Corrosion Science 44 (2002) 24252438 www.elsevier.

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XRD and SEM studies of the layer of corrosion products for carbon steel in various dierent environments in the province of Las Palmas (The Canary Islands, Spain)
J.J. Santana Rodr guez, F.J. Santana Hern andez, J.E. Gonz alez Gonz alez *
Department of Process Engineering, Universidad de Las Palmas de Gran Canaria, Campus Universitario de Tara, C.P. 35017, Islas Canarias, Espan ~a, Spain Received 17 October 2000; accepted 27 February 2002

Abstract A study was carried out in order to identify the various elements which make up the layer of rust which is produced on carbon steel exposed to the atmosphere in the province of Las Palmas (The Canary Islands, Spain). XRD and SEM analyses were used in order to identify and describe the various corrosion products produced over dierent areas on the islands: rural, urban, marine and marine-industrial. The main product found was akaganeite, which is typical of marine areas, followed closely by lepidocrocite, goethite and magnetite. Likewise, another formerly unidentied corrosion product for carbon steel, such as is green rust II, was detected. It has been found that the protective capacity of corrosion products increases over the rst year of exposition and then levels o. Likewise, a hyperbolic law was used to model the protective eect of the layer of corrosion products which gave extremely good regressive values both in the case of each station individually and when grouped together by corrosion category (r2 > 0:98). 2002 Published by Elsevier Science Ltd.
Keywords: Atmospheric corrosion; Carbon steel; Corrosion products; Green rust II; Akaganeite; Hyperbolic law

Corresponding author. Tel.: +34-928-451933; fax: +34-928-451932/933. E-mail addresses: juanj@cicei.ulpgc (J.J. Santana Rodr guez), javiers@cicei.ulpgc.es (F.J. Santana Hern andez), emilio@cicei.ulpgc.es (J.E. Gonz alez Gonz alez). 0010-938X/02/$ - see front matter 2002 Published by Elsevier Science Ltd. PII: S 0 0 1 0 - 9 3 8 X ( 0 2 ) 0 0 0 4 7 - 1

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1. Introduction The study of the corrosion products which form on carbon steel test-pieces is of enormous interest in that it allows us to detect the mechanism of transformation of the same and to evaluate their protective eect [14]. Various factors have a bearing on the formation and characteristics of these elements [5,6]. Of the various factors which intervene in the corrosion process [711], we found that the most important were the length of time exposed to humidity (TOW) [12] dened as the number of hours when RH is over 80% and the T a > 0 C, the level of the contaminants (chlorides and SO2 ) and other factors which aect the distribution of the corrosion products, the temperature, the rainfall, winds etc. Generally speaking, the protective eect of the corrosion products for carbon steel diers considerably in time perspective from what can be observed in the case of other metals in that, in the former case, more time is required for this to be produced [13] and when such occurs, it is to a much lesser degree due to the fact that the mechanism of onset is dierent [14] from the situation for other non-iron metals. Likewise, the initial conditions of exposure are of great importance in that they determine the degree to which the test-pieces will be aected [15]. The corrosion rate to be observed on a carbon steel test-tube is high in the initial phases of exposure [16] leveling o with time [16,17]. This may be due to the fact that the layer of oxide which is formed on the test-tube becomes more compact over time, in function of the type of environment and the level of contamination. The situation in The Canary Islands (Spain) is one of varying micro-climates, depending upon altitude, over short distances. Thus, it is vital that we study and dene the corrosion products which are formed on carbon steel in order to detect the dierent mechanisms involved in corrosion. This study was carried out within the framework of the atmospheric corrosion map in The Canary Islands. Zinc, copper, aluminium and galvanised steel were also studied.

2. Experimental The metal test-pieces used in the experiment were made of carbon steel in the percentages detailed in Table 1. These test-pieces were 100 40 2 mm3 and were duly coded in order to facilitate subsequent identication. The study test-pieces were distributed to a total of 39 stations over the three larger islands which make up the province of Las Palmas. Four dierent environments were taken into account: rural, urban, marine and marine-industrial. In Fig. 1, we give the layout of the Canary
Table 1 Percentage of composition in carbon steel samples C Composition (%) 0.060 Mn 0.370 Si 0.080 P 0.009 S 0.014 Fe Rest

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Fig. 1. Location of The Canary Islands and the corrosion stations.

Archipelago together with the approximate location of the corrosion stations. The exact location, predominant environmental conditions and degree of corrosion for carbon steel, in line with the ISO 9223 norm for weight loss (WL) [18] are detailed in Table 2. This study was carried out over a two-year period between February 1996 and 1998. The XRD and SEM analyses were carried out on the test-pieces after one and two years exposure. The corrosion stations consisted in a metallic support for the metal test-pieces, tilted NNE 45. In the back part of the support, there were SO2 traps which used the lead toggle method outlined in the ASTM D 2010-85 norm to analyze content [19] and the chloride trap, which used the damp toggle method indicated under the ISO 9225 norm [20]. The carbon steel test-pieces were cleaned according to the procedure described in the ASTM G1-90 norm [21], previous to exposure. The analyses of

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Table 2 Location of the corrosion stations and type of environment predominating Station Altitude (m) Longitude Latitude Environment/corrosion category accord to ISO 9223 Rural/C2 Humid rural/C3 Industrial marine/C5 Marine/C4 Rural/C2 Humid rural/C2

Fuerteventura 1 Ayuntamiento de Puerto del Rosario n UNELCO en 2 Subestacio Corralejo 3 Central T ermica Las Salinas 4 Centro Cultural del Cotillo 5 Tenencia de alcald a de Gran Tarajal n UNELCO Costa 6 Subestacio Calma Lanzarote 7 Cabildo Insular de Arrecife 8 Central T ermica Punta Grande 9 Aeropuerto de Lanzarote 10 Ayuntamiento de Har a 11 Almac en Municipal de Teguise 12 Ayuntamiento de Yaiza Gran Canaria 13 Central T ermica de Jin amar 14 Ayuntamiento de Arucas 15 Central T ermica Juan Grande 16 Ayuntamiento de Santa Br gida 17 Cabildo Insular de Gran Canaria  blico Sardina del Norte 18 Colegio Pu 19 Ayunt. San Nicol as de Tolentino 20 Ayuntamiento de Moya 21 Ayuntamiento de Gu a 22 Inst. Canario de Ciencias Marinas 23 Colegio Pbl. Placido Fleitas (Telde) 24 Plt. Desal. ELMASA (San Agust n) 25 Aeropuerto de Gran Canaria  blico de San Mateo 26 Colegio Pu 27 Ayuntamiento de Tejeda 28 Ocinas Municipales de Arguinegu n 29 Almac en Municipal Santa Luc a  blico de Mog 30 Colegio Pu an 31 Ayuntamiento de Agaete  blico Valle de Agaete 32 Colegio Pu imes 33 Ayuntamiento de Agu n de 34 Centro de Formacio Valleseco

23 50 38 35 10 100

28 300 0000 28 420 1300 28 320 0100 28 400 5400 28 120 4900 28 090 4200

13 510 0600 13 540 0200 13 500 2200 14 000 4500 14 010 1300 14 130 5500

25 25 15 278 280 180 30 250 30 520 40 50 70 485 185 20 200 40 50 850 1060 30 100 280 50 255 290 150

28 28 28 29 29 28 28 28 27 28 28 28 27 28 28 27

570 590 560 080 030 570 020 070 480 020 060 090 590 060 080 590

5700 2000 5100 5100 4000 0800 3500 1400 1600 0200 1600 1000 1000 4000 2700 2700

13 13 13 13 13 13 15 15 15 15 15 15 15 15 15 15

320 300 350 300 330 450 230 300 250 290 240 410 460 340 370 210

0000 0000 5800 0200 2100 5500 4300 3600 3300 1300 2000 1000 4000 1700 1200 3400

Rural/C3 Humid industrial/C3 Rural/C2 Humid rural/C3 Humid industrial/C4 Humid rural/C2 Industrial marine/C4 Rural/C2 Industrial marine/C4 Rural/C2 Urban/C2 Humid rural/C2 Rural/C2 Humid rural/C3 Rural/C2 Industrial marine/C5 Humid rural/C3 Humid rural/C3 Humid Humid Humid Humid industrial/C3 rural/C2 rural/C2 rural/C3

28 000 0000 27 460 2100 27 28 28 27 27 27 28 28 27 28 550 000 000 450 510 530 060 050 540 070 5400 4800 0000 1600 0000 1000 2400 1900 2400 3000

15 240 2000 15 310 5000 15 15 15 15 15 15 15 15 15 15 220 310 360 400 270 430 420 390 260 260 3000 0000 2500 1500 3200 0900 0500 3800 0100 4700

Rural/C2 Rural/C2 Rural/C2 Rural/C2 Rural/C2 Rural/C3

J.J. Santana Rodr guez et al. / Corrosion Science 44 (2002) 24252438 Table 2 (continued) Station Altitude (m) 600 100 350 15 980 Longitude Latitude

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Environment/corrosion category accord to ISO 9223 Rural/C2 Industrial marine/C3 Humid rural/C3 Industrial marine/C3 Urban/C2

35 36 37 38 39

Ayuntamiento deTeror Centro C vico pol gono Jinamar Edf. Departamental de Ingenier a FEDEX. Muelle de la Luz ISCANARIAS, S.L., Las Torres

28 28 28 28 28

030 010 040 080 010

4000 5400 2900 5900 5900

15 15 15 15 15

320 220 260 240 340

0800 2000 2800 1000 4400

chlorides, SO2 and TOW denition were carried out monthly over the two year period of exposure. The XRD analysis was carried out directly on the metallic plate adapted to the equipment sample support and on metal powder which had been previously prepared in a morter. The equipment used consisted in a SIEMENS D-5000 X-ray diractometer with a ne structure air-insulated X-ray tube (of the type FK 60-04), ) and with a wavelength scintillation detector with a copper anode (Cu Ka1 5406 A 0.027 nm < k < 0:05 nm, with the following measurement conditions: aperture 0.025; exposure 1 s; scan speed, 1.5/min and scan angles between 5 6 2h 6 35. One of the lateral faces of the carbon steel test-tube was led in order to carry out the SEM studies. This was done using ground aluminium oxide in an automatic buer until the layer of corrosion products was clearly dierenciated from the metallic substrate. The ESM used was the model Jeol JSM-T220A.

3. Results and discussion The XRD studies showed that the corrosion products were akagaenite (bFeOOH), lepidocrocite (c-FeOOH), goethite (a-FeOOH), magnetite (Fe3 O4 ) and hematite (Fe2 O3 ) which are typical in the case of carbon steel as seen in other studies [2225]. The elements which are to be detected in the rst months of exposure are lepidocrocite, akaganeite and goethite such as has been registered in other studies [26]. However, we have also detected an element not formerly mentioned in the literature, which is green rust II, Fe3:6 Fe0:9 (O,OH,SO4 )9 together with iron oxide phosphate, b-Fe2 (PO4 )O. Of the various elements detected, akagaenite is the predominant component. Goethite was only found at four stations (3, 11, 22 and 37), and only one, in the second year of exposure. The fact that this element is scarcely to be found may be due to the fact that in environments with high levels of chlorides, akagaenite is formed instead of goethite. If we dene the relationship between the concentration of chloride ions and hydroxile ions as: r0 Cl =OH , then when r0 6 6 goethite will be formed [27], whereas for r0 values between 6.5 and 7.5, we will get a goethite akaganeite mix. For r0 values equal to, or over 8, we will get akagaenite, which was exactly the situation which occurred in most of our corrosion stations.

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The hematite which is formed may be the result of the akaganeitehematite transformation [28]. The akaganeite disappears after long periods of exposure. Akaganeite, b-FeO(OH), was to be found in all the stations in the study with the exception of numbers 26 and 27, both in the countryside and with C2 levels of potential corrosion. This is due to the fact that both stations are in the hinterlands of the islands and have the lowest levels of chlorides registered over the whole of the province. In Figs. 24(ac), we can see the average values of the speed of contami-

Fig. 2. (a) Variation in chlorides depositions rate in Fuerteventura Island throughout the two years of exposure. (b) Variation in chlorides depositions rate in Lanzarote Island throughout the two years of exposure. (c) Variation in chlorides depositions rate in Gran Canaria Island throughout the two years of exposure.

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Fig. 3. (a) Variation in SO2 depositions rate in Fuerteventura Island throughout the two years of exposure. (b) Variation in SO2 depositions rate in Lanzarote Island throughout the two years of exposure. (c) Variation in SO2 depositions rate in Gran Canaria Island throughout the two years of exposure.

nating deposits (Cl and SO2 ) together with the corresponding TOW at 3, 6, 9, 12, 18 and 24 months for the three islands which make up the province of Las Palmas (The Canary Islands, Spain). This conrms the fact that this element only appears when there is contamination by chlorides [29] as has been shown in other studies where akaganeite was only found in marine environments [3037]. Nevertheless, from the studies carried out, there would appear to be a limit of chloride concentration, as of which said element is not formed. The presence of akaganeite was evident in stations

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Fig. 4. (a) Variation of TOW in Fuerteventura Island throughout the two years of exposure. (b) Variation of TOW in Lanzarote Island throughout the two years of exposure. (c) Variation of TOW in Gran Canaria Island throughout the two years of exposure.

which were classied a priori as rural but which had concentrations of chlorides over 1416 mg/m2 /day which was not the case for stations 26 and 27. Thus, it can be deduced that the chloride concentration must remain above these values for akaganeite to be formed. When compared with other stations, such as 11 or 18, both of which had SO2 and TOW levels similar to stations 26 and 27, but which were in marine environments, it can be seen that chloride concentration is the decisive factor when determining whether or not akaganeite will be formed. In Figs. 57, we compared TOW and level of contaminants over six stations. Here, it is clear that stations 26 and 27 had three times less chloride level than station 2 (Fig. 5)

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Fig. 5. Variation in chlorides depositions rate in the corrosion stations number 2, 11, 18, 25, 26 and 27 throughout the two years of exposure.

Fig. 6. (a) Variation in SO2 depositions rate in the corrosion stations number 2, 11, 18, 25, 26 and 27 throughout the two years of exposure. (b) Variation in SO2 depositions rate in the corrosion stations number 2, 11, 18, 26 and 27 (except station 25) throughout the two years of exposure.

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Fig. 7. Variation of TOW in the corrosion stations number 2, 11, 18, 25, 26 and 27 throughout the two years of exposure.

whereas the levels of SO2 and TOW are similar to those to be found in the rest of the stations. However, both stations 2 and 25 diered from the rest. Station 25 had the highest level of chlorides, SO2 and TOW whereas station 2 diered from the rest in respect of SO2 levels. Akaganeite was detected in these two stations after two years exposure. When compared with other stations with the same level of chlorides, it was found that there were signicant dierences in SO2 levels as can be seen in Fig. 6(a and b). It would seem that the presence of SO2 conditions the appearance of akaganeite as opposed to goethite. Misawa et al. [38] and other authors [39] have forwarded the following mechanism for the transformation of lepidocrocite in goethite: cFeOOH; bFeOOH; Fe3 O4 ! FeOx OH32x ! aFEOOH The lepidocrocite, akaganeite and the Fe3 O4 may be transformed into a hydroxide in an intermediate phase before becoming goethite. The presence of high levels of SO2 may facilitate the production of more compact corrosion products which impede water ltering through the layer and, thus, the chloride ion dissolving. The fact that stations 2 and 25 had relatively high levels of SO2 as compared to the rest of the stations could mean that the nal transformation into goethite will not occur, which would explain the predominant presence of akaganeite. The analysis via SEM for these two stations allowed us to see that akaganeite had already formed over the rst year. If we compare the results obtained via SEM with stations which could be considered to be a priori more aggressive, such as stations 22 and 15, with corrosion index C5 and C4 respectively (according to ISO 9223), we can observe how the surface of the test-tube looks much rougher than the rest of the stations, due to the extremely high levels of SO2 , higher than any of the other stations as can be veried in Figs. 2b, 3b, and 4b. The attack suered by these stations is of such a magnitude that it is possible to observe patches of non-corrode metal dotted around the layer of corrosion product. The analysis via SEM has allowed us to check the degree of corrosion suered by the various test-pieces exposed to dierent environments and to conrm that the

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highest categories of corrosion correspond to rougher layers of corrosion products. We also determined that corrosion was uniform in all cases apart from at station 22 where it consisted in corrosion spots scattered over the metallic surface (the marineindustrial environment). There are authors [40,41] who have attempted to describe the buer eect of corrosion products mathematically. They use a hyperbolic relationship between the quotient for WL suered by the test-tube and the accumulated WL (AM) over time of exposure. The procedure consists in dening the quotient between the data for WL over long periods of exposure and the respective values accumulated monthly in order to be proportioned criteria with respect to the protective eect of the rust. This model tted extraordinarily well to all the stations and gave us the interval frequency for the regression intervals shown in Table 3 [42]. We can see how in 92.4% of the cases, there was a regression index of over 0.90. After detailed analysis of the graphs charted with the WL/AM over time of exposure, we get a steep line over the rst year of exposure which, as of then, levels o. This is to be seen over the 39 stations studied. The same study was carried out, only categorising the stations by level of corrosion, which gave the results to be seen in Table 4. We can see how the t is excellent in either case. The evolution of the quotient WL/AM is the same for each of the stations: a steep slope over the rst year and a buer eect over the second year [43]. The analysis allows us to conclude that the corrosion products categorised as C5 are least protective and that C3 category is more protective than other more

Table 3 Intervals of frequencies of the regression indexes obtained when applying the hyperbolic law to corrosion products developing on carbon steel Intervals of regression indexes 0.860.90 0.900.91 0.910.92 0.920.93 0.930.94 0.940.95 0.950.96 0.960.97 0.970.98 0.980.99 0.991.00 % 7.6 2.6 10.2 5.1 12.8 7.6 10.2 12.8 10.2 15.4 5.1

Table 4 Regression indexes obtained when applying the hyperbolic law to dierent corrosivity categories Corrosivity categories C2 C3 C4 C5 R2 0.992 0.989 0.987 0.988

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aggressively corrosion categories. This is in line with observations of other authors [43] who show that in urban environments (which relate to the C3 category), the corrosion products are less protective than those formed in other environments. No reference was found to relate the two elements indicated at the beginning of this article, green rust II, Fe3:6 Fe0:9 (O,OH,SO4 )9 and iron oxide phosphate, b-Fe2 (PO4 )O, with atmospheric corrosion. The iron oxide phosphate may be the result of sporadic contamination such as seagulls or pigeons droppings. However, the origin of the green rust II is by no means clear. The various possible sources of the same are the following: oxidation of green rust I producing green rust II (the sulphide becomes a sulphate) [44] or by induced microbiological corrosion on the steel [45]. This element was found on steel structures which are in direct contact with seawater and it forms below layers of biolm. Therefore, it would seem that one of the main sources of this element may be microbiological in nature, as triggered by micro-organisms carried by the sea breeze. This theory would seem to be the most plausible given the proximity of said stations to the coastline. Nevertheless, there is a specic project already underway to determine the source of said corrosion product.

4. Conclusions It was seen that akaganeite was the main corrosion product formed in marine environments from the studies carried out. It was followed, by order of importance, by goethite and lepidocrocite. Other corrosion products have been detected which had not been mentioned previously in the literature relating to atmospheric corrosion: iron oxide phosphate and green rust II. The former was considered to be the result of sporadic fouling by birds whereas the latter may have a microbiological source. Likewise, we tested the validity of the hyperbolic law used to dene the protective capacity of the layer of corrosion products on carbon steel and found that it tted adequately.

Acknowledgements Our thanks go to UNELCO S.A. for their assistance without which this article would not have seen the light.

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