Engineering Failure Analysis 11 (2004) 199206 www.elsevier.

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Caustic stress corrosion cracking of a graphite cast iron component

R.K. Singh Raman*, B.C. Muddle
Centre for Advanced Materials Technology, School of Physics and Materials Engineering, Monash University, Melbourne 3800, Australia Received 1 July 2002; accepted 21 May 2003

Abstract This paper presents failure analysis of an ex-service cast iron component exposed to aggressive caustic solutions during Bayers process for alumina processing. The cracks and the neighbouring areas in the ex-service samples were examined using conventional metallography, scanning electron microscopy (SEM), the extraction replica technique in the transmission electron microscope (TEM) and Auger electron spectroscopy (AES). The features include intergranular stress corrosion cracking and grain boundary embrittlement ahead of the crack-tips. The paper also argues the possibility of hydrogen-assisted crack propagation. # 2003 Elsevier Ltd. All rights reserved.
Keywords: Caustic stress corrosion cracking; Caustic embrittlement; SG Cast iron

1. Introduction The extraction of alumina from mineral bauxite using Bayer process makes extensive use of aggressive caustic solutions at elevated temperatures. Eective containment of the highly corrosive caustic solutions presents a special challenge in infrastructure maintenance. Cracking and failures in the reaction vessels, digesters and in pipework linking major vessels in the processing plant are ongoing problems, and continuous maintenance, materials replacement and lost production time are major cost to the industry. Most common failures in these conditions result due to caustic stress corrosion cracking (SCC), which is a common form of materials failure [17], a major concern for component integrity and safety, and a major cost in infrastructure maintenance in the alumina processing industry. Reaction vessels for most of processing line are generally constructed out of carbon/mild steels, it is not uncommon to use cast iron for some low temperature (typically, < 100  C) processing. The most widely accepted SCC mechanisms suggest that the cracking susceptibility may be governed by metal dissolution and oxide lm growth at potentials near to the active-passive transition or may involve
* Corresponding author. E-mail address: raman.singh@spme.monash.edu.au (R.K.S. Raman). 1350-6307/$ - see front matter # 2003 Elsevier Ltd. All rights reserved. doi:10.1016/j.engfailanal.2003.05.007

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hydrogen embrittlement. The present work, which involves an extensive microstructural and microanalytical characterisation of the ex-service samples of a cast iron, critically examines possibility of hydrogen embrittlement as the reason for the in-service SCC failures.

2. Experimental procedures Ex-service circular section of spheroidal graphite (SG) cast iron component had a change in internal diameter mid-section. Samples of this component were sectioned approximately normal to the principal cracking plane, polished and etched by conventional metallographic methods. The etchant used was 2% nital. Carbon extraction replicas were prepared from polished and etched specimens using a technique described in detail elsewhere [8] and all such specimens were examined in a Philips EM420 transmission electron microscope operating at 120 kV. To explore the mode of cracking, partially cracked specimens were carefully sectioned and impact fractured at liquid nitrogen temperature, using the pre-existing crack as an eective notch. The aim was to extend the existing crack and examine the freshly-formed fracture surfaces in a Jeol 840A scanning electron microscope (SEM). Additional pre-cracked specimens were prepared for Auger electron spectroscopy (AES). These specimens were 4423 mm in dimensions, with the pre-existing crack located at approximately mid-length providing once again an eective notch. They were fractured by slow bending at liquid nitrogen temperature under conditions of ultra-high vacuum in an Auger electron spectrometer. Analysis of the freshly-formed intergranular fracture surfaces was carried out with an electron probe nominally 60 mm in diameter.

3. Results The ex-service sample had a single large crack extending from the inner surface of the sample to a depth of approximately 15 mm (in a 30 mm section). The crack had nucleated at a position of apparent stress concentration associated with a change in the internal diameter of the component, as shown schematically in Fig. 1. Microstructure of the SG cast iron contained small colonies of pearlite and coarse spheroidal nodules of graphite dispersed in ferrite matrix.

Fig. 1. Schematic diagram of the section through the ex-service sample of SG cast iron.

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3.1. Reected light microscopy The major crack, shown in the montage in Fig. 2, appeared to have initiated at the point of stress concentration (at the inner surface). Crack propagation was exclusively intergranular in character, following the ferrite grain boundaries. Where the crack encountered graphite nodules, further propagation involved decohesion at the nodulematrix interface. Near to the surface and in the early stages of crack growth, there is some evidence of cracking of individual grain boundaries adjoining the main crack path, but little secondary branching of the main crack. However, towards the tip of the crack, there appears an increased tendency to such secondary cracking. An important feature of this specimen was the enhanced sensitivity of the ferrite grain boundaries immediately adjacent to and ahead of the crack tip to normal etching in 2% nital. As emphasized in the higher magnication micrograph of Fig. 3, the ferrite grain boundaries are exclusively highlighted at and ahead of the crack tip, and the grain boundaries in areas more remote from the crack are not clearly resolved (due presumably to a less sensitivity to etching). It is not clear at the resolution available whether this sensitivity is associated with decohesion at these boundaries, but in most cases there is no obvious separation of the grains across the grain boundaries, i.e. no obvious cracking. The presence of these highlighted grain boundaries creates the impression of a sensitised or embrittled zone of materials immediately ahead of the crack, extending for a distance of approximately 1.0 mm. 3.2. Scanning electron microscopy To further examine the possibility of an embrittled zone at the crack tip, a slice of the cracked sample containing the crack at approximately mid-section was subjected to impact loading at both ambient and liquid N2 temperatures to extend the existing crack to complete fracture. Selected SEM micrographs from the resulting fracture surfaces are shown in Fig. 4. Fig. 4a was recorded from a region of fracture surface corresponding to the pre-existing crack and reveals a predominantly intergranular fracture path and the

Fig. 2. Montage of reected light micrographs showing a section through the full length of the crack observe in the SG cast iron and represent schematically in Fig. 1.

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occasional exposed graphite nodule, consistent with the metallographic section shown in Fig. 2. The debris on this surface corresponds to oxide and/or corrosion product expected on such a surface exposed to the caustic environment. Energy dispersive X-ray spectroscopy (EDXS) from individual intergranular fracture facets in this region invariably revealed predominantly Fe, a small concentration of Si, and a signicant concentration of Al. The extent of the pre-existing open crack across the fracture surface could clearly be established in the SEM by the presence of the debris and the signicant Al peak in corresponding EDXS spectra. Beyond the region of pre-existing fracture surface, the cracking was observed to remain exclusively intergranular for a distance of approximately 1 mm. Fig. 4b shows a typical region of intergranular fracture in the zone immediately ahead of the pre-existing crack tip. This zone of fresh intergranular fracture is clearly distinguished from the pre-existing intergranular fracture surface by the smoothness and cleanliness of the fracture facets and the absence of corrosion product on the surface. Analysis from such facets revealed only the presence of Fe and a small concentration of Si. The extent of this zone of fresh intergranular fracture correlates well with the zone in which sensitised ferrite grain boundaries were revealed in the metallographic sections, and appears to conrm the existence of a zone of intergranular embrittlement immediately ahead of the crack tip. Beyond the zone of fresh intergranular fracture, a clear transition from an intergranular to a transgranular mode of fracture in the ferrite was observed, as is evident from Fig. 4c. The EDXS spectrum from a transgranular cleavage as expected, reveals only a strong Fe peak (with a small subsidiary Si peak). 3.3. Transmission electron microscopy (TEM) of carbon replica Carbon extraction replicas, prepared from polished and etched sections and examined in the TEM (Fig. 5), failed to reveal any evidence for the cause of the sensitised ferrite grain boundaries observed ahead of the crack tip. Because of the cracking, it proved dicult to remove replica sections intact from regions immediately adjacent to the crack. However, in all sections of replica obtained selectively from regions as near to the crack tip as possible, the grain boundaries appeared to be free of precipitation of a scale that would be readily extracted on such replicas. The extraction replicas provided no evidence of a grain boundary lm or discrete precipitation. It should be ackowledged that the extraction replica technique may not be eective in extraction of very ne-scale particles ( < 5 nm) at a grain boundary. However, it is unlikely that such ne-scale precipitates would be sucient to promote the observed intergranular failure, even if present. The observations in these extraction replicas are consistent with those from the freshly-formed

Fig. 3. Reected light micrograph of ferrite grain boundaries in the immediate vicinity of the crack tip (the area with the greater etchsensitivity is the area immediately ahead of the crack tip).

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Fig. 4. Scanning electron micrographs of fracture surfaces from pre-cracked SG iron, fractured to failure under impact loading at liquid N2 temperature: (a) pre-existing service fracture. (b) Fresh fracture surface immediately ahead of pre-existing cracks. (c) Transition from intergranular to transgranular clevage in the region remote from the pre-existing crack.

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intergranular fracture facets in Fig. 4b, where the facets are smooth and there is no evidence of grain boundary precipitates resolved on these facets. 3.4. Auger electron spectroscopy (AES) of grain boundaries AES examinations have failed to reveal any evidence of local elemental grain boundary segregation that might account for the observed embrittlement. Typical AES spectra of the fracture surfaces revealed a high, but variable, concentration of oxygen superimposed on the Fe spectrum, with lower but signicant levels of Na ( $ 20 at.%), C and N, and small concentrations of S and occasionally P. Aside from the Fe, the elements detected in this region are anticipated to be largely the result of corrosion product and surface contamination. Aside from Fe, C and O, and the occasional trace of P, no other elements were detectable on the fresh, intergranular fracture surface at the concentration levels likely to promote signicant grain boundary embrittlement. Analyses from the fresh, intergranular fracture surface could not be distinguished qualitatively from those recorded from the transgranular cleavage surfaces observed over the remainder of the fracture surfaces.

4. Discussion The most interesting and important result from the present work was the clear evidence of a local zone of grain boundary embrittlement extending ahead of the tip of the major cracks examined. Optical microscopic examinations have provided evidence as shown from the enhanced sensitivity of the ferrite grain boundaries immediately adjacent to and ahead of the crack tip to normal etching in 2% nital. However, the results of the microanalytical characterisation have failed to reveal any evidence of local elemental grain boundary segregation that might account for the observed embrittlement. In hindsight this may not be too surprising. If indeed the intergranular embrittlement is localised to the immediate vicinity of a crack tip, then it seems unlikely that such embrittlement will be attributable to global grain boundary segregation of, for example, a trace impurity element such as phosphorus or sulphur during processing of the material or extended elevated temperature exposure. It seems more likely that if cracking is associated with boundary segregation, this segregation is conned to the strain eld at the crack tip and perhaps arises from exposure to the corrosive environment. In the absence of evidence of any other embrittling species on the exposed intergranular facets, the question arises as to whether there may be sucient concentrations of hydrogen available at the crack tip to promote such embrittlement.

Fig. 5. Transmission electron micrograph recorded from carbon replica taken from the section near to the crack tip zone.

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There are conicting points of view [911] regarding possibility of hydrogen embrittlement mechanism during caustic corrosion of steels; with more reports in favour of the lm breakdown or dissolution theory [9,10]. Nevertheless, there are evidences [12] of hydrogen-assisted intergranular cracking in steels, but hydrogen is not readily detected directly and there appears to be little work done on hydrogen evolution in caustic environments. However, Dahl et al.s [11] electrochemical studies have suggested that the free corrosion potential (FCP) during SCC tests on a stainless steel in 20% sodium hydroxide was in the active region, and hence the conclusion that hydrogen available at the cathodic sites could play a role in the SCC process. Yasuda [13] has also reported FCP to be situated in the active range during SCC tests in caustic environment. That hydrogen plays an important role in the SCC mechanism of stainless steels in hot caustic solutions was also suggested by Rhondelli et al. [14]. Most of the reports supporting hydrogen induced cracking mechnism during caustic SCC are for stainless steels. However, it is interesting to note that the embrittlement zone extending ahead of the crack-tip (as shown in Figs. 2 and 3) is similar to the observations by Chen and Gerberich [15]. Chen and Gerberich have also proposed a model in support of the mechanism for formation of a zone of highest stress somewhat ahead of the crack-tip and thus acting as hydrogen traps leading to embrittlement. There are evidence [12,16] of hydrogen-assisted intergranular cracking in similar materials to those examined here.

5. Conclusions SG cast iron components exposed in service to high temperature caustic solutions in Bayer process suer stress corrosion cracking. The following phenomena are associated with the cracking, crack-tips and the areas ahead of crack tips: 1. The cracking is initiated at the surface exposed to the corrosive environment and it appears that crack nucleation may have been aided by local stress concentrations and/or zones of local residual stress concentration. 2. The fracture mode is almost exclusively intergranular and the crack path follow ferrite grain boundaries. Crack branching and secondary cracking are features of the damage in all specimens. 3. There are evidence of a local zone of grain boundary embrittlement extending ahead of the tip of the major cracks examined in the planes normal to the approximate cracking plane. Formation of an embrittlement zone ahead of the crack-tip nds similarity with the reported literature on other material. 4. In the absence of evidence of any other embrittling species on the exposed intergranular facets, there arises the possibility of hydrogen being involved in the embrittlement.

Acknowledgements Authors are thankful to the Queensland Alumina Ltd. (Australia) and Australian Research Council for their support for this investigation.

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