August 2002

Materials Letters 55 (2002) 312 317 www.elsevier.com/locate/matlet

AES and EDS microanalysis of a petroleum well tubing in cross-section

A. Cosultchi a,b,*, J.R. Vargas a, B. Zeifert a, E. Garciafigueroa b,c, a-Bo rquez c, V.H. Lara d, P. Bosch d A. Garc
b a Department of Metallurgical Engineering, ESIQIE-IPN, Mexico City, Mexico Instituto Mexicano del Petroleo, 152 Eje Central L. Cardenas, 07730 Mexico City, Mexico c ESFM-IPN, UPALM, Ed. 9, 07738 Mexico City, Mexico d UAM-I, Av. Michoacan y Purisima, Iztapalapa, 09340 Mexico City,Mexico

Received 15 February 2001; received in revised form 19 October 2001; accepted 25 October 2001

Abstract Two techniques, Auger electron spectroscopy (AES) and energy dispersive spectroscopy (EDS), were applied to obtain the composition of the cross-section of a piece of tubing used within a petroleum well. The structure and composition of the steel wall and of the internal oxide layer were achieved. Physical and chemical changes of the original iron oxide layer induced by petroleum compounds were discussed. D 2002 Elsevier Science B.V. All rights reserved.
Keywords: Auger electron microscopy; EDS; XRD; Microanalysis; Pipe; Iron compounds; Pyrrhotite; Petroleum organic compounds

1. Introduction Selection of a tubing string used in petroleum extraction is governed by mechanical properties, which are based on the well depth and operation conditions. The pipe furnished to form the coiled tubing string is normally an API grade, seamless and manufactured by hot working and, subsequently, coldfinished [1]. The internal surface of the tubing is usually covered with a thin iron oxide multi-layer, which offers protection against atmospheric corrosion [2,3]. Assuming that light hydrocarbons are natural
* Corresponding author. Instituto Mexicano del Petroleo, 152, Eje Central L. Cardenas, 07730 Mexico City, Mexico. Tel.: +525-3337013; fax: +52-5-5678776. E-mail address: acosul@imp.mx (A. Cosultchi).

corrosion inhibitors [4,5], the initial oxide layer composition is expected to prevail on the tubing surface after its contact with petroleum. However, when carbon steel is working in ambient containing sour (H2S) or sweet (CO2) gases, the surface is damaged by corrosion or sulfide stress cracking [6 9]. Additionally, petroleum organic material is often found adhered on the tubing surface. Consequently, the internal diameter of the tubing is reduced, which contributes to the declination of the petroleum flow. So far, the interaction between petroleum and iron oxide scale has not been considered in the study of the mechanism of organic deposition in petroleum wells. In this work, the AES and EDS characterization of the modified iron oxide scale as a consequence of its contact with petroleum compounds is presented and the mechanism of the organic deposit formation is discussed.

0167-577X/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved. PII: S 0 1 6 7 - 5 7 7 X ( 0 2 ) 0 0 3 8 4 - 1

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Auger electron spectroscopy (AES) provides a surface microanalysis with a sampling depth on the order of 1 nm, whereas the characteristic X-ray (EDS) sampling depth was 0.3 Am (or 300 nm). Therefore, the AES information was assumed as surface composition, whereas the EDS results were assumed as bulk composition.

2. Experimental A tubing string was extracted from a well located in a southeastern Mexican field, which produces a 29.5j API crude oil from the upper Jurassic Kimmeridge age zone reservoir with a bottom hole temperature of 420 K. A tubing piece with a black layer of solid material of 2 cm thickness adhered on its internal surface was collected. Coupons of 1.5 1.5 cm2 and 0.3 cm thickness were lathe-turned at low velocity and one of the cross-sections was polished. The bulk elemental composition was obtained using a scanning electron microscope (SEM) JEOL JSM 6300 fitted with a NORAN energy dispersive X-ray analysis facility (EDS) [10]. The operating conditions for the chemical composition obtained by EDS were 15 keV for the initial electron energy, Cu Ka radiation and a working

distance of 39 mm. A scanning electron microscope JEOL JAMP 30 fitted with Auger electron spectroscopy (AES) and using an electron beam of 10 KeV performed the surface elemental composition. Each area was sputtered with Argon during 30 min previous to the spectrum recording. Additionally, the element concentrations were calculated using their relative Auger sensitivity factors from literature [11]. The quantitative analysis precision is affected by the factors selection process and, consequently, the expected errors used to be not less than F 20%. A Siemens D500 X-ray diffractometer (XRD) with CuKa radiation and a diffracted beam monochromator was used. In order to study the coupon surface with adhered material, the coupon was placed in the diffractometer sample holder in order to fulfill the Bragg condition. Thus, information on the preferred orientation of the crystalline compounds was obtained.

3. Results A layer of material with a thickness of 8 to 15 Am covers the surface of the coupon, as previously reported [12]. The diffraction pattern of this surface layer, shown in Fig. 1, exhibits intense and sharp peaks

Fig. 1. XRD diffractogram of the L-80 coupon surface with adhered material.

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Fig. 2. Micrograph of the tubing cross-section showing the position and the EDS and AES recorded spectra.

corresponding to crystalline phases identified as magnetite (JCPDS 11-0614) and pyrrhotite (JCPDS 220358). The relative intensities of the peaks corresponding to magnetite do not reproduce the values of the JCPDS card; the crystals are, therefore, oriented toward the direction of the most intense peak (311). Apparently, the steel substrate and its manufacturing conditions influenced the growth of the magnetite crystals. Such is not the case for pyrrhotite crystals, as the peak heights reproduce the JCPDS reported intensities.
Table 1 Surface (AES) and bulk (EDS) elemental compositions (in wt.%) Element Zone 1 AES Fe O Mn Si S C Cr Mo Al Ca Cl K Na 51.6 28.74 6.47 EDS 97.54 0.56 1.52 0.37 Zone 2 AES 18.85 57.72 5.42 2.6 15.41 EDS 80.35 17.94 1.42 0.29

The SEM micrograph in Fig. 2 shows a view of the polished cross-section of the coupon. The bulk metal, shown in Fig. 2, apparently exhibits a martensitic structure [13]. The bulk metaloxide scale interface (Z3) is irregular and exhibits a stripes-like morphology penetrating the bulk metal. The oxide scale and the coupon border also exhibit irregular morphologies, with valley and edge-like structures (Z4 and Z5, respectively). EDS and AES spectra were recorded from five zones across the tube section, as indicated in Fig. 2. The elemental composition results obtained by these two techniques are presented in Table 1 and summarized as follows. (1) The surface composition of Zone 1 (Z1) indicates that iron is oxidized and there are higher amounts of manganese, chromium and molybdenum than the bulk composition shows. (2) The surface composition of Zone 2 (Z2) evidences an increase of oxygen content as well as the presence of carbon and silicon. The bulk composition indicates also an increment of the oxygen content. (3) The surface composition of Zone 3 (Z3) confirms the presence of sulfur, which is associated with an increase in the oxygen content and a decrease in the carbon amount. Additionally, the Auger KLL peak of carbon splits into two, at 272 and 270 eV, which suggests that there may be at least two types of carbon bonds. The bulk composition is similar to the previous zone with aluminum as an additional element.

Zone 3 AES 14.79 64.01 3.40 1.86 11.18 4.76 EDS 81.42 16.64 1.05 0.52

Zone 4 AES 6.66 22.56 38.68 27.21 4.89 EDS 71.27 15.74 1.18 2.26 2.69 0.07 5.38 0.64 0.22 0.55

Zone 5 AES 20.47 41.32 23.61 14.6 EDS 80.11 10.76 1.36 0.28 5.38 1.07 0.12 0.19 0.19 0.26 0.29

8.16 5.03

0.23 0.15

The error estimation for EDS is F 4%, while for AES is F 20%.

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(4) The surface composition of Zone 4 (Z4) shown in Fig. 3a indicates high amounts of sulfur and calcium, while the bulk composition exhibits high amounts of aluminum. Additionally, the bulk composition registered the same iron oxidation degree as Zone 3. In this zone, the Auger KLL oxygen peak underwent a change of shape and the splitting of the signal.

(5) The surface composition of Zone 5 (Z5) shown in Fig. 3b indicates that the oxygen content has decreased and the sulfur content has increased. The bulk composition indicates a less than ideal iron oxidation degree (O/Fe atomic ratio is 0.47). Carbon, sulfur and other elements were also identified in the bulk composition. The Auger peaks of Fe at 598 and 652 eV shift to 601 and 655 eV, respectively.

4. Discussion The AES and EDS spectra registered from different zones across the tubing wall depict the variation of concentration of the main elements on the surface and in the bulk steel, respectively. The steel composition is nonuniform, as shown in the bulk composition from Zones 1 to 3. However, this composition corresponds to an L-80 grade type 1, which is usually produced from a C Mn or C Mn Mo steel [6]. Most of the petroleum compounds involved in the formation of the adhered layer of organic deposit are polar molecules containing N, O and S along with C and H atoms. Additionally, inorganic compounds are constantly carried out from the reservoir, together with the petroleum flow. Furthermore, rupture of the original iron oxide layer might be induced within the well by different events such as the geothermal gradient as well as by mechanical stress originated by the freely suspended tubing string weight. The contact between the iron oxide layer and petroleum increases as the surface is enlarged, and moreover, the bulk metal is exposed to petroleum ambient. Therefore, the morphologies and composition of the scale layer, Zones 4 and 5, reveal such events. The coupon border, which corresponds to the internal surface of the tubing, exhibits irregular structures, which are associated with the presence of high amounts of sulfur, carbon, calcium and aluminum. Thus, the valley-like structures (Z4) are related to surface composition rich in sulfur, carbon and calcium, although sulfur was not observed in the bulk composition. Therefore, the source of the surface sulfur amount must be BaSO4 as determined elsewhere [14], being one of the drilling mud components. As to carbon, the presence of organic compounds on the coupon surface was established by FTIR in the reflection mode. Accordingly, the infrared

Fig. 3. AES and EDS spectra registered from (a) Z4 and (b) Z5 coupon zones.

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spectrum, presented elsewhere [12], revealed the characteristic vibration bands of methyl and methylene groups corresponding to saturate and aromatic hydrocarbons, together with some other minor vibration band assigned to oxygen bearing compounds like hydroxyl and carbonyl compounds. Changes in the shape and splitting of the Auger KLL oxygen peak indicate that, in this zone, there may be at least two different types of oxygen-bearing compounds, organic as well as inorganic compounds.

In the edge-like structures (Z5), the Auger Fe peaks are shifted from their normal positions, which indicates the presence of new iron bonds. Indeed, as shown elsewhere [14], the Mo ssbauer Spectroscopy identified compounds such as magnetite, maghemite, pyrrhotite, lepidocrocite and goetite in the scrapped oxide layer. Petroleum sulfur compounds and, especially, the H2S molecules are adsorbed mainly on noncoordinative iron sites on the steel surface, thus, sulfur atoms left on the surface reacts with Fe followed by the formation of iron sulfide phases [15]. Therefore, the original iron oxide layer experienced chemical and physical changes as a consequence of its contact with petroleum. Magnetite, which is the main compound of the scale layer, crystallizes in a cubic inverse spinel structure. The surface structure of Fe3O4 (111) yields a strongly relaxed bulk termination with a quarter monolayer of Fe atoms exposed and raised above a complete monolayer of oxygen. Maghemite (g-Fe2O3) is formed by hydrolysis as a passivating layer on the magnetite surface [9]. Iron cations on the iron oxide surfaces has Lewis acidic character [16], although when hydroxyl groups are adsorbed on the oxide surface, they may act as Bro nsted acidic sites, which may dissociate and protonate adsorbed bases [15,16]. Therefore, specific chemisorption of organic compounds on steel or preoxidized steel surface is a very complex process, in which case, molecules with high donor orbital energy are strong bonded to a surface with low acceptor orbital energy [17]. Moreover, the strength of the surface bond is directly correlated to the electronegativity of the organic molecule functional groups. Eventually, the steel and scale wettability by water or by hydrocarbons is critical in the formation process of corrosion products or organic deposits on the tubing surface inside the petroleum wells. Fig. 4 shows schematically the structure of the scale layer before and after petroleum contact.

5. Conclusions The EDS and AES techniques let us determine the chemical composition at different depths and from different zones through the cross-section of the petroleum tubing. Thus, a nonuniform composition of the

Fig. 4. Scheme of the structure of the scale (a) formed at room temperature and (b) in petroleum ambient.

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steel as well as changes in the structure and composition of the iron oxide scale are identified. The surface chemical transformations are related to the formation of new iron phases as a consequence of steel surface contact with petroleum compounds and organic compounds chemisorption. Likewise, physical changes of the tubing internal border reflect the consequences of the scale fracturing and the adherence of organic and mineral compounds as a thick layer on this surface.

Acknowledgements This research was supported by Instituto Mexicano del Petroleo Grand FIES 97-06-I.

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