(b)

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Fig. 4. PEELS spectra from the complex in Steel B shown inset: (a) from point a where the cap overhangs the edge of the C support lm, which is present in the top left-hand corner of the image; (b) from point b where the cap is over the C support lm; (c) from point c where the (core+cap) overhangs the edge of the C support lm.

shows the spectrum from point b where the cap is over the C support lm. Note that despite its low intensity in the ADF image, the amorphous C lm makes a very large contribution to the C K-edge in the spectrum. An O K-edge is also present. The corresponding EDX spectrum shows the presence of Fe. The association of O with Fe and the C support lm was common and is likely to be the result of residual etching product [25]. Caps from a further eight capped particles, none of which overhung the edge of the amorphous C lm, were examined. Six of these had average lateral dimensions in the range 2030 nm and Ti was undetectable by EELS. In four of the cases, EDX showed a contribution of 2 at% Ti. The white lines of the Ti L2,3-edge should allow Ti to be detected in the EELS spectrum at this concentration. It may be that, in these small particles, the probe was placed sufciently close to the interface between the cap and

the core that the heavy Nb atoms in the cap scattered electrons into the core generating the Ti X-rays. One of the remaining two complexes was 30 nm60 nm and the other was 100 nm100 nm. The cap of the former contained 25 at% Ti while that of the latter contained 15 at% Ti. Thus there appear to be two populations of caps whose composition depends on size. Fig. 4(c) shows a PEELS spectrum from point c where the (core+cap) material is overhanging the hole. Also shown is a linear combination of the edge signals from NbC (scaled to match the Nb edges from the precipitate) and TiN0.88 (scaled to match the N edge from the precipitate). It is clear that the spectrum from the precipitate complex contains more Nb than is necessary for stoichiometric NbC. Detailed analysis shows that the Ti present is slightly less than that required for stoichiometric TiN. Thus the Nb in excess of that required to combine with the C to form the stoichiometric NbC cap is assumed to be incorporated in the core to make up the Ti decit. On these assumptions, the best estimate of the core composition is (Ti0.84Nb0.16)N0.89. The Nb/Ti ratio is uncertain by 20% while the N/Ti ratio is uncertain by 10%. Data were also obtained from one cuboid particle with dimensions of 60 nm. At rst sight, this particle had no cap. The spectrum shows strong Ti L2,3 and N K-edges, whose intensity ratio is consistent with stoichiometric TiN, but it also shows weaker Nb Medges and a weak C K-edge intermediate in shape between that from NbC and that from amorphous C. After subtracting a NbC spectrum (scaled to match the Nb edges), the residual C K-edge shape was close to that from amorphous C. Thus, given that the composition of the other cap material in this steel is NbC, the best interpretation is that the core was close to stoichiometric TiN but was covered by a thin layer of NbC which itself was overlayed by some amorphous C. The N/Ti ratios were measured in the (core+cap) region of four complexes which showed little or no Ti in the cap. This ratio was also measured in three uncapped particles. The mean value of all nine N/Ti ratios was 0.92 with a standard deviation of 0.05. Assuming that the mean value of the Ti/(Ti+Nb) ratio is the same as that in Table 2, the mean value of N/(Ti+Nb) is 0.84 with a standard deviation of 0.05. The inset to Fig. 5(a) shows a complex from Steel C. The C lm in this specimen was thicker than in the earlier specimens and no particles were found overhanging the edge of the lm. Fig. 5(a) is the PEELS spectrum from point a in the cap and this shows that the cap now contains signicant Ti in addition to the Nb. This was again conrmed in the EDX spectrum. The C K-edge intensity is much greater than in NbC and its shape is different, reecting the large contribution from the underlying C lm. Fig. 5(b) is the PEELS spectrum from (cap+core) at point b showing the presence of Ti, N

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values of z could not be determined because of the large contribution from amorphous C. The N/Ti ratio was measured for an additional seven capped or coated complexes. For all nine particles, the values lay in the range from 0.3(5) to 0.9, with a mean value of 0.6(5) and a standard deviation of 0.2. There was no dependence of the ratio on the size of the complex. Assuming the cores had the average value of Ti/(Ti + Nb) in Table 2, the average value of N/(Ti + Nb) in the cores is 0.6 with a standard deviation of 0.2.
4. DISCUSSION

Fig. 5. PEELS spectra from the complex in Steel C shown inset: (a) from point a where the cap is over the C support lm, which is present over the whole image; (b) from point b where the (core+cap) is over the C support lm.

and a small amount of Nb with a large contribution from the C support lm. Thus the overall picture is the same but the details of the partitioning of the elements have changed. The presence of the signal from amorphous C precludes determination of the C content or the determination of the occupation of the non-metal sub-lattice. The approximate composition of the cap is (Nb0.7Ti0.3)Cw where w is undetermined. A further eight particles ranging in size from 20 to 100 nm with either distinct caps or coatings were examined. In most of them, no N was detectable, as would be expected from Houghtons calculations [14]. In two of them, a small amount of N was detected and, in these cases, it is assumed that the coating was thin and the probe was positioned at a point where some of the core was in the irradiated area. The mean value of the Nb/(Ti+Nb) ratio was 0.76 with a standard deviation of 0.07. Fig. 5(b) also shows a comparison of the N and Ti edges from TiN0.88 with those from point b after the contributions from the lower lying edges have been stripped off. This indicates a considerable decit of N in the core. Detailed analysis gives a core composition of (TixNb(1 x))(NyCz). The value of (1 x) is the subject of considerable experimental error with values of 0.16 0.16 and 0.04 0.02 being the best estimates for the two cores it was possible to analyse in detail. The corresponding values of y were 0.46 0.04 and 0.71 0.07, respectively, while the

Table 3 summarises the results of the composition measurements. Most of the values are from the PEELS analysis. However, the Ti/(Ti + Nb) ratios for the core are taken from Table 2. The justication for this is that Table 2 also shows that the mean lattice parameters in the capped and uncapped cores agree within the combined error indicating that there are no signicant differences in composition. The few cases in which the PEELS analysis was able to determine the Ti/(Ti + Nb) ratio support this. Table 3 gives the mean value of each parameter in the general formula for the cap phase, (NbtTi1 t)CuNv, and the core phase, (TixNb1 x)NyCz. Where sufcient data points were obtained, the estimated standard deviation is given in square brackets. In the cases where an element was undetectable (or was at a very low concentration), no standard deviation is given for the relevant mean value, e.g. Ti was not detected in the caps in Steel A and so no standard deviation is given for t. In situations where it was only possible to nd a few values, the mean value is preceded by . In the case of the cap material in Steel B, there appear to be two distributions of metal ratios and so the mean for each is given. In the case of Steel C, no data was obtained for the C content and this is shown as *** in the table. 4.1. Discussion of the observations on the cores In the liquid state there is a much stronger interaction between Ti and O atoms than between Ti and N atoms. However, no TiOx particles were detected in these (Ti,Nb)(C,N) complexes. O, when detected, appeared to be associated with residual etching product [25]. In addition to the particles studied here, there were much larger Ti-rich particles present. These are likely to be TiN and were presumably formed very early in the cooling process. As such, oxide particles may form their cores. Since such large precipitates are too thick for PEELS analysis, it was not possible to conrm this hypothesis. For the complexes considered in Section 3, Fig. 2 shows that the uncapped cores have a range of values for both acore and Ti/(Ti+Nb) and that there is not a strong linear correlation between them. As noted above, there is good agreement between the values of acore> for the capped and uncapped cores in each

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Table 3. Compositions found for cores and caps using PEELS. The values are the means of the observed values. The standard deviations of the distributions are given in square brackets, where available. In cases where an element was undetected or at a very low concentration, no standard deviation is given. Numbers preceded by indicate that it was only possible to obtain a few measurements of the parameter. In the case of the Nb content of Steel B, there appeared to be a bi-modal distribution and the means for each are given. *** indicates no reliable values could be obtained Cap (NbtTi1 Nbt A B C 1.0 1.0 or 0.8 0.76 [0.07] Cu 0.7 1.0 ***
t

)CuNv Nv 0.30 [0.05] 0.0 0.0 Tix 0.86 [0.04] 0.91 [0.03] 0.91 [0.03(5)]

Core (TixNb1 Ny

)NyCz Cz 0 0 ***

1 0.84 [0.05] 0.6 [0.2]

of Steels A, B and C in Table 2. Thus the composition of the cores is independent of whether they are capped or not. The same may not be true for Steel A since Table 2 shows that the values of acore> for capped and uncapped cores differ by more than the combined standard errors in the mean. It is also clear from Fig. 2(ac) that the distributions of the points for Steels A, B and C overlap each other but not that for Steel A . Steels A, B and C have different compositions but the same solidication and thermomechanical history. The mean values of Ti/(Ti+Nb) for Steels A, B and C in Table 2 are all 0.9 and change relatively little despite the much larger change of this fraction in the steels as a whole. Table 4 shows that the Nb/Ti ratios in the steels as a whole are much greater than those in the cores, in agreement with Houghtons calculations [14]. These calculations show that the Nb/Ti ratio in precipitates in equilibrium at high temperature is always small. However, one might expect the change in the average Nb/Ti ratios in the steels to be reected in the values in the cores. This is true on going from Steel A to Steel B but it is not clear that there is a further change in the core value on going from Steel B to Steel C. Thus the absolute metal fraction in the cores is not very sensitive to the equivalent overall metal fraction in the steel for a given solidication and thermomechanical history but does reect it to some extent. On the other hand, Table 2 shows that Ti/(Ti + Nb)> in the cores differs signicantly between Steels A and A . These steels have similar mean compositions but have undergone different solidication and thermomechanical treatments in that the nal sheet thickness of Steel A is circa 50 mm whereas that of Steel A is circa 16 mm. This implies

a slower cooling rate for Steel A . Thus the observation is in qualitative agreement with Houghtons calculations [14] which show that the precipitates come out of solution at high temperature with a composition approaching TiN. As the temperature is lowered, the Nb content rises but remains relatively low, even under equilibrium conditions, until the temperature falls to a point where other phases start to precipitate. In practice, the cores will have formed at high temperature during casting. The slower the cooling of the steel, the higher will be the resulting Nb/Ti ratio, as observed in Steel A . Thus, it is clear that the major factor determining the mean metal fraction of the cores is not the steel composition but its solidication and thermomechanical history. Table 4 also compares the mean value of the nitrogen to metal ratios in the cores with the equivalent mean value in the steel as a whole. While the value of the N/Ti ratio in the core differs signicantly from the average value in the steel, the values of the N/(Ti + Nb) ratios are very much closer. It is now worth considering the observed values of the lattice parameters in more detail. In the ideal case of data without random or systematic errors, the lattice parameters corresponding to compounds with a N/(Ti+Nb) ratio of unity would lie along a smooth curve. The best estimate of this smooth curve is given by the data of Duwez and Odell [21], shown in Fig. 2 as the lower dashed line. Substitution of C for N will push a point above this curve while substitution of vacancies for N will push a point below it. Substitution of a C atom has approximately twice the effect on the lattice parameter as substitution of a vacancy [26]. In reality, there are random and systematic errors. There is some uncertainty about the data of Duwez

Table 4. Comparison of some atomic fractions in the steels and in the cores of the (Ti,Nb)(C,N) complexes A Nb/Ti N/Ti N/(Ti+Nb) Steel Core (a-r) Steel Core (a-r) Steel Core (a-r) 1.43 0.14 3.0 1.2 1.23 1.0 B 0.88 0.10 1.7 0.9 0.89 0.84 C 0.37 0.10 0.8 0.8 0.56 0.6

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and Odell [21] because the lattice parameter of NbN is signicantly lower than the currently accepted value [26]. Thus it is likely that the true curve gradually deviates upward from that shown as the value of Ti/(Ti + Nb) decreases from unity. At a value of Ti/(Ti + Nb) of 0.7, the deviation might be 0.6 pm. There are also residual systematic errors in the values of the data points plotted in Fig. 2. However, these residual errors should be the same on all points, effectively shifting all the points by the same amount with respect to the line of the Duwez and Odell data. To investigate this, the difference between the measured lattice parameter and that expected from the Duwez and Odell data for the corresponding value of Ti/(Ti + Nb) was evaluated for each data point from Steels A, B and C. Table 5 gives the mean, the standard deviation and the standard error in the mean for the resulting distribution for each steel. With the exception of normalised Steel C, all the distributions have the same mean value of 1 pm within the standard errors in the mean. However, the mean of the distribution from normalised Steel C differs from the others by approximately twice the combined errors in the means. Since Steel A is close to a stoichiometric nitride, the mean value of its distribution in Table 5 would be close to zero in the absence of residual systematic error. Hence the actual value of the mean is the best estimate of the residual systematic error in the lattice parameter measurements, i.e. 0.7 0.4 pm. If this estimate is subtracted from all the measured values then the resulting points spread above and below the DuwezOdell line. A signicant number of points lie further from the DuwezOdell line than the 1 pm error on the individual measurements and such points are found both above and below the line. This suggests that the sites not occupied by N atoms can be either vacant or occupied by C atoms, with the proportion varying from complex to complex. To see if the results are compatible with such a hypothesis, the spread of lattice parameters expected from it can be estimated and compared to that observed. In Steel B, on average 16% of the nonmetal sites do not contain N. Placing C atoms on all these sites will increase the lattice parameter by 1.3 pm relative to that of the stoichiometric nitride while placing vacancies on all these sites would reduce the lattice parameter by 0.7 pm giving an overall spread

of 2 pm. In Steel C, the equivalent percentage is 24% giving a spread of 3 pm. These values can be compared to twice the standard deviations of the distributions in as-rolled Steels A, B and C, which are 1.8, 2.0 and 3.2 pm, respectively. Thus the spread of the data points increases in the predicted way on going from Steel B to Steel C and Figs 2(b) and (c) show this increased spread clearly. After normalising, the distribution of the results for Steel B differs little from the as-rolled distribution whereas there is a very clear change in that for Steel C, as can be seen in Fig. 2(c) and Table 5. The mean increases from 0.8 to 1.8 pm, the difference being 2 times the combined standard errors. The standard deviation also drops from 1.6 to 1.1 pm. Further, after normalising, no points from Steel C are left more than 0.5 pm below the DuwezOdell curve, even after correcting for the estimated residual systematic error. The majority of points are now well above the line, indicating a very signicant C content. Thus the observations are consistent with the normalising process allowing further C to diffuse into the core to ll some or all of the vacancies present in the as-rolled state. Such a process will increase the mean of the distribution and make it narrower, as observed. In Steel A , the cruciform precipitates observed were based on (Ti,Nb)N. The large excess of N and the particular local cooling rate in this sample obviously led to the continued growth of the (Ti,Nb)N, presumably with an increasing Nb content as the precipitation proceeded. This would explain the variation of the Ti/(Ti + Nb) ratio with position along the arms. It is not clear why this extended growth should occur in preference to overgrowths of Nb(C,N) which occurred elsewhere in the sample and which some ADF images suggest may also be present on the surface of some cruciforms. 4.2. Discussion of the observations on the caps Table 2 shows that acap> is the same in Steels A , A and B to within the combined standard errors in the mean. However, acap> in Steel C is signicantly lower, making it closer to that of the core. This convergence is likely to be the explanation for the greater number of caps found in Steel C since it will make nucleation of the cap more likely by lowering the energy barrier. The change in lattice parameter is also consistent with the compositions of the caps given in Table 3. In Steel A, the excess N present has been incorporated into the cap while it is the excess Ti that has been incorporated in the cap in Steel C. Ti substitution for Nb has a much bigger effect on the lattice parameter than N substitution for C. Hence the similar lattice parameters for the caps in Steels A , A and B but the smaller value in Steel C. The compositions of the caps are much more sensitive to the mean composition of the steels than are the cores, as can be seen in Table 3. If there is far more N than required to combine with the Ti, as in Steel A, all the Ti goes into the cores and the excess

Table 5. The means, standard deviation and standard error in the mean of the distribution of lattice parameters relative to the stoichiometric lattice parameters of Duwez and Odell [21] Steel A (a-r) B (a-r) B (n) C (a-r) C (n) Mean (pm) 0.7 1.0 1.0 0.8 1.8 Std. dev. (pm) Std. error (pm) 0.9 1.0 1.1 1.6 1.1 0.4 0.4 0.4 0.4 0.4

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CRAVEN et al.: COMPLEX HETEROGENEOUS PRECIPITATIONI. AcknowledgementsThe authors would like to thank the EPSRC for support under grant GR/G12832 and Dr D.J. Price of British Steel for support under contract DJP/223/136.

N appears in the cap. If there is insufcient N, as in Steel C, then it all goes into the cores and some of the excess Ti goes into the caps.
5. CONCLUSIONS

REFERENCES 1. Kanasawa, S., Nakashima, A., Okamoto, K. and Kanaya, K., Trans. Iron Steel Inst. Japan, 1976, 16, 486. 2. Wang, G. R., Lau, T. W., Weatherly, G. C. and North, T. H., Metall. Trans., 1989, 20A, 2093. 3. Crowther, D. N. and Morrison, W. B., in Titanium Technology in Microalloyed Steel, T. N. Baker. Institute of Materials, London), 1997, p. 44. 4. He, K. and Baker, T. N., Mater. Sci. Eng, 1993, A169, 53. 5. Repas, P. E., in HSLA Steels, Technology and Application, M. Korchynsky. ASM, Metal Park, OH, 1984, p. 203. 6. Tirnanic, S., Curcic, R., Tirnanic, D. and Drobnjak, D., Steel Res., 1989, 60, 561. 7. Houghton, D. C., Weatherly, G. C. and Embury, J. D., in Thermomechanical Processing of Microalloyed Austenite, A. J. DeArdo, G. A. Ratz and P. J. Wray. TMS-AIME, New York, 1982, p. 267. 8. Chen, Z., Loretto, M. H. and Cochrane, R. C., Mater. Sci. Technol., 1987, 3, 836. 9. Grujicic, M., Wang, I. J. and Owen, W. S., Calphad, 1988, 12, 261. 10. Zou, H. and Kirkaldy, J. S., Metall. Trans., 1991, 22A, 1511. 11. Strid, J. and Easterling, K. E., Acta metall., 1985, 33, 2057. 12. Emenike, C. O. I. and Billington, J. C., Mater. Sci. Technol., 1989, 5, 566. 13. Lehtinen, B. and Hansson, P., Scandinavian J. Metall., 1989, 18, 295. 14. Houghton, D. C., Acta metall., 1993, 41, 2993. 15. Craven, A. J., He, K., Garvie, L. A. J. and Baker, T. N., Acta mater., 2000, 48, 3869. 16. He, K., Garvie, L. A. J., Craven, A. J. and Baker, T.N., Electron Microscopy 1994, Proceedings of the XIIIth International Congress on Electron Microscopy, Vol. 1, B. Jouffrey, C. Colliex, J. P. Chevalier, F. Glas, P. W. Hawkes, D. Hernandez-Verdun, J. Schrevel and D. Thomas, Les editions de physique, Les Ulis, France, 1994, p. 665. 17. Craven, A. J., He, K. and Baker, T. N., IOP Conf. Ser., 1997, 153, 605. 18. Zaluzec, N. J., Bull. Electron Microsc. Soc. Am., 1984, 14(1), 67. 19. Craven, A. J. and Buggy, T. W., Ultramicroscopy, 1981, 7, 27. 20. Roberts, A. C. and Evans, H. E., in Mechanical Behaviour and Nuclear Applications of Stainless Steels at Elevated Temperatures. Metallurgical Society, London, 1982, p.51. 21. Duwez, P. and Odell, F., J. Electrochem. Soc., 1950, 97, 279. 22. Norton, J. T. and Mowry, A. L., Trans. Am. Inst. Min. Engrs, 1949, 185, 133. 23. Egerton, R. F., in Electron Energy Loss Spectroscopy in the Electron Microscope. Plenum, New York, USA, 1986. 24. MacKenzie, M., Craven, A. J., Scott, A. and Brydson, R., to be published. 25. Baker, T. N. and Ubhi, H. S., in EMAG 87 Analytical Electron Microscopy, G. W. Lorimer. Institute of Metals, London, 1988, p. 135. 26. Goldschmidt, H. J., in Interstitial Alloys. Butterworths, London, 1967.

The least soluble phase is that based on TiN and it forms the cores of the (Ti,Nb)(C,N) complexes. Its precipitation occurs at high temperature, i.e. early in the process. The Nb/Ti ratio in such cores is much lower than the average value in the steel and changes relatively little as the average value changes. However, for a given value in the steel, the Nb/Ti ratio in the core is markedly affected by the cooling rate during solidication and thermomechanical processing. The N content in the core reduces as the excess of N over Ti decreases and there is a close agreement between the N/(Ti + Nb) ratio in the core and that in the steel as a whole. Where the average N/(Ti + Nb) ratio is less than unity (e.g. Steels B and C), some of the non-metal sites are not occupied by N. In the asrolled state it appears that some of these sites remain vacant and some are occupied by C. If the value of N/(Ti + Nb) is particularly low, the vacancy concentration in the as-rolled state may be quite high, e.g. Steel C. In this case, further C diffuses in to ll some or all of the vacancies when the steel is normalised. However, the population of the metal sub-lattice is not signicantly changed by this process. The composition of the cap phase that precipitates out at lower temperatures is much more sensitive to the mean composition of the steel. The cap composition varies from Nb(C,N) to NbC to (Nb,Ti)C as the N and Nb content is reduced and the Ti content is increased on going from Steel A to Steel C. Once Ti starts to substitute for Nb in the cap phase, the lattice parameter of the cap moves signicantly towards that of the core. This reduces the energy barrier for the nucleation of the cap leading to an increased number of caps on the cores. The use of SAD plus EDX was very valuable in that it allowed the rapid study of many complexes but suffered from the inability to fully interpret the data from complexes composed of several phases. The ADF technique proved very useful as it showed up the multiple phases very clearly and allowed a high spatial resolution probe to explore the variation of composition with position. PEELS was particularly valuable, allowing the compositions of the individual phases to be estimated reasonably accurately in the cases where particles could be found overhanging the edge of the carbon support lm. The results obtained show that future studies designed with this aim in mind will be able to achieve much more.