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Characterization of the carbides and the martensite phase in powder-metallurgy high-speed steel

Matjaž Godec a, , Barbara Šetina Batič a , Djordje Mandrino a , Aleš Nagode a , Vojteh Leskovšek a , Srečo D. Škapin b , Monika Jenko a

a Institute of Metals and Technology, Lepi pot 11, 1000 Ljubljana, Slovenia b Jozef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia




Article history:

A microstructural characterization of the powder-metallurgy high-speed-steel S390

Received 16 July 2009 Received in revised form 28 January 2010 Accepted 1 February 2010


Microclean was performed based on an elemental distribution of the carbide phase as well as crystallographic analyses. The results showed that there were two types of carbides present: vanadium-rich carbides, which were not chemically homogeneous and exhibited a tungsten-enriched or tungsten-depleted central area; and chemically homogeneous


tungsten-rich M 6 C-type carbides. Despite the possibility of chemical inhomogenities, the crystallographic orientation of each of the carbides was shown to be uniform. Using electron

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Tool steel

backscatter diffraction the vanadium-rich carbides were determined to be either cubic VC or


hexagonal V 6 C 5 , while the tungsten-rich carbides were M 6 C. The electron backscatter


diffraction results were also verified using X-ray diffraction. Several electron backscatter


diffraction pattern maps were acquired in order to define the fraction of each carbide phase


as well as the amount of martensite phase. The fraction of martensite was estimated using


band-contrast images, while the fraction of carbides was calculated using the

crystallographic data.




carbides that are present are really VC. Q.L. Yong et al. [4] reported

Powder metallurgy is an important alternative route for tool-steel production. Its main advantage is the possibility to obtain a refined steel that is almost free of inclusions and has a uniform microstructure, which then leads to a steel with isotropic performance [1,2]. The high-speed steel produced by powder metallurgy contains primary carbides that are rich in vanadium, tungsten and molybdenum. These carbides play an important role in the mechanical properties of the steel, including the hardness, the wear resistance and the temperature resistance. It is known that in S390 Microclean, as well as in steels with similar compositions, two carbide types, i.e., tungsten-rich M 6 C and vanadium-rich MC, are formed [3]. However, with regard to the vanadium-rich carbide phase, it is not clear whether the

that it is usual for most of the vanadium carbides in this type of steel to be V 8 C 7 or V 6 C 5 . Later experiments [5] using TEM identified the vanadium-rich carbides as V 6 C 5 in PM HSS Vanadis 4 (V4). The main goal of this study was to identify the carbide phases in powder-metallurgy S390 Microclean by using the electron backscatter diffraction (EBSD) technique, which was originally developed for microtexture analysis. However, progress in instrumentation and the development of software now mean that it is possible for this technique to be used for phase analyses [6]. Although one of the first applications of the EBSD technique for the identification of carbides in steel was performed by V. Randle and G. Laird in 1993 [7], publications concerning the characterization of carbides using EBSD are still rare. However, there is some related work concerning carbide analyses in

Corresponding author. Tel.: +386 14701900; fax: +386 14701939. E-mail address: (M. Godec).

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different steels [810]. Besides carbide identification this tech- nique was also used for martensite determination based on EBSD pattern quality images (band contrast). A similar approach was successfully applied by S. Zaefferer et al. [11]. In contrast to our investigation where the martensite was separated from the carbides to determine the fractions of each phase, S. Zaefferer used this method to distinguish between bainite and ferrite. The EBSD results in this study were confirmed by themore established X-ray diffraction (XRD) method. Since the carbides were not homogenous, chemical characterization in the form of energy- dispersive spectroscopy (EDS) and Auger electron spectroscopy (AES) line profiles were performed.



The material used was Böhler S390 Microclean with the following chemical composition: C 1.6%, Cr 5%, Mo 2%, W 10.5%, V 5%, Co 8%, and Fe balance. A plate specimen (Φ20 mm×9 mm) was cut and machined from a bar and subsequently heat treated in a horizontal vacuum furnace with uniform, high-pressure gas quenching using N 2 at a pressure of 5 bar. The specimen was preheated in three steps: first to 650 °C, then to 850 °C and finally to 1050 °C. After this last preheat the specimen was heated (25 °C/min) to the austenitizing temperature of 1130 °C, soaked for 2 min, and then gas quenched to 80 °C. The specimen was then triple tempered at 540 °C for 2 h. The specimen was metallographically prepared using a standard procedure, followed by colloidal silica oxide polishing for 3 min and then cleaning in an ultrasonic bath. The specimen was analyzed by a FE-SEM JEOL JSM 6500F field-emission scanning electron microscope using energy-dispersive X-ray spectroscopy (EDS), an INCA X-SGHT LN2 type detector, INCA ENERGY 450 software, and an HKL Nordlys II EBSD camera using Channel5 software. The Auger electron spectroscopy (AES) was performed in a VG Microlab 310F SEM/AES. The microstructures were revealed by nital (HNO 3 and alcohol). The plate specimen was analyzed by X-ray diffraction (XRD) using Cu Kα radiation in the angular 2Θ range from 30 to 70° with a step size of 0.02° and a collection time of 10 s (D4 Endeavor, Bruker AXS, Karlsruhe, Germany). For the EDS analyses a 12-kV accelerating voltage and a probe current of 0.7 nA were used. The parameters chosen represent a good compromise between the size of the analyzing volume and the overvoltage needed to detect the chemical elements that are present. The EBSD was performed at a 20-kV accelerating voltage and a 2.7-nA probe current. The AES line profile, which examined the same carbide particle as was analyzed using the EDS and EBSD, was measured in the VG Microlab 310F. In this case a 10-kV accelerating voltage was used, and prior to the acquisition of the line profile the specimen's surface was sputter cleaned using 3-kV Ar + to eliminate any surface contamination resulting from exposure to the atmosphere. The image analyses of the backscattered electron micro- graphs were performed over 10 randomly chosen fields of view using AnalySIS PRO 3.1 software. Each image of 2000× magni- fication (an area of 2730 µm 2 ) contains about 530 darker carbide particles and about 200 brighter carbide particles. The EBSD mapping is a lengthier procedure and so only five fields of view, with the same size as the backscattered electron micrographs,

were used. The obtained crystallographic data were analyzed using the Channel5 software.



The final microstructure of the investigated steel consisted of a martensite matrix and a carbide phase. The carbides were evenly distributed within thematrix and were close to a regular spherical shape with a diameter of less than 1 µm. Fig. 1(a) shows the microstructure of a nital-etched specimen obtained with the secondary-electron detector, whereas Fig. 1(b) was recorded with the backscatter detector using a polished specimen. Two carbide types could be seen in the BE-mode image: a very bright-colored carbide containing higher-atomic-number elements and a grey carbide containing lower-atomic-number elements. Using image- analysis software the volume fraction of each phase was estimated to be 12.7±0.8% and 4.2±0.3% for the grey and the bright phases, respectively. Thematrix consisted of hardened and tempered martensite without proeutectoid carbides precipitated on the prior austenite grain boundaries. No retained austenite was observed in the matrix, and this preliminary evaluation was later confirmed by XRD. A higher-magnification BE image reveals the details of the carbide morphology (Fig. 2). The bright carbides are homogenous,

MATERIALS CHARACTERIZATION 61 (2010) 452 – 458 453 different steels [8 – 10] . Besides carbide

Fig. 1 Microstructure of the specimen: (a) SE image, (b) BE image.



whereas the grey carbides have a chemically inhomogeneous microstructure, as is clear from the contrast in the image. The EDS spot analyses and maps indicated that there were two types of carbides, with chromium andmolybdenum being present in both. The elemental distributions of vanadium, iron and tungsten are shown in Fig. 3, while the EDS spot analysis is presented in Fig. 4. In this image, only the main peaks are labelled, and there is a significant overlap of the vanadium and chromium peaks. The main difference between the two carbide phases relates to their composition: the phase that is brighter in the BE image is rich in tungsten and iron, while the darker one is rich in vanadium and tungsten. The EDS line analyses showed the chemical uniformity of the tungsten-rich carbides. Two neighboring vanadium-rich carbides one with a white pattern in the center and the other with a white area forming a star pattern (along the line in Fig. 2) were chosen and the EDS line analyses were performed across these two carbides. On the basis of the 12-kV accelerating voltage and the 0.2-µm spot distances in the EDS analyses a significant overlap of the analyzed volumes was expected. This means that an exact composition could not be accurately determined for the spot of the analysis; however, a difference in the concentration profile along the line across the carbide, which corresponds to the darker and lighter areas in the carbide itself, could be identified (Fig. 5). Significant changes in the vanadium and tungsten contents were observed, which proves that the analyzed carbides were chem- ically inhomogeneous. In order to verify the results an AES line profile was performed; this technique is surface sensitive and a significantly smaller analysis volume is required. The results show a very similar chemical distribution in the vanadium-rich carbide phase (Fig. 6). However, the changes in the vanadium and tungsten contents along the line are not as pronounced as in the case of the EDS line profile, which is due to the higher signal-to-noise ratio. The chemical inhomogeneity of the vanadium-rich carbide was confirmed by the EDS and AES analyses; however, it is not clear whether the chemical inhomogeneity also leads to crystal-

454 MATERIALS CHARACTERIZATION 61 (2010) 452 – 458 whereas the grey carbides have a chemically inhomogeneous

Fig. 2 BE image of the carbide phases. Note that the lighter carbides appear to be homogeneous, while the darker ones exhibit differences in coloration. The line corresponds to the EDS and AES line analyses and the points mark the spots of the EBSD analyses. EBSD patterns from the darker vanadium-rich phase (spots 1, 2, 3) are shown in the image.

lographic differences in a single carbide. Therefore, EBSD was performed on the two carbide types (Fig. 7). The EBSD pattern of the tungsten-rich carbide was best matched by the cubic Fe 3 W 3 C pattern. The candidates for the vanadium-rich carbide phase were the cubic VC and the hexagonal V 6 C 5 , because of their similar V:C ratios. Despite having different crystal symmetries, they give very similar EBSD patterns. Nevertheless, the crystal orientation within a single carbide particle seems to be uniform, regardless of the chemical differences in the VC phases. The EBSD patterns from points 1, 2 and 3 in Fig. 2 are practically the same, i.e., no rotation of the crystal lattice was observed; therefore, it can be concluded that the crystal structure is uniform. XRD was performed in an attempt to distinguish between the VC and the V 6 C 5 . Unfortunately, however, theXRDmeasurements did not provide a straightforward answer. In spite of the fact that VC has a cubic symmetry and V 6 C 5 has a hexagonal symmetry, both phases have their main peaks at the same positions. The tungsten-rich carbides Fe 3 W 3 C have peaks that are shifted to higher 2θ values or to lower d values (Fig. 8). Considering only the positions of the peaks is not enough. However, taking into account the peak intensities, the carbides are closer to cubic VC. The main three peaks of the measured vanadium-rich carbides had the normalized intensity 920/999/310, whereas the VC and V 6 C 5 standards had 991/999/449 and 999/872/784, respectively. The lattice parameters determined from the XRD data were 1.103±0.002 nm and 0.418±0.001 nm for Fe 3 W 3 C and VC, respec- tively. The corresponding reference values [12] are 1.108 nm and 0.416 nm. The size, distribution, type and fraction of the carbide phase to a large extent determine the properties of powder-metallurgy high-speed steels. In order to obtain the carbide fraction of each carbide type EBSD phase-map analyses were performed. Based on previous results (EDS, EBSD and XRD) the VC and Fe 3 W 3 C phases were chosen for the EBSD mapping (Fig. 9(a)). The fraction of VC was 12.4±0.5%; the fraction of Fe 3 W 3 C was 3.7±0.2%; and the balance belongs to martensite. These fractions were determined from the crystallographic data obtained from the EBSD measure- ments using the Channel5 software. The band-slope map [13] in Fig. 9(b) confirms that the martensite pattern is of poorer quality (they are darker in the image), whereas the carbides have a higher band-slope value (they are brighter in the image). The band-contrast (pattern quality) grey image level clearly separates the carbide phase from the martensite phase, particularly because of the diffuse martensite patterns. This also means that it is harder to obtain a good-qualitymartensite pattern and therefore it is impossible to crystallographically determine the fraction of martensite. The band-contrast image with the rainbow-color threshold (Fig. 9(c)) was used to separate the martensite phase from the carbide phase. Fig. 9(d), the rainbow-color histogram, exhibits two peaks. The peak at the lower value belongs to the martensite phase, while the broader peak at higher values belongs to the two carbide phases. Using such a calculation the fraction of martensite is 83± 1% and the balance is the two carbide phases.



Specimen preparation is of crucial importance for EBSD mapping as well as for BE imaging, especially for the determination of an



MATERIALS CHARACTERIZATION 61 (2010) 452 – 458 455 Fig. 3 – (a) SE image and the

Fig. 3 (a) SE image and the corresponding X-ray elemental distributional images: (b) V Kα 1 , (c) Fe Kα 1 , (d) W Mα 1 . In (a), the points from which EDS spectra were acquired are marked.

individual phase fraction. In the ideal situation the specimens should have as little topography as possible. However, a problem arises when the material is composed of phases that have different hardnesses. Since the carbides are harder than the matrix, longer polishing, ion etching or another method of

material removal, leads to a more pronounced topography. The best results were obtained by using shorter polishing times with colloidal silica oxide and by rotating the specimen and the polishing cloth in the same direction. To preserve the specimen surface and to remove the residual dirt a special acetone-soluble

MATERIALS CHARACTERIZATION 61 (2010) 452 – 458 455 Fig. 3 – (a) SE image and the

Fig. 4 EDS spectra from the points marked in Fig. 3. The front spectrum is Spectrum 1, representing the W-rich region and the back spectrum is Spectrum 2, representing the V-rich region. The main peaks in both spectra are labeled.



456 MATERIALS CHARACTERIZATION 61 (2010) 452 – 458 Fig. 5 – EDS line profile along the

Fig. 5 EDS line profile along the line shown in Fig. 2.

polymer foil was used, which was applied to the surface using a drop of acetone and removed just before inserting the specimen into the vacuum chamber of the SEM. The spatial resolutions of the AES and EDS techniques are different. While AES is a surface-sensitive technique and the Auger electrons exiting the specimen come from the top few layers of the surface, with EDS it has to be taken into account that the X-rays generated in a certain volume depend on the accelerating voltage and the density of the material [14]. Comparing the results from the EDS and AES analyses (Figs. 5 and 6) it is clear that there is a better correspondence of the EDS line profile with the BE image (Fig. 2). It is believed that this is due to two reasons: firstly, the X-rays are produced at a similar depth to the backscattered electrons and, secondly, the signal-to-noise ratio was much better in the case of the EDS analysis, so it was possible to observe smaller changes in the compositions. Smaller fluctuations in the composition were observed in the case of the AES. Another problem also lies in the quantitative analysis being not as accurate. However, the AES analysis is a better measure of the surface composition,

456 MATERIALS CHARACTERIZATION 61 (2010) 452 – 458 Fig. 5 – EDS line profile along the

Fig. 7 Representative EBSD patterns acquired from the carbide phases: (a) is determined to be Fe 3 W 3 C and (b) is determined to be VC.

where the compositional differences are smaller [15]. The compositional differences in the vanadium-rich carbides arise from the production process and from their physical

456 MATERIALS CHARACTERIZATION 61 (2010) 452 – 458 Fig. 5 – EDS line profile along the

Fig. 6 AES line profile along the line shown in Fig. 2.

456 MATERIALS CHARACTERIZATION 61 (2010) 452 – 458 Fig. 5 – EDS line profile along the

Fig. 8 X-ray pattern. X-ray peak positions corresponding to Fe 3 W 3 C, VC and V 6 C 5 and α-Fe are marked.



MATERIALS CHARACTERIZATION 61 (2010) 452 – 458 457 Fig. 9 – EBSD maps. (a) Band-contrast image,

Fig. 9 EBSD maps. (a) Band-contrast image, (b) phase image, (c) rainbow color image, (d) band-contrast histogram.

properties: the free formation enthalpy, the solubility and the diffusivity of carbide-forming elements. In the XRD spectrum a large, almost, linear background signal as well as a lot of noise can be observed. This is the well known effect of fluorescence [16]. The noise could also be caused by amorphous material; however, this is not the case here. Another feature that can be observed in the XRD pattern is the broadening of the Fe peaks. Since the iron is in the martensite phase, it was assumed that this phenomenon is associated with a non-uniform lattice distortion. The EBSD Kikuchi pattern of the martensite also appears as diffuse, which can be attributed to the same cause. Certain problems were encountered in the analysis of the vanadium-rich carbides. The Fe 3 W 3 C analysis was relatively straightforward, since there were no alternative phases that could match the EBSD patterns and the composition. However, it is worth mentioning that in this case Fe 3 W 3 C can also mean that other carbide-forming elements are present to form M 6 C carbides.It was much harder to distinguish between the VC and the V 6 C 5. Both phases have their main XRD peaks in the same position and their EBSD diffraction patterns were virtually the same. In principle, the FCC and HCP structures have the same packing ratio and a similar structure [17]. Since both XRD and EBSD are diffraction techniques, similar phenomena and similar problems can be expected. However, one of the advantages of

XRD is that the peak positions can be accurately determined and the lattice parameters can be calculated, whereas with EBSD it is possible to investigate an individual carbide. Using electrolytic carbide extraction would probably have given better results for the XRD analysis, as there would be no Fe peaks present, and it would also be possible to identify the less-intense carbide XRD peaks [18,19]; however, in this case XRD was used to support the EBSD measurements and to provide information about the carbide type. Since VC and V 6 C 5 have virtually the same EBSD patterns (the mean angular deviation differs by only 0.004, which is negligible) it is not possible to distinguish between them based only on the EBSD method. Thus, it was necessary to resort to XRD. Due to the method of the PM steel's preparation, which includes gas atomization, powder encapsulation, hot isostatic

Table 1 Comparison of carbide and martensite fractions using different analytical approaches.


BE image EBSD phase map

Band contrast


83.1 ± 1 12.7 ± 0.8 4.2 ± 0.3

Balance 12.4 ± 0.5 3.7 ± 0.2

83 ± 4 Balance Balance

VC Fe 3 W 3 C



pressing, the carbides have no texture. Therefore, it was possible to use the peak-intensity ratios for the determination of the carbide types. In this case it was clear that VC was the more likely candidate. It is very important to characterize all the carbide phases present in the material because the mechanical properties are largely determined by their shape, size, distribution and their volume fraction. To determine the amount of carbides and martensite in the specimen, three independent methods were used. In the analysis of the BE images additional problems arise from the nature of backscattered electrons, which are generated at a certain depth, rather than on the surface itself. This means that more carbides could be counted. In the EBSD mapping the main source of measurement errors is the local topography of the specimen and the inaccuracy in the pattern solving. However, the latter can be improved by using some level of noise reduction. The third method was used to separate the martensite from the carbides using EBSD pattern band contrast. In this case the measurement uncertainty was relatively high because the two separate peaks overlap significantly. The results are presented in Table 1, where the volume fraction of each phase obtained in different ways is compared.



During isostatic pressing of the powder-metallurgy alloy, the eutectic carbide phase spherodised and formed two cubic carbide phases: Fe 3 W 3 C and VC. Auger electron spectroscopy and electron-backscatter diffraction microchemical analyses showed that the M 6 C carbide was chemically uniform, while the VC seemed to be non-uniform. The backscatter-electron images indicated a dendrite morphology of the carbide particles, which most probably occurred during the spherodisation. Crystallo- graphically, both carbides were uniform and monocrystalline. Electron-backscatter diffraction and X-ray diffraction were applied to confirm the carbide types. Due to the very similar electron-backscatter diffraction patterns and the same X-ray diffraction peaks for the VC and the V 6 C 5 carbides, it was hard to distinguish between them. However, the carbides had no texture and therefore the XRD peak intensity indicated a higher probability of them being the VC carbide. Three different ways to obtain the amount of each phase were demonstrated, with the most precise result coming from the electron-backscatter- diffraction phase map.


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