CROATICA CHEMICA ACTA CCACAA 77 (1–2) 141¿151 (2004) ISSN-0011-1643 CCA-2911 Original Scientific Paper The Effect of Bicarbonate/Carbonate Ions on the Formation of Iron Rust* Svetozar Musi},a Israel Nowik,b Mira Risti},a,** Zvonko Orehovec,a and Stanko Popovi}c aRu|er Bo{kovi} Institute, P. O. Box 180, HR-10002 Zagreb, Croatia bRacah Institute of Physics, The Hebrew University, IL-91094 Jerusalem, Israel cDepartment of Physics, Faculty of Science, University of Zagreb, P. O. Box 331, HR-10002 Zagreb, Croatia RECEIVED MARCH 12, 2003; REVISED JULY 18, 2003; ACCEPTED AUGUST 12, 2003 The effect of bicarbonate/carbonate ions on the formation of iron rust in an aqueous medium has been investigated using XRD, Mössbauer and FT-IR spectroscopies. Corrosion of carbon steel in doubly distilled water was monitored as a reference process. Lepidocrocite as the dom- inant phase and magnetite were detected in rust generated in doubly distilled water in a period from three weeks to one year at room temperature. At 90 °C, magnetite and small amounts of hematite/goethite were formed in a period from one day to three weeks. In these rust samples, FT-IR spectroscopy detected a very small amount of lepidocrocite, which dissolves and thus occurs in overall phase transformations in rust. On the other hand, goethite was found as the dominant phase in rust formed in natural water containing a significant amount of bicarbonate ions, whereas magnetite and lepidocrocite were minor phases. In 0.005 M Na2CO3, goethite and magnetite were generated at room temperature, and after one month of corrosion, magne- Key words tite was present only in traces. Corrosion in 0.005 M Na2CO3 at 90 °C generated Fe2(OH)2CO3 iron rust and magnetite. A certain analogy between the precipitation of FeIII-oxyhydroxides from iron-salt carbon steel solutions containing carbonates and the formation of goethite and lepidocrocite in rust was bicarbonate/carbonate ions shown. Mössbauer spectroscopy showed that microstructural properties of the oxide phases also lepidocrocite varied. Magnetite showed substoichiometry (Fe3–xO4) and in some cases it was difficult to dis- g goethite tinguish between Fe3–xO4 and maghemite ( -Fe2O3). Mössbauer spectra, recorded as a function hematite of temperature, showed poor crystallinity and/or superparamagnetic behavior of goethite particles. magnetite Also, the Mössbauer spectra of the rust formed in carbonate solutions provided evidence of the basic iron carbonate amorphous fraction, which is in agreement with XRD. The difference between the results of Mössbauer the present investigation and those obtained by other researchers can be attributed to the electro- FT-IR chemical stimulation of steel (iron) surfaces in bicarbonate/carbonate aqueous media and the XRD shorter corrosion times used in their experiments. INTRODUCTION such as a-, b-, g- and d-FeOOH, as well as oxides such g a Iron oxyhydroxides and oxides are typical constituents of as Fe3O4, -Fe2O3 and -Fe2O3 were found in iron rust. rust, generated by the corrosion of steel surface in con- The phase composition of the rust depends on the physico- tact with water. All polymorphs of iron(III) oxyhydroxide, chemical factors of the corrosion process, such as elec- * Dedicated to Professor Nenad Trinajsti} on the occasion of his 65th birthday. ** Author to whom correspondence should be addressed. (E-mail: [email protected]) 142 S. MUSI] et al. trolyte composition, pH, type of steel, temperature and TABLE I. Chemical composition of natural water(a) time of rusting. Fe(OH) produced at the surface of cor- 2 Cation or anion Concentration / mg dm–3 roding steel undergoes complex phase transformations, Sodium (Na+) 158.2 starting from its first appearance up to the time of rust + sampling. Many examples showed that Fe(OH) is not Potassium (K ) 5.3 2 + (b) always formed in the early stages of iron (steel) corro- Lithium (Li ) 2+ sion in an aqueous medium. Iron(III) oxyhydroxides, or Calcium (Ca ) 86.7 mixtures of iron oxyhydroxides and oxides are formed Magnesium (Mg2+) 33.6 instead. In specific cases, rust may contain a significant Strontium (Sr2+) (b) amount of amorphous fraction and/or very fine oxide par- Iron (Fe2+) (b) ticles. Investigations of phase composition of rust and Manganese (Mn2+) 0.2 the corresponding phase transformations in rust are very Aluminium (Al3+) (b) important in studying the mechanism of steel corrosion. Chloride (Cl–) 60.1 The present work is focused on the formation and phase Fluoride (F–) (b) composition of rust produced in the presence of bicar- Bromide (Br–) (b) bonate/carbonate ions in an aqueous medium in order to Iodide (I–) (b) obtain more data about steel rusting in laboratory condi- - Bicarbonate (HCO 3 ) 734.3 tions. However, the importance of this work is not merely 2- Sulfate (SO 4 ) 27.8 academic. Bicarbonate/carbonate ions are present in natural, (a) –3 The content of not dissociated H2SiO3 is 13.5 mg dm . service and waste waters and therefore they may influ- (b) Concentrations are 0.1 mg dm–3 or less. ence the corrosion process in practice (iron/steel facili- ties, pipelines, etc.). Mössbauer and FT-IR spectroscopies and X-ray powder diffraction were used in rust analysis. TABLE II. Analysis of ten metals on steel surface, as determined (a) Mössbauer spectroscopy is a specifically useful technique with PIXE in the investigation of corrosion processes, for example, Element w /% the formation of atmospheric rust1 and rust in a water Fe 98.695 medium,2 corrosion inhibition,3 metal/organic coatings,4 and metal/metal coatings.5 More details about the appli- Mn 0.565 cation of Mössbauer spectroscopy in corrosion science and Cu 0.174 engineering are given in a book by Ujihira and Nomura.6 Ni 0.137 Zn 0.080 Ca 0.074 EXPERIMENTAL Ti 0.043 K 0.035 Carbon steel was chosen in the corrosion experiments be- V 0.018 cause it has a suitable corrosion rate and yields a suitable Cr 0.015 amount of rust for Mössbauer measurements in transmittance mode. Rusting was monitored in natural water with a high Total amount 100 % content of bicarbonate ions, in solutions with dissolved so- (a) The w/% of a particular metal is calculated against the total amount dium carbonate, as well as in doubly distilled water used as of the ten metals measured. a reference corrosion medium. The aqueous medium used was not deaerated before contact with steel. However, when the carbon steel specimens were immersed in an aqueous PIXE analysis represents also the bulk composition of the medium, the vessels were hermetically closed to eliminate material. The results of PIXE analysis for ten qualitatively the influence of atmospheric oxygen during the corrosion known metals in carbon steel are given in Table II. The experiments. The chemical composition of natural water is concentrations of metals measured in ppm were recalculat- given in Table I. ed in w /%. Alloying metals (copper is a typical example) may in- After the required corrosion time elapsed, rust was scrap- fluence the steel corrosion rate. For this reason, elemental ed, then analyzed by 57Fe Mössbauer and FT-IR spectrosco- composition of the investigated steel was determined using pies and X-ray powder diffraction. the Proton Induced X-ray Emission (PIXE) facility at the 57Fe Mössbauer spectroscopic measurements were per- Ru|er Bo{kovi} Institute, Zagreb. Protons of 3.0 MeV were formed using a 57Co/Rh source (50 mCi) and the conven- used. PIXE analysis is a fast and non-destructive analytical tional constant acceleration Mössbauer drive. Spectra of the technique, providing simultaneous determination of most samples were collected in transmittance mode at 300 and elements (Z > 13) with detection limits in ppm range de- 90 K, and in specific cases also at 4.2 K. The spectra were pending on the element analyzed. Since the penetration of analyzed by the least-square fit program, which allows a sum protons into steel is ~35 microns, it can be supposed that of magnetic sextets with the distribution of hyperfine fields Croat. Chem. Acta 77 (1–2) 141¿151 (2004) FORMATION OF IRON RUST 143 TABLE III. Phase composition of rust samples produced in doubly distilled water and natural water at rt, as found by XRD Corrosion medium Corrosion time Phase composition Estimated crystallite size (approx. molar fractions) of the dominant component / nm (a) doubly distilled water 1 w L + M (0.30) 25(7) doubly distilled water 3 w L + M (0.30) 30(8) doubly distilled water 6 m L + M (0.35) 30(7) doubly distilled water 1 y L + M (0.40) 35(8) natural water 3 w G + L (0.05) + M (?) 18(5) natural water 4 m G + M (0.25) + L (0.05) 15(4) natural water 9 m G + M (0.20) + L (0.10) 13(4) natural water 1 y G + L (0.30) + M (0.05) 10(3) Key: w = week; m = month; y = year; L = lepidocrocite; G = goethite; M = magnetite. (a) Numbers in brackets: estimated standard deviations of the last significant figure. and quadrupole doublets subspectra. The analysis enabled a reduction in the hyperfine interaction parameters and the relative intensities of various subspectra. FT-IR spectra were recorded at room temperature using a Perkin-Elmer spectrometer (model 2000). The FT-IR spectro- meter was operated with the IRDM (IR Data Manager) pro- gram. Specimens were pressed into a spectroscopically pure KBr matrix. X-ray powder diffraction measurements were performed at room temperature using a Philips counter diffractometer (model MPD 1880, CuKa radiation, proportional counter, graphite monochromator). RESULTS Corrosion of Carbon Steel in Doubly Distilled Water at Room Temperature Table III shows the composition of rust samples produced in doubly distilled water at room temperature (rt), as found by XRD.