Engineering Failure Analysis 79 (2017) 431–440

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Engineering Failure Analysis

journal homepage: www.elsevier.com/locate/engfailanal

Failure analysis of stress corrosion cracking of 316L structured MARK

packing in a distillation tower
Mahdi Hamzeha,b,⁎, M. Mahdi Karkehabadia, Reza Jalalib
a
Department of Materials Engineering, Isfahan University of Technology, Isfahan 84156-83111, Iran
b
Department of Inspection Engineering, Khuzestan Petrochemical Complex, Mahshahr, Iran

AR TI CLE I NF O AB S T R A CT

Keywords: The present study was done to find the probable causes of AISI316L structured packings (SPs)
316L structured packing failure in a dewatering phenol tower. In this tower, the SPs would provide a high contact surface
Chloride between streams to maximize and accelerate the distillation process. Increasing vibration of
Crack discharging pump showed that there were detached pieces of SPs in pump's strainer. During plant
Stress corrosion cracking (SCC)
overhaul, corrosion inspection was done and some of the broken packings were gathered for
further analysis. The samples were evaluated by visual observation, optical and scanning electron
microscope. Transgranular cracks in packing sheets and screws, used for restraining layers of
packing together, were seen. Energy-dispersive X-ray spectroscopy (EDS) of corrosion products
on packing and the fracture surface of the screw was conducted. The results showed the
occurrence of chloride stress corrosion cracking. Even though the chlorine contents of tower
streams were low, it seemed that process fluids have been mal-distributed leading to the local
concentration of the chlorine on SPs surface. In addition to chlorine, high working temperature
and applied stress provided a favorable condition for stress corrosion cracking.

1. Introduction

Austenitic stainless steels (SS) are widely used as corrosion resistant materials in various industries. However, in certain
circumstances, they can undergo serious damages. Pitting and stress corrosion cracking (SCC) are most troublesome in the wide
application of 3XX series. The formation of SCC cracks depends on the combined action of tensile stress in applied, thermal or residual
form, high temperature and an aqueous chloride, caustic or H2S solution. Cracks usually initiate from corrosion pits or crevices on the
surface, and then propagate through the material.
The fracture modes are classified as intergranular, where cracks travel along the grain boundaries, and transgranular, where
cracks go across the grains. In the case of austenitic SS, transgranular stress corrosion cracking (TGSCC) commonly occurs in
environments containing a high amount of chlorine (~ 1 M) when the temperature is high (around boiling [1], 60–200 °C [2]) [3,4].
However, there is no absolute safe threshold for chloride concentration. For example, under insulation or intermittent wet/dry cycles,
SCC has been observed at ambient temperature and chloride concentrations as low as 5 ppm [4].
In sensitized condition, where zones along the grain boundaries are anodic to the main body of the grains, SCC progresses
intergranularly [5,6]. Low amount (Up to 10− 2 M) of thiosulfate or polythionate at ambient temperature or aerated water at high
temperature and low amount stimulate intergranular stress corrosion cracking (IGSCC) of austenitic SS [1]. Addition of alloying
elements like Ti, Nb or Cb and grain boundaries engineering have been used to minimize the sensitization, but there are some reports

⁎
Corresponding author at: Department of Materials Engineering, Isfahan University of Technology, Isfahan 84156-83111, Iran.
E-mail address: m.hamzeh@ma.iut.ac.ir (M. Hamzeh).

http://dx.doi.org/10.1016/j.engfailanal.2017.05.019
Received 15 May 2016; Received in revised form 6 April 2017; Accepted 1 May 2017
Available online 02 May 2017
1350-6307/ © 2017 Elsevier Ltd. All rights reserved.
M. Hamzeh et al. Engineering Failure Analysis 79 (2017) 431–440

Fig. 1. Schematic illustration of the distillation process.

of IGSCC of the stabilized grade of austenitic SS in industry [7,8].

It should be noted that crack mode can change from the speculated one by warm/cold working or heat treatment. Bijayani Panda
et al. [9] reported IGSCC of a 316L SS bellows where the chloride concentration and temperature were 6%wt and 100 °C,
respectively. Nevertheless, there was no evidence of carbide precipitation in grain boundaries. They mentioned that the presence of
deformation-induced martensite phase in the microstructure facilitated intergranular crack propagation [9]. In another study, Garcia
et al. [10] evaluated the effect of cold working and sensitization on SCC of 304 SS. They illustrated that cold working < 10%
followed by sensitization heat treatment increased the IGSCC susceptibility; and for deformations over 30% followed by sensitization
heat treatment the susceptibility to TGSCC increased.
Different studies have been done by researchers on diverse equipment including pipes, heat exchangers and so on for an
explanation and prevention of SCC in industrial scale [11–17]. The fluid of process, thermal stress, isolation components, and residual
contaminations on the surface were mentioned to be the causes of SCC in plant field. Removing or changing one of the three factors
(susceptible material, tensile stress, and specific environment) has been suggested as one practical solution.
In this study, the failure analysis is performed on corroded SP in a dewatering phenol tower. SPs are made of corrugated sheets
arranged in a crisscrossing relationship to create flow channels for the vapor phases in the chemical distillation process. This
honeycomb-like construction can be formed of metals, plastics, and ceramics with different sizes, shapes, and angles depending on

Table 1
The process data of the dewatering phenol tower at different points according to Fig. 1.

Point Chemical Components wt% (Phase) Temperature °C Pressure Bar a

Acetone Phenol Water Other Products

Inlet A 10 (g) 60 (g) 24.44 (g) 6.4 (1.42 g + 5.01 L) 140 1.2
B 98.51 (L) – 1.49 (L) – 40 1.2
Outlet C 74.48 (g) 0.03 (g) 24.49 (g) – 70 1.13
D 0.87 (L) 96.42 (L) 0.36 (L) 2.35 (L) 170 4.4

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Fig. 2. (a) A typical layer of structured packing composed of 8 segments, (b) Layers of corrugated sheets in a segment (these sheets are held by using long screws).

the chemical process variables. This structure is not only a packed structure, but also in close contact with chemical substances, which
are usually in high temperature; therefore, the occurrence of corrosion is probable. Any failure of SP can be responsible for the
significant decrease in distillation efficacy or chemical product quality. On the other hand, SPs are the internal parts of distillation
columns or towers, which in the case of damage, replacing the new packing required unscheduled shutdowns that imposed much
higher cost. Finding out the corrosion mechanism occurring in structure packing could help to prevent corrosion and decrease further
high costs. Therefore, failure analyses of corroded SP in a distillation tower were done based on place inspection and lab examination.

2. Description of the process condition and failure

Schematic illustration of the tower is shown in Fig. 1. Table 1 lists the chemical analysis of inlet and outlet fluids according to
process and fluid design. Moreover, the Cl ions concentration of inlet and outlet fluids which were monitored regularly by the quality
control unit, had not exceeded 15 ppm for a period of one month before detecting the failure.
In the process, a mixture of phenol, water and acetone at 140 °C is fed to the lowest layers of the SP at the bottom of the tower. A
stream of nearly pure acetone is showered from the top of the tower. The packing provides a high surface area for liquid and vapor
streams; therefore, the separation process will be expedited. Water and acetone vapor will be exhausted from the top outlet, while the
liquid phenol will be circulated by using a re-boiler at the bottom to maximize the separation process.
All tower internals were A240-TP 316L and the corrosion allowance was zero. The occurrence of corrosion was revealed after the
severe vibrations of discharging pump showed the accumulation of detached pieces of SP sheets in the strainer. Due to the repetition
of choking in the following days, it was noticed that the packing was under serious damage. As can be seen in Fig. 1, two beds of the
SPs are located in the tower; one near the bottom with an accumulated height of about 4 m, and the other at the top of the tower with
a height of 10 m. During an inspection by a technical inspector, the corrosion was seen only in the lower floor bed.
A fine bed of SP with a compact honeycomb structure is shown in Fig. 2. Each segment consists of numbers of 100 μm corrugated
sheets held together by long screws. A corroded segment is illustrated in Fig. 3. A sheet of failed packing (gathered and cleaned from
corroded region) and the deteriorated holder screw were used for subsequent failure analysis.

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Fig. 3. (a) A segment after corrosion consisting of sound and deteriorated region, and (b) A lot of detached pieces gathered at the bottom of the tower or the strainer of
the discharging pumps. (For interpretation of the references to color in this figure, the reader is referred to the web version of this article.)

3. Results

3.1. Sheet

3.1.1. Visual examination

A typical ruined segment of SP in Fig. 3 shows the decayed area covered with a green deposit and the unaffected area without any
sign of corrosion. Green products were cleaned by brush (the green powder did not have any cohesion to the underlying surface and
was easily cleaned) and collected for subsequent study. Then, the surface was washed with distilled water to make the surface
features seen clearly.
Two characteristic features can be distinguished in Fig. 4. Firstly, numerous cracks mostly originated from circle holes; and
secondly, material fragmentation in some regions may be because of a coalescence of crossed cracks (Fig. 3b).

Fig. 4. A piece of failed sheet gathered from corroded region after cleaning.

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Fig. 5. The result of EDS analysis on green products. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this
article.)

3.1.2. Chemical and microscopic analysis

The EDS spectrum and chemical analysis of green deposit on the sheet are depicted in Fig. 5. There is also 3100 ppm of chlorine
and 4100 ppm of sulfur, which could be interpreted as the existence of corrosive atmosphere according to literature [11,15,18,19].
The chemical analysis of sheet was done by optical emission spectroscopy. Table 2 shows that the chemical composition is in
consistence with 316L SS and meets the ASTM A240 requirement.
Fig. 6 demonstrates the cross-sectional view of the sheets after surface preparation including mounting, grinding, polishing and
etching with Aqua-regia. As illustrated, there are some narrow and deep pits. In an area far from the pitting, the structure is a typical
mono-phase austenite nearly without significant detrimental abnormality like grain boundary carbides. Fig. 6b and c are related to
other corroded sheets, which exhibit the imminent detachment of pieces from the sheet. Such behavior is not typical for pitting
according to ASTM-G46 [20].
The study of these cracks may lead us to the origin or causes of the failure. One feasible route for evaluating cracks is the study of
fractured surface morphology or metallographic examination of crack behavior. Unfortunately, the thin corrugated nature of sheet
made it impossible for precise optical or scanning electron microscope observation. Corroded samples with much more thickness and
simplicity were really needed. During the corrosion inspection, the tower's internals included supports, tower inside walls and
distributers were all in good circumstances without any evidence of corrosion. The best candidate for more detailed metallographic
study was the screws used for holding the sheets together. Fortunately, the inspection showed some cracks on screws. Besides, they
were located in service condition similar to sheets.

3.2. Screw

3.2.1. Visual examination

Fig. 7 illustrate a corroded screw. The screw is nearly straight, which means it has not been overloaded; moreover, there were no
distinct proofs of notable macroscopic corrosion or cracks, capable of being seen by naked eye. Since the detection of very fine cracks
could be very difficult by visual examination, to find the condition and location of probable cracks, the screw was bent by hand. There
were at least three points at which the screw broke easily. In Fig. 7b, a closer view of the outer surface of the bent screw just before
rupture is shown with several opened cracks.

3.2.2. Chemical and microscopic analysis

According to Table 3, chemical analysis of screw material is also 316L SS; just like the sheet. Metallography on deteriorated
screws in axial direction presents an austenitic phase with some equiaxial grains containing annealing twins. Fig. 8a points to the area

Table 2
Chemical composition of packing's sheet.

Element C Cr Ni Mo Mn Si P S N Fe

Measured 0.026 16.6 11.03 1.99 0.99 0.64 0.033 0.021 – Balance
ASTM A240 ≤ 0.03 16–18 10–14 2–3 ≤2 ≤ 0.75 ≤ 0.045 ≤ 0.03 ≤0.1 Balance

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Fig. 6. Microscopic structure of corroded structure packing' sheet.

of screw without cracks. In the failed area, there are cracks which originated from surface pitting and have penetrated into the
material in transgranular mode (Fig. 8b).

3.2.3. Fracture surface

Fig. 9 demonstrates the SEM image of the screw near the fracture surface after the cracks were revealed by bending. The surface is
covered with corrosion products, a large aggregation of which can be seen in region A near the fracture line. EDS analysis of this point
in Fig. 10 shows very high amount of chlorine. This can be the zone where pitting has developed, cracks have nucleated and then
gradually penetrated through the thickness of the screw. Fig. 9b presents the SEM image of fracture surface at higher magnification.
Identifying the mode of crack propagation by examining the fracture surface morphology is not possible since fracture feature has
been obliterated, and the surface is covered with corrosion products. There are also secondary cracks supposed to be opened or
propagated when the screw was deformed to reveal cracks.

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Fig. 7. The screw used for holding the sheets together (a) before and after bending by hand and (b) a closer view of the outer surface of the narrowed point just near
the rupture.

4. Failure analysis

Visual inspection revealed local corrosion of A240-316L SP in a dewatering phenol tower (Fig. 3). In ref. [21], the 316L is
mentioned as a corrosion resistant material in carbolic acid; therefore, the wrong material selection is not the case here.
Metallographic examination did not reveal significant microstructure abnormality as well. However, the pits, cracks and corrosion
deposits were the main signs of corrosion. Despite pitting corrosion, numerous cracks on the surface and detached pieces from the
sheets (Fig. 4) are indicative of another common corrosion mechanism of austenitic SS, i.e. SCC. Because of very thin and corrugated
nature of sheets, the detailed study of crack behavior for sure conclusion was not possible; therefore, the holder screws were used as
the alternative samples for supplementary study. The emerged cracks after bending the screw with flawless appearance (Fig. 7)
clearly show that cracks were created during SCC.
Different systems in which SCC can happen are listed in ref. [18] for austenitic SS. The result of EDS analysis on green deposits
revealed the existence of both sulfur and chlorine (Fig. 5). Sulfur can lead to Polythionic Acid Stress Corrosion Cracking (PASCC) and
Chlorine may cause Chloride Stress Corrosion Cracking (Cl SCC) [21]. In both, moisture is crucial. The existence of about 3600 ppm
liquid water is inevitable in the fluid circulating at the bottom (Table 1). In addition, accumulation weights of upper packing's
segments provide the other contributing factor for SCC i.e. applied stress on lower SPs.
From the findings, it can be concluded that PASCC cannot be the predominant corrosion mechanism. It happens due to sulfur
acids formed from sulfide scale, air and moisture acting on sensitized austenitic SS, and cracking propagates intergranularly.
Sensitization usually occurs between 400 and 815 °C [21]. Thus, PASCC is not responsible for SCC by considering the following
reasons:

Table 3
Result of optical emission spectroscopy on screw.

C Cr Ni Mo Mn Si S P Fe

0.028 17.39 10.99 2.12 0.92 0.6 0.029 0.018 Balance

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Fig. 8. Optical microscopic structure of spoiled screw in axial cross-section (a) far from decayed area, and (b) in cracked area.

1) The highest working temperature of tower was not in sensitized range for austenitic SS. The austenitic structure did not show
sensitized grain boundaries induced by service condition or manufacturing process, and subsequent intergranular mode of crack
propagation (Figs. 6 and 8).
2) There was a very high amount of chlorine but no sulfur in the corrosion products on the fracture surface of screw (Fig. 10).

Based on the above, it seems that ClSCC acted as the main mechanism of corrosion. According to API 571, increasing
temperature > 60 °C increases the susceptibility to cracking [21]. In this study, the temperature is obviously provided for ClSCC at
the bottom of tower (140–170 °C). The SPs are under applied stress, aqueous chloride is presented, and the structure is not sensitized.
Because of this condition, the cracks have originated from surface pitting and have propagated predominately across the grains
(Figs. 6 and 8). TGSCC is also reported in other austenitic SS industrial components where the environment is chlorinated and the
temperature is high (80–220 °C) [1,2,17,22,23].
No practical lower limit for chloride exists because there is always a potential for chlorides to concentrate; consequently, the
regions where chlorides can deposit would be in danger of SCC. It is reported that a chloride concentration of < 10 ppm is sufficient
to cause Cl SCC in austenitic SS if the metal temperature is higher than 60 °C [13]. Therefore, chloride amount of 15 ppm in the
distillation process can be sufficient for triggering Cl SCC.
The much higher amount of chloride in corrosion products than fluid's chloride value implies the local concentration of chloride
on the sheets. This increment has resulted in local corrosion of SP (Fig. 3) which can be attributed to the non-uniform distribution of
fluid passing through complicated routes between corrugated sheets. Because of Cl SCC, some pieces have been detached from sheets
and have moved to the outlet until being trapped in the strainer of the discharging pumps. Some other detached pieces have been
trapped in the space between honeycombs structures; therefore, easy flow of vapor within the channels has been blocked. The
misdistribution could also arise from other different causes such as drawback in equipment design, inaccuracy during installation of
SPs, malfunction of distributers and so on [24]. Nearly all these factors are associated with flows parameters inside the columns that
have been broadly discussed in other references [25–29]; hence, the results of this study were sent to the control process unit for
detailed consideration.

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Fig. 9. SEM image of the fracture surface of the screw.

5. Conclusion

1. Visual and microscopic examination revealed that chloride stress corrosion cracking happened in the structured A240-316L
packing of a dewatering phenol distillation tower.
2. Local corrosion of structured packing originated from the local concentration of Chloride on packing sheets. Even though the
chloride concentration of streams was not higher than 15 ppm, EDS analysis on corrosion products showed a very high amount of
chloride. It was due to maldistribution of fluid passing within the structured packing routes at the bottom of the tower.
3. Working temperature between 140 and 170 °C, concentrated chloride, moisture, and applied tensile stress provided an
appropriate atmosphere for transgranular stress corrosion cracking. As a result, the holder screws have failed and the sheets

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Fig. 10. The result of EDS analysis of corrosion products on fracture surface (point A).

have been broken into pieces.

References

[1] R. Cottis, Stress Corrosion Cracking: Guides to Good Practice in Corrosion Control, The National Physical Laboratory, Tech. Rep, 2000.
[2] A. Handbook, Corrosion, ISBN: 0-08170-019-0, 13 ASM International, USA, 1987.
[3] S.M.R. Ziaei, J. Mostowfi, M. Golestani Pour, S.A.R. Ziaei, Failure analysis: chloride stress corrosion cracking of AISI 316 stainless steel down hole pressure
memory gauge cover, Eng. Fail. Anal. 33 (2013) 465–472.
[4] M.F. Hurley, C.R. Olson, L.J. Ward, B.J. Jaques, K.A. Johnson, J.K. Gunnerson, et al., Transgranular stress corrosion cracking of 304L stainless steel pipe clamps
in direct use geothermal water heating applications, Eng. Fail. Anal. 33 (2013) 336–346.
[5] T.N. Prasanthi, C. Sudha, P. Parameswaran, R. Punniyamoorthy, S. Chandramouli, S. Saroja, et al., Failure analysis of a 304 steel component aged at 623 K, Eng.
Fail. Anal. 31 (2013) 28–39.
[6] L.K. Zhu, L.J. Qiao, X.Y. Li, B.Z. Xu, W. Pan, L. Wang, et al., Analysis of the tube-sheet cracking in slurry oil steam generators, Eng. Fail. Anal. 34 (2013) 379–386.
[7] J. Swaminathan, R. Singh, M.K. Gunjan, B. Mahato, Sensitization induced stress corrosion failure of AISI 347 stainless steel fractionator furnace tubes, Eng. Fail.
Anal. 18 (2011) 2211–2221.
[8] V. Kain, Stress Corrosion Cracking (SCC) in Stainless Steels. Stress Corrosion Cracking: Theory and Practice, 199 (2011).
[9] B. Panda, M. Sujata, M. Madan, S.K. Bhaumik, Stress corrosion cracking in 316L stainless steel bellows of a pressure safety valve, Eng. Fail. Anal. 36 (2014)
379–389.
[10] C. García, F. Martín, P.D. Tiedra, J.A. Heredero, M.L. Aparicio, Effects of prior cold work and sensitization heat treatment on chloride stress corrosion cracking in
type 304 stainless steels, Corros. Sci. 43 (2001) 1519–1539.
[11] A.N. Delavar, M. Shayegani, A. Pasha, An investigation of cracking causes in an outlet RTJ flange in ISOMAX unit, Case Stud. Eng. Fail. Anal. 1 (2013) 61–66.
[12] P. Roffey, E. Davies, The generation of corrosion under insulation and stress corrosion cracking due to sulphide stress cracking in an austenitic stainless steel
hydrocarbon gas pipeline, Eng. Fail. Anal. 44 (2014) 148–157.
[13] M. Suresh Kumar, M. Sujata, M.A. Venkataswamy, S.K. Bhaumik, Failure analysis of a stainless steel pipeline, Eng. Fail. Anal. 15 (2008) 497–504.
[14] S. Xu, C. Wang, W. Wang, Failure analysis of stress corrosion cracking in heat exchanger tubes during start-up operation, Eng. Fail. Anal. 51 (2015) 1–8.
[15] S. Ziaei, A. Kokabi, M. Nasr-Esfehani, Sulfide stress corrosion cracking and hydrogen induced cracking of A216-WCC wellhead flow control valve body, Case
Stud. Eng. Fail. Anal. 1 (2013) 223–234.
[16] Y. Li, N. Xu, X. Wu, J. Shi, L. Zhang, M. Zhao, et al., Failure analysis of the 304 stainless steel tube in a gas analyzer, Eng. Fail. Anal. 20 (2012) 35–42.
[17] T.M. Ahmed, A. Alfantazi, J. Budac, G. Freeman, Failure analysis of 316L stainless steel tubing of the high-pressure still condenser, Eng. Fail. Anal. 16 (2009)
1432–1441.
[18] R. Treseder, NACE Corrosion engineer's Reference Book, (1980).
[19] S.H. Khodamorad, N. Alinezhad, D. Haghshenas Fatmehsari, K. Ghahtan, Stress corrosion cracking in Type.316 plates of a heat exchanger, Case Stud. Eng. Fail.
Anal. 5–6 (2016) 59–66.
[20] A. G46-94, Standard Guide for Examination and Evaluation of Pitting Corrosion, ASTM International, West Conshohocken, PA, 2005.
[21] R. API. 571, Damage Mechanisms Affecting Fixed Equipment in the Refining Industry, (2003).
[22] W.B. Kan, H.L. Pan, Failure analysis of a stainless steel hydrotreating reactor, Eng. Fail. Anal. 18 (2011) 110–116.
[23] G. Yang, K.B. Yoon, Y.C. Moon, Stress corrosion cracking of stainless steel pipes for methyl-methacrylate process plants, Eng. Fail. Anal. 29 (2013) 45–55.
[24] A.N. Pavlenko, X. Li, H. Li, X. Gao, O.A. Volodin, A.S. Surtaev, et al., The influence of the microtexture, corrugation inclination angle, and perforation of
corrugated surfaces on the character of liquid spreading, Tech. Phys. Lett. 41 (2015) 774–777.
[25] A.N. Pavlenko, N.I. Pecherkin, V.Y. Chekhovich, V.E. Zhukov, S. Sunder, Houghton, Experimental study of the effect of maldistribution at the structured packing
inlet on the freon mixture separation efficiency, Theor. Found. Chem. Eng. 43 (2009) 1–11.
[26] Y. Yao, A.N. Pavlenko, O.A. Volodin, Effects of layers and holes on performance of wire mesh packing, J. Eng. Thermophys. 24 (2015) 222–236.
[27] S.V. Alekseenko, D.M. Markovich, A.R. Evseev, A.V. Bobylev, B.V. Tarasov, V.M. Karsten, Experimental study of liquid distribution in a column with a structured
packing, Theor. Found. Chem. Eng. 41 (2007) 417–423.
[28] J. Chen, C. Liu, X. Yuan, G. Yu, CFD simulation of flow and mass transfer in structured packing distillation columns, Chin. J. Chem. Eng. 17 (2009) 381–388.
[29] B. Szulczewska, I. Zbicinski, A. Górak, Liquid flow on structured packing: CFD simulation and experimental study, Chem. Eng. Technol. 26 (2003) 580–584.

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