ADVANCED DISCRIMINATION OF HEMATITE AND MAGNETITE BY AUTOMATED MINERALOGY

German Figueroa, Kurt Moeller, Michael Buhot, Gerda Gloy, David Haberlah FEI Australia, Centre of Excellence for Natural Resources, P.O. Box 2269, Milton, QLD 4064, Brisbane, Australia Abstract Better mineral characterisation is required for reliable and quantitative characterisation of iron ore sources. Studying mineral liberation of hematite and magnetite is important to predict iron extraction behaviour. Similar elemental composition makes their discrimination by automated scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDS) a challenge. Similar backscattered electron (BSE) intensities further complicate prior image segmentation performed by the mineral liberation analyser (MLA) to better define energy-dispersive X-ray (EDX) spectra acquisition. Here, a new automated characterisation for hematite and magnetite is demonstrated, it involves (1) measurement parameter optimisation; (2) flexible EDX spectra acquisition of single geometric centre points or mapping on saturated segmented regions with a regular grid; and, (3) a new classification algorithm combining EDX and BSE characteristics. This automated SEM-EDS based approach is shown to accurately discriminate hematite from magnetite, and quantify mineral associations and locking without increasing considerably measurement times. Keywords: hematite, magnetite, iron ore, scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDS), mineral liberation analyser (MLA), segmentation, liberation

1 1.1

INTRODUCTION General In recent years there has been a notable increase in the global demand for iron ore. Chinas steel production, for instance, has exceeded the sum of all steel production in important producer countries such as Japan, USA, Russia, Germany and South Korea [1]. Innovation is driving the whole industry from iron ore extraction to processing. Advanced mineral characterisation of hematite and magnetite, including microstructural mapping of phases and quantifying liberation, is becoming increasingly important to optimise iron ore extraction [2]. Iron oxides such as hematite, magnetite, goethite and limonite are the principle sources of iron. The mineral liberation analyser (MLA) and QEMSCAN have become important tools for characterising iron ore minerals and their processing products despite facing difficulties in discriminating magnetite from hematite [3]. These minerals normally occur in complex association with each other and with gangue minerals. Although magnetite (Fe3O4) and hematite (Fe2O3) can be easily distinguished qualitatively using optical microscopy (Figure 1a), quantitative characterisation by automated scanning electron microscopy/energydispersive X-ray spectroscopy (SEM-EDS) solutions, such as the MLA, is challenging because hematite and magnetite are similar in their chemical composition and backscattered electron (BSE) brightness. In the MLA approach, mineral phases are first distinguished by their BSE grey levels during on-line segmentation and then by their energy-dispersive X-ray (EDX) spectrum [4,5] (Figure 1b). As a result, minerals associated with a similar BSE value are segmented into a single phase (Figure 1c). By applying an

Broekmans, MATM (editor) Proceedings, 10th International Congress for Applied Mineralogy (ICAM) 1-5 August 2011, TRONDHEIM, Norway ISBN-13: 978-82-7385-139-0

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advanced workflow and doubling the grey level contrast, hematite and magnetite can be separated (Figure 1d). In order to prevent combining different bright (saturated) mineral phases and limit highlighting and separating of mineral defects, a BSE threshold value is set to map saturated areas, separately. The present approach is based on the MLA, an automated mineralogy solution by FEI Company (Hillsboro, Oregon, USA), applied to iron-oxide minerals containing sulphides and gangue minerals, mainly quartz and feldspars. 2 2.1 METHODOLOGY Sample preparation A synthetic sample combining several relevant minerals was selected to study the complex intergrowth between hematite and magnetite. The sample contained 20 wt% sulphides, comprising galena, pyrite, and sphalerite; 50 wt% gangue minerals, mainly quartz, orthoclase, and calcite; and 30 wt% iron oxides. The size fraction ranged from 50 to 149 m. Sample preparation followed the standard MLA protocol involving a 30 mm diameter block: mounting the mineral particles into epoxy; hardener impregnation (15/2); heating to 35C over 3 h for curing; grinding; and polishing [6]. A conductive coating of carbon is applied to prevent charging on the surface. The final representative 2D cross section of the sample is presented for MLA analysis. 2.2 Sample measurement All measurements were run on the FEI Quanta 600 Tungsten SEM platform equipped with two XFlash 4010 Silicon Drift Detector (SDD) by Bruker Optics Inc. (Ettlingen, Germany). All analyses were performed using the MLA Suite v.3.0 software package. Mineral liberation analyser The MLA Suite v.3.0 is an advanced software package for automated SEM-EDS measurements and mineral and metallurgical data analysis. The MLA measurements module controls the hardware settings of the SEM, including accelerating e-beam voltage, SEM magnification, BSE brightness and contrast, spot size, and working distance. Particles and mineral grains are segmented by their BSE brightness, the value of which is a function of the average atomic number of the measured phase [7]. This information is used by a segmentation process, identifying similar phases and separating them. The MLA phase segmentation outlines regions of similar BSE values and assigns the predominant BSE value to the segmented phase. The underlying assumption is that discrete mineral phases correspond to a discrete range of BSE values [4,5]. Subsequently, either a single centroid or a regular grid of EDX spectra is collected from each segmented region for mineral identification. In the MLA Mineral Reference module, a list of representative EDX spectra is defined by the operator for the subsequent classification of the sample. Mineral classification is performed by the MLA image processing module, comparing measured spectra with reference spectra using a modified Chi-squared matching method. Finally, in the data view module, mineral and textural properties are calculated on a particle-by-particle and grain-by-grain basis. This information is here used to study mineral association, locking and liberation of hematite and magnetite. Measurement modes The MLA software offers a number of measurement modes to best address a wide range of sample types, and to meet different mineralogical information requirements. In this study, two measurement modes were selected taking into consideration the variable mineralogy of the sample; XBSE and GXMAP [4,5]. In the extended BSE liberation analysis or XBSE mode, as in all other measurement modes in MLA, the BSE image

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is segmented to allow the collection of a single EDX spectrum from the geometric centres of each region/phase, thereby significantly reducing the overall need for x-ray collection. Alternatively, in the grainbased X-ray mapping or GXMAP mode, a regular grid of EDX spectra is obtained across the segmented phase defined either by a BSE threshold or an EDX trigger. GXMAP is particular applicable for phases that are similar in BSE brightness and commonly not segmented into individual mineral phases (Figures 2 and 3). 2.3 Modified settings BSE stretch Standard BSE calibration is set so that the mounting media (resin) is kept at backscatter brightness values below 15, and gold at a value of 250. This setting covers the BSE range of all common minerals. Iron oxides typically range from 115 to 120 (Figure 2a). When the contrast and brightness is increased to extend the mounting media to a backscatter brightness close to 0, and chalcopyrite to 250 (Figure 2b), a bimodal peak for iron oxides ranging from 195 to 215 emerges and can then be separated into its two modes representing hematite (200) and magnetite (208), respectively. Modified parameters allowing discrimination of hematite and magnetite can be set in the XBSE and GXMAP measurement modes. For this study, GXMAP was selected using an EDX mapping threshold for BSE values higher than 230 for the saturated phases. As a result, different mineral phases within the saturated (combined) segmented regions are discriminated based on their EDX spectra. The delineation between separate phases now follows the pixel spacing, defined by the EDX acquisition stepping interval (Figure 3). As a result, any mineral phases with an average atomic number higher than chalcopyrite, such as barite, galena and gold, are now oversaturated registering BSE values close to 255. Additional measurement parameters are optimised to improve the modified BSE segmentation. Here, the standard specimen current is increased from 7.0 to 18.0 nA on the Faraday cup. The working distance is kept at 10 mm to maintain a high X-ray count rate. The resolution and magnification need to be adjusted depending on the physical aspects of the sample, that is, size, texture, and mineralogy. For this study, 1200 sq-pixels and an SEM magnification of 400 are selected. The total acquisition time is set to 12 ms, translating to ~3000 counts on iron oxide minerals. BSE-EDX phase classification A new feature in the MLA Suite v.3.0 is the capability to combine BSE and EDX characteristics in mineral identification and classification. For a segmented phase, the average BSE value is recorded and available as a parameter for mineral identification. BSE matching compares the average BSE value of an unknown segmented phase to user-defined BSE ranges. These reference BSE ranges are identified on the segmented BSE histogram of the sample, by plotting phase area distributions versus BSE channels within the default range of 0255. Subsequently, segmented phases are compared to the reference mineral/phase EDX spectra. Best matches are established using a modified Chi-squared method, and assigned a score of 0100 as a confidence metric. The higher the score, the greater is the similarity between the measured and reference spectra. A user-defined confidence threshold can be specified, below which a segmented phase is classified as unknown. This could indicate that more reference spectra need to be collected. Segmented phases that fall within the defined BSE ranges are classified based on both BSE and EDX characteristics. In this study, the BSE classification was selected from 190 to 204 for hematite and 205230 for magnetite (Figure 4).

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RESULTS AND DISCUSSIONS Five measurements were carried out. As baseline mineralogy, the first three consist of XBSE measurements using standard BSE settings (not differentiating hematite/magnetite). Two measurements were performed on 20,000 particles and one on 10,000 particles, establishing the reproducibility of the data. Subsequently, two combined GXMAP measurements using the modified BSE settings were run on 10,000 particles, now discriminating hematite and magnetite (Table 1) and mapping oversaturated phases. In general, all MLA measurements modes can be adjusted to detect hematite and magnetite. Modal mineralogy, mineral association and iron oxide locking reports were generated for each measurement. These data were compiled into modal results (Figure 5), free surface and association (Table 2), and a liberation table quantifying iron oxide and discriminating hematite and magnetite (Table 3). 3.1

Modal mineralogy The modal mineralogy is presented as weight percentage and shows little variation between the different measurement modes. Iron oxides in the three standard XBSE measurements are identified in similar quantities to the combined hematite and magnetite classes in the modified GXMAP measurements. Other minerals, such as sulphides and gangues, also report near identical results. This supports the notion that by modifying the BSE brightness and combining XBSE and GXMAP measurement modes, overall modal results remain comparable. It further demonstrates that impurities and defects now highlighted by the BSE stretch have little influence on the overall composition (Figure 5). Mineral associations The mineral association report differentiates liberated minerals sharing a boundary with the resin (free surface) from minerals sharing a boundary with another mineral/phase. The data obtained from the sectioned sample surface are expressed in area percent. Similar liberated and associated results are reported across all measurements, for example, undifferentiated iron oxide liberation 83%; association with quartz and feldspars (others) 16%, and sulphides 1.0% (Table 2a,b). The liberation of hematite and magnetite are given as 40% and 54%, respectively (Table 2c). 3.3 Mineral locking Mineral locking describes mineral associations, either as liberated, binary (contact between two minerals), or ternary between three or more. Similar results were obtained across all measurements and expressed as wt% (Table 3). The ratios of liberated hematite (20 wt %) and magnetite(53 wt%) are related to each other but different, with low concentrations locked with sulphides. 3.4 Hematite and magnetite discrimination Variation in the BSE brightness can be caused by mineral impurities, defects and boundaries with resin, resulting in overlap between the BSE ranges of hematite and magnetite. This overlap cannot be fully resolved by a simple BSE threshold, resulting in a slight overestimate of mineral locking. Visual inspection of the data shows that the classification of both hematite and magnetite can be affected, however without significantly impacting the overall results. Coarse magnetite grains appear more often surrounded by hematite than fine magnetite grains (Figure 6). The MLA software provides tools to correct any misclassified phases. 3.2

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CONCLUSIONS This study demonstrates an advanced approach to quantitative discrimination of hematite and magnetite using the MLA. BSE and EDX based mineral classification are combined with automated measurement modes (XBSE, GMAP), providing a robust discrimination of the chemically similar iron oxides and all other minerals in the sample. The automated phase-by-phase approach characterises hematite and magnetite minerals in terms of quantitative modal composition, mineral association, liberation and locking reports. The outlined approach shows significant potential to improve iron ore extraction and processing. It can also be applied to non-metallic mineral characterisation, by discriminating other similar phases such as clay minerals and some solid solution series. 5 [1] [2] [3] [4] [5] [6] [7] REFERENCES Zou, J (2007): Advances of iron ore beneficiation in China. In: AusIMM Australian Institute of Mining and Metallurgy: Iron Ore Conference 2007, Perth, Western Australia: 3133. Gomes, O, and Paciornik, S (2008): Iron ore quantitative characterisation through reflected lightscanning electron co-site microscopy. In: AusIMM Australian Institute of Mining and Metallurgy: Ninth International Congress for Applied Mineralogy, Brisbane, Queensland: 699702. Shaffer, M (2009): Discriminating hematite and magnetite and quantifying their associations using the JKTech Mineral Liberation Analyzer. In: The 48Th Annual Conference of Metallurgists, Laurentian University, Sudbury, Ontario: 73. Gu, Y (2003): Automated scanning electron microscope based mineral liberation analysis. Journal of Minerals and Materials Characterization and Engineering (2/1): 3341. Fandrich, R, Gu, Y, Burrows, D, and Moeller, K (2006): Modern SEM-based mineral liberation analysis. International Journal of Mineral Processing (84): 310320. MLA System User Operating Manual Module 1 (2004): Julius Kruttschnitt Mineral Research Centre. Jones, M (1987): Applied Mineralogy: A Quantitative Approach. Graham & Trotman, London.
TABLE 1: Summary of measurement parameters. SEM parameters MLA parameters References Results Analyses References XBSE_1,2 XBSE_3 GXMAP_1,2 Measurements: XBSE_1,2 XBSE_3 24.9 24.8 24.8 Scan speed 16 16 Saturation and alignments Resolution (sq pixels) 1000 1000 10 10 10 Pixel size (um/px) 0.85 0.64 10 10 ~17 Acq. time (mms) 15 35 7.9 7.4 8.2 Fe-oxide EDX count 2100 4700 300 400 400 N/A N/A Step size (pixels) 80.6 80.5 79.5 GXMAP trigger N/A N/A 20.3 24.2 23.7 Particle count ~20,000 ~10,000 Gold 250 Gold 250 Chalpy. 252 Time (h:mm:ss) 2:49:20 2:29:56

Analyses Measurements: Voltage (KV) Filament (W) Working dist. (mm) nA Spot size Magnification Brightness Contrast BSE calibration

Results GXMAP_1,2 16 1200 0.53 12 3300 10 10 BSE > 235 ~10,000 3:20:00

TABLE 2: Free surface (liberation) and association data. (a) Reference measurements (b) Results measurements (c) Result measurements (GXMAP_1,2 (XBSE_1, 2, 3 combined). Fe-oxide (GXMAP_1, 2 combined). Fecombined). Hematite/magnetite classification (area%) oxide classification (area%) discrimination (area%) Minerals FeO Sul Oth Minerals FeO Sul Oth Mineral Hem Mag FeO Sul FS 83.0 82.7 90.9 FS 82.6 81.8 90.3 FS 40.8 54.0 81.8 90.3 FeO 0.0 1.6 5.1 FeO 0.0 1.4 5.3 Hem 0.0 37.7 0.7 2.9 Sul 1.2 0.0 4.0 Sul 1.1 0.0 4.4 Mag 46.9 0.0 0.7 2.4 Oth 15.8 15.7 0.0 Oth 16.3 16.9 0.0 FeO 0.7 0.6 0.0 4.4 Total 100.0 100.0 100.0 Total 100.0 100.0 100.0 Sul 11.6 7.8 16.9 0.0 FS: free surface, FeO: Fe-oxides, Sul: sulphides, Oth: others, Hem: hematite, Mag: magnetite Total 100.0 100.0 100.0 100.0

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Measurements: Wt% locking of... Liberated (%) Total binary (%) Total ternary (%) Total (%) Wt% locked in... Magnetite/hematite1 Pyrite Galena Chalcopyrite Sphalerite Barite Others Total (%) Wt% locked in... Magnetite/hematite1 Pyrite Galena Chalcopyrite Sphalerite Barite Others Total (%) 1Corresponding value. C: combined.

TABLE 3: Numerical mineral locking report. XBSE_1,2,3 C GXMAP_1,2 C GXMAP 1, 2 C Fe-oxide Fe-oxide Hematite Magnetite 78.4 79.4 20.7 53.8 20.2 19.4 56.6 37.9 1.3 1.2 22.7 8.3 100.0 100.0 100.0 100.0 Binary Binary Binary Binary N/A N/A 45.4 30.061 0.1 0.2 0.1 0.1 0.4 0.4 0.0 0.3 0.9 0.6 0.3 0.4 0.0 0.0 0.0 0.0 0.2 0.1 0.0 0.2 18.7 18.0 10.7 6.8 20.2 19.4 56.6 37.9 Ternary Ternary Ternary Ternary N/A N/A 13.0 4.901 0.1 0.0 0.3 0.0 0.1 0.1 0.3 0.3 0.2 0.2 0.5 0.1 0.1 0.0 0.0 0.0 0.2 0.1 0.1 0.1 0.8 0.7 8.6 2.9 1.3 1.2 22.7 8.3

Figure 1: (a) Hematite and magnetite discrimination based on: (1) optical microscopy; (2) the modified BSE image; (3) segmented phases with EDX acquisition points; and, (4) the compositional map based on the MLA classification results. (b) Particle segmentation by the MLA approach (adapted Figure 2 [4]), (c). Similarities between EDX spectra and BSE brightness of hematite and magnetite resulting in a single segmented phase. (d) BSE brightness and contrast modification separating hematite and magnetite.

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Figure 2: Segmented BSE histograms. (a) Histogram reflecting standard BSE calibration, (b) as well as the modified settings discriminating hematite and magnetite.

Figure 3: (a, b) Comparison between standard and enhanced BSE conditions, EDX locations; (c) corresponding segmentation showing EDX acquisition points; (d) final mineral classification results.

Figure 4: BSE classification based on (a) BSE values associated with segmented phases, (b) bimodal BSE distribution reflecting hematite and magnetite, and (c) numerical values used to define BSE threshold.

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Figure 5: Reproducibility of modal mineralogy report for all measurements.

Figure 6: Comparison of modified BSE images and hematite/magnetite images.

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