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FACTORS AFFECTING THE NANO-SCALE INVESTIGATION OF PASSIVE LAYER FOR CORRODING STEEL BARS IN CONCRETE UNDER SEVERE

ENVIRONMENTAL CONDITIONS
Raja Rizwan HUSSAIN (1), Abdulrahman ALHOZAIMY (2), Abdulaziz Al NEGHEIMISH (3) and Rajeh Al ZAID (4) (1) Asst. Professor, Center of Excellence for Concrete Research and Testing, Civil Engineering Department, King Saud University, Riyadh, Saudi Arabia. (2) Professor, Center of Excellence for Concrete Research and Testing, Civil Engineering Department, King Saud University, Saudi Arabia. (3) Executive Director and Associate Professor, Center of Excellence for Concrete Research and Testing, Civil Engineering Department, King Saud University, Riyadh, Saudi Arabia. (4) Professor, Center of Excellence for Concrete Research and Testing, Civil Engineering Department, King Saud University, Riyadh, Saudi Arabia. Keywords: Nanotechnology, Corrosion, Passive Layer, SEM, XRD, EDS, Reinforced Concrete. Author contacts Authors First Author E-Mail Fax Postal address PO Box: 800, CoE-CRT, raja386@hotmail.com +966-1-4696355 King Saud University, Riyadh, 11421, Saudi Arabia. PO Box: 800, CoE-CRT, +966-1-4696355 King Saud University, Riyadh, 11421, Saudi Arabia. PO Box: 800, CoE-CRT, +966-1-4696355 King Saud University, Riyadh, 11421, Saudi Arabia. PO Box: 800, CoE-CRT, +966-1-4696355 King Saud University, Riyadh, 11421, Saudi Arabia.

Second Co-author

Third Co-author

Fourth Co-author

Contact person for the paper: Dr. Raja Rizwan Hussain, Asst. Professor, Center of Excellence for Concrete Research and Testing, Civil Engineering Department, King Saud University. e-mail: raja386@hotmail.com, Tel:+966-562-556969, Fax: +966-1-4696355,

Postal address: PO Box: 800, Riyadh, 11421, Saudi Arabia.

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Chloride ions and high temperature break the passive film on the reinforcement steel surface in concrete protecting the steel from corrosion which is believed to be in nanometers and primarily composed of iron oxides. A comparison of steel bar with passive layer showed a uniform repeating pattern in contrast to the surface without passive layer at the nano-level. XRF. Riyadh. However. ground water. Riyadh. King Saud University. Civil Engineering Department. The nano-scale investigations conducted in this paper revealed that the steel bars with passive oxide layer have an orderly structure in contrast to what was expected. Saudi Arabia. Center of Excellence for Concrete Research and Testing. Abdulrahman ALHOZAIMY (2). (3) Executive Director and Associate Professor. Center of Excellence for Concrete Research and Testing. Saudi Arabia. Three Iron-oxides (β-Fe2O3. Saudi Arabia. Saudi Arabia. To address these key issues. little is known about the chemical composition and the structure of the passive film as well as its breaking process. King Saud University. Civil Engineering Department. Civil Engineering Department. Abstract The presence of ambient hot weather and chloride ions in the soil. This makes it difficult to classify corrosion. proven by the fact the chloride threshold value of steel measured by conventional electro-chemical techniques under variable temperature conditions can vary greatly. Center of Excellence for Concrete Research and Testing. Abdulaziz Al NEGHEIMISH (3) and Rajeh Al ZAID (4) (1) Asst.92O 2 . This is an interesting and novel finding which will be further explored and reported in the future. King Saud University. (2) Professor. XRD. as well as in the concrete raw materials is a major cause of corrosion in reinforced concrete structures.FACTORS AFFECTING THE NANO-SCALE INVESTIGATION OF PASSIVE LAYER FOR CORRODING STEEL BARS IN CONCRETE UNDER SEVERE ENVIRONMENTAL CONDITIONS Raja Rizwan HUSSAIN (1). Center of Excellence for Concrete Research and Testing. Professor. Metallography) have been addressed to obtain a more precise characterization of passive film as well as its breaking in terms of nano-micro structural material properties. Fe0. factors and limitations affecting the nano-techniques (such as SEM. EDS/EDX. Riyadh. (4) Professor. This paper focuses on factors and limitations affecting the characterization of passive layer at the nano-scale using different techniques. the growth and deterioration of passive film actually takes place on nano-scale and is governed by the elemental compositions and nano-microstructure of the steel as well as the chemistry of the concrete pore solutions around the rebar. While this technique measures corrosion in a macro scale. King Saud University. Civil Engineering Department.

The effect of chloride and nitrite ions on the passivity of steel in alkaline solutions was also investigated at the nano-scale [18]. repeatability. A theoretical impedance function was deduced by the use of nanotechnology [15] for a proposed mechanism of passive film formation of steel in contact with alkaline aqueous media involving two reaction intermediates: mixed oxide with similar stoichiometry to magnetite and Fe(III)-oxides. it was found from the previous data that there exists a difference of opinion among various researchers. its break down and corrosion products at the nano-scale level using nano technology have been analysed which has limited research data in the past. The influence of stress on passive behaviour of steel bars in concrete pore solution was studied with electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy [19]. Furthermore. one billionth of a meter: a nanometre. al. In the recent past. In one of the previous reported researches [16]. However. Conducted at the level of the atom and molecule.1M was investigated by C. Several nano-techniques are available for analysing materials at the nano-scale level in the present era. M Aberu et. the behaviour and evolution of passive films generated on AISI 304L has been studied at the nano-scale for a long immersion time in chloride containing media. Evolution of the passive films formed on AISI 304L and duplex stainless steel SAF 2205 in NaOH 0. Corrosion damage investigation in RC (reinforced concrete) structures has become important field of study in civil engineering. the results presented in this paper are preliminary and will be elaborated in detail in the future.e. difference of opinion and factors affecting the quality. INTRODUCTION Despite the substantial amount of research work reported. quantitative nano-scale investigation of passive layer characterization and its breakdown for corroding steel in concrete under severe coupled environmental conditions of chloride and high temperature has yet to be fully explored. the corrosion resistance of C+Mo dual-implanted H13 steel was studied using multi-sweep cyclic voltammetry and nanotechnology. In this research paper. However. at nano-scale [17] using X-ray photoelectron spectroscopy (XPS). 3 . 1.and Fe3O4) as well as Iron hydroxide (Fe (OH)3) were identified in this passive layer. with the goal of continuous and periodic assessment of the safety and integrity of the corroded civil infrastructure.. the struggle to deal with the detrimental effects of several environmental loadings on RC structures such as hot weather in countries like Gulf region has been a major area of concern for researchers. i. However. Xray photoelectron spectroscopy (XPS) had also been used to study the properties of passive oxide film that form on carbon steel in saturated calcium hydroxide solution and the effect of chloride on the film properties [20]. For decades. the nano-scale techniques used in all the above reported research studies have several limitations. In the previous research [14]. problems regarding the study of passive layer. the scale of such research is generally ten times the diameter of a water molecule. nano-scale investigation of passive layer complete characterization as well as its breakdown and corrosion products formation for reinforced concrete under several environmental actions is yet to be fully explored [12. the authors of this paper have been involved deeply in the research related to the corrosion of reinforced concrete structures under variable environmental actions from macro to micro scale [1-11]. 13].

D and E in this paper (Details are provided in the following sections). KSA. Bulk Specific Gravity: OD basis = 2. However. The Nano-Experimental techniques have been used by many researchers in the past to study the surface characteristics of many materials at the nanometer scale. Absorption. 20 mm coarse aggregates. KSA. procured from Saudi Ready Mix Company.41. procured from Saudi Ready Mix Company.04. % = 1. Bulk Specific Gravity: OD basis = 2. Korean Steel which is deliberately named as steel source A.58. Sabic Hadeed Steel 2.62. metallographic analysis for steel reinforcement x-section was also conducted to reveal TM and PF rings in TMT bars which are very important for passive layer successive characterization. Energy Dispersive Spectroscopy/Energy Dispersive X-ray (EDS/EDX) elemental analysis was carried out for passive layer and interfacial transition zone characterization. EXPERIMENTATION A general plan of experimental program is outlined including the broad design and methodology that has been adopted in this research.56. Absorption. procured from Al-Yammamah Cement Company. North Riyadh. Photo Electron Spectroscopy for material characterization and elemental constituent analysis of metals was conducted for various types and brands of steel available in the local market of gulf region.58. C. KSA. Crushed sands. 1. % = 1.58. North Riyadh. nano-scale studies on the characteristics of iron oxide surface passive films formed on steel rebars in concrete pore solution have been reviewed which have limited data in the past and there exists a difference in opinion as well between various researchers with regards to this passive iron oxide nano-layer. Material Properties The materials used and their properties are as follow: • Reinforcing Steel: Steel bars were procured from five different locally available sources namely. Absorption. procured from Saudi Ready Mix Company. North Riyadh. X-ray Diffraction (XRD) peak location and compound identification of passive layer as well as the corrosion products was performed at low angle (2θ) special attachment for thin film analysis. B. procured from Saudi Ready Mix Company. • • • • • 4 . % = 2. Cement.reproducibility and reliability of nano-scale investigation results which needs to be clearly pointed out and remains for future studies. Fine Modulus = 1. KSA with chemical composition satisfying ASTM C-150 for Type I cement.00. in this research. 10 mm coarse aggregates. KSA. Bulk Specific Gravity: OD basis = 2. Absorption.17. China Steel and 5. Along with that. Fine Modulus = 4. Silica sands. North Riyadh. FT-IR material orientation analysis was also conducted to observe the geometry and arrangement of particles. Scanning Electron Microscopy (SEM) both Tungsten and Field Emission imaging was used from micro to nano scale for steel passive layer and corrosion products as well as the Interfacial Transition Zone (ITZ) between the embedded steel and concrete. Ittefaq Steel 3. 2. % = 0. Bulk Specific Gravity: OD basis = 2. This leads to the objectives of this research paper.376. Various nano-technological experimental testing techniques were employed in this research. Muhaidib Steel 4.

Specimen Preparation Mild Steel (MS) rebar specimens were prepared from a 12 meter long as received deformed and plain black steel rebars from five different production sources. The extracts were then collected by filtration. Cement Extracts: Ordinary Portland cement was sieved through 150µm sieve and extract was prepared as 100 g of the cement was mixed with 100ml of distilled water and shaken vigorously using a microid flask mechanical shaker for about 1 hour. In general. Aggregates together with absorption water were added into the mixer first. measuring 6-14 mm in nominal diameter. This was necessary to remove insoluble CaO from the solution. concrete ingredients were mixed by following ASTM C-192 “Standard Method of Making and Curing Concrete Test Specimens in the Laboratory”. PH meter is used to monitor the leached pore solution. NaCl Pore Solution: Another set of solution was prepared as above and NaCl was added to these solutions to simulate aggressive conditions prone to corrosion. KSA. The rebars were cut into 1000mm. standard tests were performed including: Slump test based on ASTM C-143 “Standard Test Method for Slump of Portland Cement Concrete” and setting time tested as per ASTM C-403 “the Standard Test Method for Time of Setting of Concrete Mixtures by Penetration Resistance”. The solution was saturated with Ca(OH)2 to simulate conditions in ordinary portland cement concrete. Then the steel bar was inserted into the concrete prism hole and the hole was filled with distilled water. polished and brown rust condition (Fig.6 g KOH per litre of saturated calcium hydroxide solution. After preparation of concrete mixes. and finally was run for another 2 minutes. the cement and the remaining water were added. Prior to its use. then left to rest for 3 minutes. The oxygen 5 . the solution was kept for 24 h under continuous magnetic stirring (Fig. Concrete Leached Pore Solution: Another technique was considered to extract the pore solution from the concrete itself. 10mm and 2 mm segments (Fig. Preparation of Pore Solutions Simulated Concrete Pore Solution: Synthetic pore solution was prepared consisting of 7.• • Sodium Chloride: 99. A concrete prism was cast with a cylindrical hole throughout the specimen having diameter just equal to the actual steel bar to be tested.9% pure sodium chloride was obtained from VWR Chemicals as a source for chloride ions in concrete and pore solution. Water: Tap water available at King Saud University. Civil Engineering Department. The mixer was run for 3 minutes after all ingredients were added into it.4 g NaOH and 36. and after a few revolutions of the mixer. The idea was to leach the actual pore solution from the concrete in the very small fitting gap between the steel bar under investigation and the concrete prism hole inner periphery. 1) to suffice the requirement of various SEM and XRD machines as well as their sample holders. 2). The five steel sources commercially available in the gulf region are being tested under three types of surface conditions including as received with black oxide mill scale. 15 grade. 3) and then filtered on Wattman paper of No.

8µS/cm. Steel ‘C’ & ‘E’ had intermediate carbon content. 6 . the bar ‘B’ & ‘D’ had maximum percentage of carbon which makes them more prone to corrosion. oxygen bubbling in the solutions was not required in general. 3 Pore solution under continuous magnetic stirring RESULTS AND DISCUSSIONS The chemical composition and structure of steel rebars was determined. differ to a great extent in steels produced by different companies. The pH of solutions was carefully checked by a Methron pH meter and was found to be around 12. While. polished and prepared in resin moulds as shown in Fig. The steel samples were cut. At first SEM-EDXA analysis was performed for various sources of rebars to find out the elemental composition of rebars but it was observed that the elemental composition of lighter elements such as ‘Carbon’ was difficult to determine with EDXA analysis. The bar ‘A’ was found to have the lowest carbon content which makes it more resistant to corrosion.1 1mm. 10mm and 2mm rebar samples 3. polished and brwon rusted rebars Fig. metallographic technique was also used to further study the surface texture of steel bars. 4.concentration of the stagnant solutions was monitored during the experiments. Fig.04 % which is relatively high and the rebar will be even more prone to corrosion due to the presence of MnS inclusions in the steel as compared to other steel sources. 5 that TM (Tempered martensite) ring of rebars which plays very important role on corrosion rate. Fig. The results of Photo-Electron Spectroscopic analysis carried out to determine the elemental constituents of various steel sources available in the Kingdom are presented in the following Table 1. Photo-Electron Spectroscopy was conducted to find out the exact chemical composition of all the elements present in steel bars obtained from different local production sources. Regarding the role of steels on nature of passive film. 2 As received. All this data is important in the sense that the successive passive layer which will be developed on the steel after immersion in alkaline pore solution environment will be influenced by all these properties of steel bars. Along with that. It can be seen from the metallographic images of etched steel samples shown in Fig. All reagents were of at least ACS grade and the solutions were prepared with distilled water with conductivity of 0. The sulphur content in steel source ‘D’ is 0.3. the micro level observations are quite evident. Therefore. The concentration of oxygen was sufficiently high in the solutions (>1 mg/L) for the oxygen reduction reaction to take place. therefore.

34 0.004 0.13 0.026 B 0.21 0.012 0.1: Elemental Composition of Various Steel Bars Element % C Si Mn P S Cr Ni Mo Al V Sn A 0.021 0.59 0.19 0.005 Fig.003 0.017 0.004 0.024 0.019 0.57 0.030 0.92 0.020 0.060 0.019 E 0.001 0.Table.85 0.002 0.015 0. The steel samples embedded in concrete were cut around the steel bar in small squares to fit in the limited space of SEM (scanning electron 7 .018 0.016 0.001 0.002 0.051 0.005 D 0.25 0.019 0.009 0.015 0.002 0.014 0.001 0.001 C 0. 5 Metallographic Images of Various Steel Sources Characterization of Passive Layer Developed on Steel Rebars in Pore Solutions The characterization of passive layer developed on steel bars under pore solution environment was carried out. 4 Various Steel Samples Prepared for Analysis sample “A” sample “B” sample “C” sample “D” sample “E” Fig.005 0.009 0.001 0.11 0.001 0.003 0.002 0.14 0.13 0.032 0.018 0.26 0.003 0.040 0.12 0.14 0. The constituent compound analysis as well as growth of passive layer was investigated under various conditions.

These images proved to be very helpful to reveal the interface of concrete and steel where passive layer is developed. close to 10 nm and then repeat the above steps. 10. As a first step. In the light of observations obtained from sensitivity analysis performed in Fig. The amount of ‘O’ also became much less confirming the fact that the analysis was being targeted in the steel area close but not in the passive layer. it was observed that the number of elements reduced. block and spot spectrums were taken at different locations around the passive layer as shown in Fig. It was observed that the surface of steel bar which seemed very smooth at macro level was still very non-uniform at micro and nano level which definitely affects the quality of passive layer. It can be concluded here that tungsten filament SEM is not capable of performing the passive 8 . 8(b)). This sensitivity analysis provided confidence and hands on experience on the machine. SEM was employed to observe the passive layer around the periphery of steel bar type ‘C’ and images were taken at different resolutions as shown in Fig. Taking a spectrum on the steel surface close to the passive layer for EDS analysis (Fig. The EDS sensitivity analysis was repeated several times to obtain expertise and confidence in the hands on experience and confidence for the exact location of analysis on the periphery of steel concrete to obtain accurate and averaged conclusion. carbon ‘C’ being a lighter element was difficult to detect correctly by EDXA-FEM analysis and should be ignored throughout the analysis considering the carbon content as erroneous and a limitation of EDS analysis. 6 Steel embedded in Concrete Being Tested in SEM As a first trial. It is to be noted that as already discussed. 9). block spectrum was taken in the concrete area around the passive layer as shown in Fig. Fig. It was decided to carry out sensitivity analysis using EDXA technique around the passive layer to study the surrounding area and its influence on the passive layer itself. Another idea was to zoom in to the nano-scale.microscope) and analyzed for the passive layer development around steel bar in the natural alkaline environment of concrete (Fig. 8. a more systematic approach was adopted to identify the passive layer. 7. 8 (a) again confirming the above said. 8. unfortunately it was observed that the tungsten filament SEM being used in this analysis did not have enough resolution to show images in beyond 200 nm as shown in the Fig. 8 (a). A certain point was fixed in the SEM and then was zoomed inside the reach the passive layer without changing the coordinates (Fig. it was noticed that the amount of carbon was much higher than expected and was therefore erroneous. The percentage of iron also increased substantially and that of calcium decreased as compared to the Fig. For this purpose. 6). Again. But.

81 29. 7 SEM Image of Steel Concrete Interface (Passive layer Orientation) Element Weight% Atomic% CK OK Na K Mg K Al K Si K SK KK Ca K Ti K Fe K 6.48 0.91 1.27 0.46 2.57 0.31 0.49 48.26 0. 8(a) EDXA Analysis of Steel Concrete Interface (Passive Layer) Element Weight% Atomic% CK OK Mg K Al K Si K Ca K Mn K Fe K 9. Fig.07 0.41 0.88 2.26 1.47 0.96 136 Fig.33 50.06 1.39 0.38 32.79 1.43 0. 8 (b) EDXA Analysis of Steel Concrete Interface (Passive Layer) Fig.20 16.layer analysis and need was felt to utilize FE-SEM (Field Emission scanning electron microscope) having enough resolution to focus deep into the nano-scale.67 0.08 Totals 100.37 14.19 1.14 2.87 11.41 0.68 6.51 78. XRD analysis was tried but since it cannot be focused on a small area of periphery of steel bar having passive layer.00 135 Fig.77 6. Also.94 0.77 0.05 0. 8 FEM-EDXA Analysis of the X-section side of passive layer 9 .32 62.30 4. Raman spectra seem to be a suitable option and should be adopted under the above circumstances. satisfactory results were not obtained.73 0.

It should be kept in mind that this sensitivity analysis was done merely for hands on experience and understanding of machine operations and specimen behavior. 10 Sensitivity Analysis of steel concrete interface to locate the passive layer The above discussion was for the case of steel embedded in concrete and being observed from the X-section side. 13. Also.Fig. Several EDS sensitivity analyses were conducted as already described in the previous section and similar conclusions were drawn. it was observed that the penetration of electrons from the SEM were deep enough to bypass the thickness of passive layer and SEM-EDS analysis may not represent the passive layer but the layer beneath it. A surface texture of passive layer developed on steel immersed in pore solution at high resolution (Fig. The corresponding systematic SEM images are as shown in Fig. 9 SEM Imaging of Passive layer existing in steel-concrete Interface Fig. 12) showed deposits of pore solution on the passive layer as contamination and should be ignored during analysis. 11 and 12. steel bars immersed in the simulated concrete pore solution (SPS) were analyzed under SEM from the top surface for passive layer EDXA analysis. In the next step. Fig. To avoid repetition. 11 SEM Imaging of Steel surface bearing passive layer in simulated pore solution (SPS) 10 . only representative results are presented in Fig.

95 0.66 20. 15 below show the FE-SEM images of steel bar with and without passive layer at the nano-scale.00 2. Images (Fig. 14 and Fig. Fig. This is a rather new and very interesting finding of this research project which has not been reported in the past that the passive oxide layer on the steel surface actually does have a uniform repeating pattern instead of just being a random non-uniformly structured layer.00 169 Fig.09 15. it was concluded that Field Emission SEM (FE-SEM) must be fetched and involved in passive layer nano-scale analysis so that the very fine passive layer (in nano-meters) can be completely analyzed and its structure understood properly.85 0.64 3. A unique and repetitive symmetrical pattern was found in the structure of passive layer at the nano-scale developed on polished steel bars while taking images under FEG SEM.Fig.80 Totals 100. 12 SEM Imaging of Steel surface bearing passive layer in SPS Element Weight% CK OK Al K Si K Cl K Ca K Fe K 56. 13 SEM-EDXA analysis of sample with passive layer (Washed and Desiccated) After obtaining the above results. In fact the field emission scanning electron 11 . 16) taken with FE-SEM at the nano-scale revealed an interesting observation that the steel bar even without the passive layer is not so uniformly structured over the surface as was thought and gives a similar non-uniform surface structural look as found in case of concrete when zoomed to the nano-scale.

5kV.5kV. 60. SEI 6.000x.5kV.3mm WD (Without passive layer) Fig. SEI 6. 100.000x. 15 Steel Surface with Passive Layer (nano-scale) FE-SEM Images 1. SEI.000x. 16 FE-EM Images of Steel Bar Surface (nano-scale) 12 . 6.5kV. 60. 15) obtained at the nano-scale revealed that the steel bars with passive oxide layer have even more orderly structure in contrast to what was expected.000x. 1.000x. 60.000x.2mm WD Fig. SEI. 100.microscope images (Fig.3mm WD 1.3mm WD Fig. 6. SEI. 14 Steel Surface without Passive Layer (nano-scale) FE-SEM Images 1. 60.2mm WD (With passive layer) 1.5kV. 6.5kV. 6.2mm WD 1. SEI.

742 0.Code 01-073-0603 01-086-2316 01-074-0953 01-074-1886 00-042-1468 01-088-0840 01-079-1968 01-079-2177 00-019-0605 00-025-1376 00-002-1044 Score Compound Name Displ.919 Fe2 O3 17 Wuestite. along with some other compounds as shown in Fig.049 0. The qualitative comparison of various XRD patterns show that the peaks observed in case of steel ‘A’. ‘B’ and ‘C’ are not same but similar probably belonging to the different phases of the same family. It was found that most of the materials present in the passive layer were not easily identifiable and needed advanced and complete set of data-base for the XRD peaks to be identified satisfactorily. X-ray diffraction (XRD) analysis was conducted on the passive layer to understand the compound analysis of this oxide layer formed on the steel surface under alkaline conditions.031 0. This opens areas of future research in this project to explore the various possibilities and reasons for these differences in the composition of passive layers developed on different steel sources shown in Fig.034 ( Fe .After revealing the above interesting information.945 O 33 W\PIstite. Magnetite.353 0.720 0.. Fe ) Si O3 UM Magnetite 1. It was seen from the XRD peaks of various steel sources that the passive layers developed on various steel sources under simulated pore solution environment are different from each other. syn 0. 17. Magnesioferrite etc.240 ( Mg .020 Fe O UM alumina 1.922 0. syn 0. 32 W\PIstite. Visible * Ref. Fe . 17 XRD Results for Passive Layers Developed on Steel Rebar 13 .346 0. Mg ) UM Magnesioferrite 1. Formula 45 Hematite.92 O 5 Enstatite. syn 1.053 Fe0. This is our present limitation that the complete database required for such sophisticated material analysis is not available. The materials identified in the passive layer comprised of various oxides of iron in different phases. Chem.232 0. such as Hematite. PIstite. syn 0.. T. syn 1. Wuestite.982 0. Fig. 17..480 Mg Fe2 +3 O4 ( Al . The XRD pattern and possible material identification is presented in Fig.119 0.018 Fe.981 0.[°2Th] Scale Fac.083 Fe2 ( Si O4 ) 32 Wuestite. Al . syn 0.902 O 23 Fe-Ringwoodite.514 Al2 O3 4 Hawaiite 0. 18.019 Fe0. ferroan 1.311 ( Mg .

the peaks of CaO are recorded. It is suspected that the reason for this observation lies in the presence of possible concrete pore solution layer over the passive layer formations in which the steel samples were immersed.5 respectively as shown in Figs. 19).Intensity (counts) 10000 6400 3600 1600 400 0 20 30 40 50 60 70 80 90 2Theta (°) Fig. In all the other cases. a couple of steel samples were analyzed under XRD for varying incidence angles of 0. quantitative XRD analysis was also carried out to identify the exact chemical compositions and phases of peaks observed in various spectra (Fig. 1. Grazing incidence diffraction was performed on two samples with different incidence angles. Fe0. Iron (Fe). The three spectra were overlapped and then compared with each other for possible variations due to different phase angles. The identified compounds along with their chemical formulas are shown in the figures 19 and 20. Fig.5. 19 XRD peak Identification for steel source (Quantitative) 14 . it is found that except steel source ‘D’. X-ray diffraction is a good technique to identify the phases in the top layer of samples. in no other case any compound of iron is identified. Fe3O4) as well as Iron hydroxide (Fe(OH)3) were identified. 3 Iron-oxides (Fe2O3. 18 X-Ray Diffraction Analysis of Passive Layer (Qualitative) Along with the qualitative analysis discussed above. While going through the analysis of XRD peaks presented in Figure 19. In another trial. samples will be washed and desiccated carefully to be analyzed under XRD to avoid such problems. where peaks of beta-Fe2O3 are observed. 20. In the future.0 and 1.92O.

5º Fig. 20(h) XRD spectra of steel ‘C’ at 1. 20 Incident angle sensitivity analysis for XRD compound and peak identification 15 . 20(c) XRD spectra of steel ‘D’ at 1.Fig. 20(f) XRD spectra of steel ‘C’ at 0.5º Fig. 20(g) XRD spectra of steel ‘C’ at 1.5º omega Fig.0º Fig.0º Fig. 1. 20(a) XRD spectra of steel ‘D’ at 0. 20(d) XRD spectra of steel ‘D’ at superimposed 0.5º Fig.5º omega Fig.5.5.0 and 1.5º Fig. 20(b) XRD spectra of steel ‘D’ at 1. 20(i) XRD spectra of steel ‘C’ at superimposed 0. 1.0 and 1.

4. method of sample preparation. skill of the worker. Tetsuya Ishida (2010) Influence of Connectivity of Concrete Pores and Associated Diffusion of Oxygen on Corrosion of Steel under High Humidity. analysis scale. Riyadh. precision and accuracy of measurement. 09-NAN674-02. 15. a lot of care is need for sample preparation that minimizes damage to the specimen. Enhanced electro-chemical corrosion model for reinforced concrete under severe coupled environmental action of chloride and temperature. Issue 6. doi: 10. Journal of Corrosion Engineering. Long Term Comprehensive National Plan for Science. Issues 9-10. Vol.1014–1019. Issue 1. conducting in-situ test. Vol. [6] Hussain Raja Rizwan and Tetsuya Ishida (2009) Critical Carbonation Depth for Initiation of Steel Corrosion in Fully Carbonated Concrete and the Development of Electrochemical 16 . equipment employed. Issue 3. Even though the minimization of the errors associated with these challenges may provide an insight into the properties of passive oxide film developed on steel reabrs in concrete and its behavior under circumstances comparable to the actual exposure conditions. 153-160. Experimental Investigation of Time Dependent Non Linear 3D Relationship Between Critical Carbonation Depth and Corrosion of Steel in Carbonated Concrete. [3] Hussain Raja Rizwan and Tetsuya Ishida. Saudi Arabia. It should be noted that there are a number of challenges associated with these techniques when used for non-uniform naturally developed layers (passive layer on steel reinforcement in conrete) that can account for the lack of consistency and accurate information. Therefore.1179/147842210X12659647007086. insitu testing technique etc. 6. CONCLUSIONS Despite of the fact that different techniques have been used for nano-scale studies of extremely thin and delicate iron oxide passive films on steel rebars in concrete. Vol. 1305-1315. Vol. REFERENCES [1] Hussain Raja Rizwan. multiple techniques that complement each other must be used to study these phenomena for future concrete. Especially. Construction and Building Materials Journal (2010). Construction and Building Materials Journal. 5. [2] Hussain Raja Rizwan and Tetsuya Ishida (2010) Development of Numerical Model for FEM Computation of Oxygen Transport through Porous Media Coupled with Micro-Cell Corrosion Model of Steel in Concrete Structures. [5] Hussain Raja Rizwan and Tetsuya Ishida. pp. proper interpretation of results and inherited limitations of the devices used in these nano-techniques. Science and Technology (2010). Technology and Innovation (NPST). the results are not consistent and strongly depend on the type of exposure conditions. 24. 88. pp. it is not practically possible to eliminate all these experimental limitations. submitted to KSCE Journal of Civil Engineering. standard library database available. 25. Computers and Structures Journal. A slight negligence in any of the above factors can lead to entirely different experiment and analysis results. Project No. pp.639–647. [4] Hussain Raja Rizwan and Tetsuya Ishida (2010) Investigation of Volumetric Effect of Coarse Aggregate on Corroding Steel Reinforcement at the Interfacial Transition Zone of Concrete. ACKNOWLEDGEMENTS This research project has been supported by King Abdulaziz City for Science and Technology (KACST). pp. 2009-2011.

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