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Platinum Metals Rev., 2012, 56, (4), 257

doi:10.1595/147106712x654907

Electrolytic Etching of Platinum-Aluminium Based Alloys

Enhanced microstructural analysis with improved safety using chloride solutions

  • By Bernard O. Odera*
  • School of Chemical and Metallurgical Engineering,
  • University of Witwatersrand, Private Bag 3, Wits 2050, South Africa,
  •  
  • African Materials Science and Engineering Network (AMSEN),
  •  
  • and DST/NRF Centre of Excellence in Strong Materials,
  • University of the Witwatersrand, Private Bag 3, Wits 2050, South Africa
  • *Email: bodera2010@gmail.com
  • Lesley A. Cornish
  • School of Chemical and Metallurgical Engineering,
  • University of Witwatersrand, Private Bag 3, Wits 2050, South Africa,
  •  
  • African Materials Science and Engineering Network (AMSEN),
  •  
  • and DST/NRF Centre of Excellence in Strong Materials,
  • University of the Witwatersrand, Private Bag 3, Wits 2050, South Africa
  • M. Jones Papo
  • Advanced Materials Division, Mintek, Private Bag X3015,
  • Randburg 2125, South Africa,
  •  
  • and DST/NRF Centre of Excellence in Strong Materials,
  • University of the Witwatersrand, Private Bag 3, Wits 2050, South Africa
  • George O. Rading
  • Department of Mechanical and Manufacturing Engineering,
  • University of Nairobi, PO Box 30197-00100, Nairobi, Kenya,
  •  
  • and African Materials Science and Engineering Network (AMSEN)
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Article Synopsis

The microstructures of as-cast and annealed platinum alloys of different compositions were revealed after electrolytic etching in hydrochloric acid/sodium chloride solution using direct current. It was shown that the etching process enhances good microstructural images of platinum-aluminium based alloys.

1. Introduction

Etching of Pt-Al based alloys has been problematic because most of the alloys are designed to withstand oxidation and corrosion. Currently, binary Pt-Al alloys have been patented in the USA (1) as a catalyst for use in fuel cells. However, in this work higher order Pt-Al based alloys are being investigated as potential replacement for nickel-based superalloys used in high temperature and aggressive environments. The resistance to oxidation and corrosion is attributed to the formation of a protective Al oxide scale (2). Electrolytic etching can be considered as ‘forced corrosion’, where a previously polished specimen surface corrodes inhomogeneously, revealing the different microstructural features (3, 4).

Previously in South Africa (57), microstructural imaging of Pt-Al based alloys was done using scanning electron microscopy (SEM) in the backscattered electron mode. All the samples had been metallographically prepared by grinding using silicon carbide down to 1200 grit, diamond polishing down to 1 μm and finally polishing with oxide polishing system (OP-S, Struers A/S, Denmark) by which polishing is achieved through a combination of chemical treatment (the solution has a pH of 8) and gentle abrasive action. It allows selective polishing of softer phases thereby achieving a limited etching effect. Although some of the images derived from this method had reasonably good contrast, in some cases, the contrast was poor to the extent that analysis was rendered impossible. Figures 16 are examples of some of the images of Pt-Al based alloys taken using SEM in the backscattered electron mode. In alloy Pt60:Al2:Cr38 (at%) (Figure 1), X-ray diffraction (XRD) analysis confirmed single phase ~CrPt (cored) and remnants of ~CrPt3 from incomplete ordering. The poor contrast in the image made it impossible to deduce the phases from the microstructure and plot of the energy dispersive X-ray (EDX) composition analysis. The same applied to alloy Pt63:Al22:Cr15 (Figure 2) whose XRD analysis confirmed the microstructure as single phase ~Pt3Al (cored). The other four alloys were electrolytically etched in HCl/NaCl solution and their microstructure in the unetched and etched conditions are discussed subsequently.

Fig. 1.

SEM-BSE of unetched, as-cast Pt60:Al2:Cr38 (at%), showing cored single phase ~CrPt and scratches (7)

SEM-BSE of unetched, as-cast Pt60:Al2:Cr38 (at%), showing cored single phase ~CrPt and scratches (7)

Fig. 2.

SEM-BSE image of unetched, as-cast Pt63:Al22:Cr15 (at%), showing cored single phase ~Pt3Al (7)

SEM-BSE image of unetched, as-cast Pt63:Al22:Cr15 (at%), showing cored single phase ~Pt3Al (7)

Fig. 3.

(a) SEM-BSE image of unetched, annealed Pt81.5:Al11.5:Cr4.5:Ru2.5 (at%), showing fine dark ~Pt3Al precipitates in light (Pt) matrix (6); (b) optical microscope image of annealed Pt81.5:Al11.5:Cr4.5:Ru2.5 (at%), after electrolytic etching in HCl/NaCl solution, showing fine dark ~Pt3Al precipitates in light (Pt) matrix more clearly

(a) SEM-BSE image of unetched, annealed Pt81.5:Al11.5:Cr4.5:Ru2.5 (at%), showing fine dark ~Pt3Al precipitates in light (Pt) matrix (6); (b) optical microscope image of annealed Pt81.5:Al11.5:Cr4.5:Ru2.5 (at%), after electrolytic etching in HCl/NaCl solution, showing fine dark ~Pt3Al precipitates in light (Pt) matrix more clearly

Fig. 4.

(a) SEM-BSE image of unetched, annealed Pt78:Al15.5:Cr4.5:Ru2 (at%), showing fine dark ~Pt3Al precipitates in light (Pt) matrix (6); (b) SEM-BSE image of etched, annealed Pt78:Al15.5:Cr4.5:Ru2 (at%), showing fine ~Pt3Al in light (Pt) matrix (6)

(a) SEM-BSE image of unetched, annealed Pt78:Al15.5:Cr4.5:Ru2 (at%), showing fine dark ~Pt3Al precipitates in light (Pt) matrix (6); (b) SEM-BSE image of etched, annealed Pt78:Al15.5:Cr4.5:Ru2 (at%), showing fine ~Pt3Al in light (Pt) matrix (6)

Fig. 5.

(a) SEM-BSE image of unetched, annealed Pt82:Al12:Cr4:Ru2 (at%), showing ~Pt3Al precipitates in light (Pt) matrix (6); (b) optical microscope image of annealed Pt82:Al12:Cr4:Ru2 (at%) after electrolytic etching in HCl/NaCl solution, showing ~Pt3Al precipitates in light (Pt) matrix as well as a eutectic

(a) SEM-BSE image of unetched, annealed Pt82:Al12:Cr4:Ru2 (at%), showing ~Pt3Al precipitates in light (Pt) matrix (6); (b) optical microscope image of annealed Pt82:Al12:Cr4:Ru2 (at%) after electrolytic etching in HCl/NaCl solution, showing ~Pt3Al precipitates in light (Pt) matrix as well as a eutectic

Fig. 6.

(a) SEM-BSE image of unetched, annealed Pt64.7:Al26.2:V9.1 (at%), showing medium contrast ~Pt3Al, light ~Pt5Al3 and dark ~PtV (5); (b) optical microscope image of etched, annealed Pt64.7:Al26.2:V9.1 (at%), showing light ~Pt3Al, dark ~Pt5Al3 with oriented needle-like precipitates

(a) SEM-BSE image of unetched, annealed Pt64.7:Al26.2:V9.1 (at%), showing medium contrast ~Pt3Al, light ~Pt5Al3 and dark ~PtV (5); (b) optical microscope image of etched, annealed Pt64.7:Al26.2:V9.1 (at%), showing light ~Pt3Al, dark ~Pt5Al3 with oriented needle-like precipitates

In Germany (8, 9), electrolytic etching of Pt-Al based alloys has been done in aqueous potassium cyanide (KCN) solution for microstructure investigation. However, there are serious health and safety concerns regarding the use of KCN and its use in South Africa is very restricted, especially in laboratories. Two images of Pt-Al based alloys etched electrolytically in aqueous KCN solution are shown in Figures 7 and 8. Heat treatment of as-cast samples by two-stage ageing (variant B) resulted in the formation of coarse γ matrix and γ´ regions in alloy Pt77:Al12:Cr6:Ni5 (at%) (Figure 7) (8). Spherical precipitates of γ´ in a γ matrix were observed in alloy Pt79:Al10:Cr3:Ni8 (at%) after solution heat treatment at 1450ºC for 24 h and ageing at 1000ºC for 120 h (Figure 8) (9).

Fig. 7.

SEM-BSE image of Pt77:Al12:Cr6:Ni5 (at%) after two-stage ageing (variant B) and electrolytically etched in aqueous KCN solution, showing coarse γ matrix and γ´ regions (8)

SEM-BSE image of Pt77:Al12:Cr6:Ni5 (at%) after two-stage ageing (variant B) and electrolytically etched in aqueous KCN solution, showing coarse γ matrix and γ´ regions (8)

Fig. 8.

SEM-BSE image of Pt79:Al10:Cr3:Ni8 (at%) after solution heat treatment and ageing, electrolytically etched in aqueous KCN solution, showing spherical γ´ precipitates in γ matrix (9)

SEM-BSE image of Pt79:Al10:Cr3:Ni8 (at%) after solution heat treatment and ageing, electrolytically etched in aqueous KCN solution, showing spherical γ´ precipitates in γ matrix (9)

Most electrolytic reagents are simple in composition, being acidic, alkaline or salt solutions. The sample is nearly always the anode, although a few cathodic etching solutions have been developed (10). Direct current (DC) is mostly used, although a few solutions require alternating current (AC). In electrolytic etching, the process is controlled by varying the voltage and time (10).

Battaini (3, 4) obtained the best results for Pt alloys in saturated HCl/NaCl solution with an AC power supply when the voltage varied from 0. 1 V to 10 V and the power supply provided a current of at least 10 A. Some of the electrolytic conditions are shown in Table I. However, the present work has shown that it is possible to get good results using a DC power supply.

Table I

Electrolytic Etching Solutions for Use with Platinum Alloys (3)

CompositionType
100 cm3 HCl (37%) + 10 g NaCl Electrolytic, 3–6 V AC
10 cm3 HCl + 90 cm3 H2O + 1 g FeCl3 Electrolytic, 3–6 V AC

2. Experimental Procedure

The specimens were ground by silicon carbide down to 1200 grit and then diamond polished down to 1 μm. The samples were then etched in a solution of 10 g NaCl in 100 cm3 HCl (32% concentration). Etching was done in a fume cupboard using a DC power supply, and a voltage range of 9 V to 12 V gave adequate results. The current density in the electrolyte was ~100 A m−2. The counter electrode was a stainless steel wire suspended in the electrolyte solution. Images were taken using an optical microscope.

3. Results and Discussion

The electron beam voltage used to obtain the SEM-backscattered electron (SEM-BSE) images was 20 kV. Figure 3(a) and Figure 4(a) are SEM-BSE images of alloys Pt81.5:Al11.5:Cr4.5:Ru2.5 (at%) and Pt78:Al15.5:Cr4.5:Ru2 (at%), while Figure 3(b) and Figure 4(b) are the optical microscope images of the same alloys after electrolytic etching in HCl/NaCl solution.

Both alloys had very fine dark ~Pt3Al precipitates in light (Pt) matrices, which were difficult to discern from the SEM-BSE images. The contrast after etching is better and shows more clearly the dark ~Pt3Al precipitates in the light (Pt) matrix, as well as the grain boundaries.

Figure 5(a) is a SEM-BSE image of alloy Pt82:Al12:Cr4:Ru2 (at%) which had a very poor contrast and after XRD analysis it was concluded that it had rounded dark ~Pt3Al precipitates in light (Pt) matrix. After etching (Figure 5(b)), the optical microscope image showed a eutectic, as well as the dark ~Pt3Al precipitates in light (Pt) matrix. Figure 6(a) is an example of an SEM-BSE image which had a reasonably good contrast and its optical microscope image after etching is shown in Figure 6(b).

4. Conclusions

There was a large improvement in contrast when the SEM-BSE images of alloys Pt81.5:Al11.5:Cr4.5:Ru2.5, Pt78:Al15.5:Cr4.5:Ru2 and Pt82:Al12:Cr4:Ru2 (at%) in the unetched conditions (Figures 3(a)–5(a)) were compared to the images of the same alloys (Figures 3(b)–5(b)) after being etched. Therefore, electrolytic etching of Pt-Al based alloys in HCl/NaCl solution using direct current gives good results, and it is safer than using aqueous KCN solution.

Acknowledgements

The authors would like to acknowledge M. B. Shongwe and S. Moqabolane, both of the School of Chemical and Metallurgical Engineering, University of the Witwatersrand, for their assistance.

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References

  1.  A. Freund, T. Lehmann, K.-A. Starz, G. Heinz and R. Schwarz, Degussa AG, ‘Platinum-Aluminum Alloy Catalyst for Fuel Cells and Method of its Production and Use’, US Patent 5,767,036; 1998
  2.  P. J. Hill, T. Biggs, P. Ellis, J. Hohls, S. Taylor and I. M. Wolff, Mater. Sci. Eng. A, 2001, 301, (2), 167 LINK http://dx.doi.org/10.1016/S0921-5093(00)01471-4
  3.  P. Battaini, Platinum Metals Rev., 2011, 55, (1), 71 LINK https://www.technology.matthey.com/article/55/1/71-72/
  4.  P. Battaini, Platinum Metals Rev., 2011, 55, (2), 74 LINK https://www.technology.matthey.com/article/55/2/74-83/
  5.  B. O. Odera, L. A. Cornish, M. B. Shongwe, G. O. Rading and M. J. Papo, ‘A Study of Some As-Cast and Heat Treated Alloys of the Pt-Al-V System at the Pt-Rich Corner’, in ZrTa2011: New Metals Development Network Conference, Magaliesburg, South Africa, 12th–14th October, 2011
  6.  M. B. Shongwe, ‘Optimisation of Compositions and Heat Treatments of Pt-Based Superalloys’, MSc Dissertation, University of the Witwatersrand, South Africa, 2009
  7.  R. Süss, ‘Investigation of the Pt-Al-Cr System as Part of the Development of the Pt-Al-Cr-Ru Thermodynamic Database’, PhD Thesis, University of the Witwatersrand, South Africa, 2007
  8.  M. Wenderoth, R. Völkl, S. Vorberg, Y. Yamabe-Mitarai, H. Harada and U. Glatzel, Intermetallics, 2007, 15, (4), 539 LINK http://dx.doi.org/10.1016/j.intermet.2006.09.009
  9.  M. Hüller, M. Wenderoth, S. Vorberg, B. Fischer, U. Glatzel and R. Völkl, Metall. Mater. Trans. A, 2005, 36, (13), 681 LINK http://dx.doi.org/10.1007/s11661-005-1000-8
  10.  G. F. Vander Voort, “Metallography: Principles and Practice”, Material Science and Engineering Series, ASM International, Materials Park, Ohio, USA, 1999

The Authors

Bernard Odera is a doctoral candidate at the School of Chemical and Metallurgical Engineering, University of the Witwatersrand, South Africa. He is on study leave from the University of Nairobi, Kenya. His doctoral research is on phase diagrams, alloy development and microstructural characterisation of platinum-aluminium based alloys.

Lesley Cornish is a Professor at the University of the Witwatersrand, South Africa, and is Director of the DST/NRF Centre of Excellence for Strong Materials, which is hosted by the University of the Witwatersrand, and the African Materials Science and Engineering Network (AMSEN). Her research interests include phase diagrams, alloy development, platinum alloys and intermetallic compounds.

Jones Papo is a PhD holder in Materials Engineering. He is currently the Head of the Advanced Materials Division at Mintek, South Africa, where he is closely associated with research in pgm alloys. He is also the Coordinator of the Strong Metallic Alloys cluster at the University of the Witwatersrand-hosted DST/NRF Centre of Excellence in Strong Materials.

George Rading is an Associate Professor of Mechanical Engineering at the University of Nairobi and the Deputy Director of AMSEN. His research interests are in fatigue and fracture; and structure-property relationships. He is involved in the development of platinum-based superalloys in conjunction with the Centre for Excellence in Strong Materials at the University of the Witwatersrand, through AMSEN.

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