Goethite Recognition by ATR on Filter Papers

M.Sc JORGE GUILLERMO DIAZ RODRGUEZ

Docente Ing. Mecatrnica Grupo de Automatizacin Modelado, Simulacin y Control de Productos y Procesos Industriales. Universidad Santo Toms de Bucaramanga djgdiaz@calvin.ustabuca.edu.co

Materials Science & Engineering Department Materials Group, University of North Texas Denton, Texas hnamduri@unt.edu Fecha de Recibido: 20/04/2008 Fecha de Aprobacin: 03/12/2008

Ph.D HARITHA NAMDURI

RESUMEN
Esta investigacin se desarroll para evaluar la posibilidad de explorar ms a fondo la identificacin de xidos ferrosos en filtros de papel usados en trampas de vapor en plantas de potencia. Se pretende con este estudio evaluar la posibilidad de pasar a un monitoreo ms frecuente del estado interno de tuberas mediante dichos filtros y no haciendo evaluacin de componentes obtenidos solamente durante paradas programadas de mantenimiento cada 18 meses. De esta forma se podra tener una mejor lectura de la integridad de la lnea secundaria en plantas de vapor. Palabras clave: xidos ferrosos, FTIR modo reflexin, filtros papel, hidrxidos, caracterizacin de materiales.

ABSTRACT
To confirm the detection by FTIR (Fourier Transform InfraRed spectroscopy) of Iron oxides on filter papers, Goethite (-FeOOH) was prepared and impregnated on commercial paper filters. FTIR in Reflectance mode (ATR) was run to test whether Goethite was detected or not. This oxide was chosen because of its deep and unique peaks. Comparison with obtained standards for Goethite showed that FTIR in reflectance mode was able to identify the 790 and 890 cm-1 absorption bands characteristic of this Iron oxyhidroxide. Keywords: Iron oxides, FTIR reflectance mode, filter papers, oxy hidroxides, materials characterization.

1. INTRODUCTION
Filter papers can be installed in steam traps along the secondary line in power plants to asses condensate quality by measuring particle size, element content, and oxide forms. Such filters cannot be placed in a regular transmittance FTIR machine, which most of the time uses KBr pellets. Because of the nature of how FTIR works, it will simply not issue any pattern due perhaps to the proximity of vibration angles of the filter papers cellulose molecules and the oxides [1, 9]. A literature review returned very few positives on Iron oxide patterns done in ATR. Lackovic et. al. [14] reported FTIR-ATR work on Goethite patterns with

Cadmium absorption at 3 different pH levels. Extensive literature is found on studies of Goethite adsorption of Carbonates, Phosphates, Calcium citrates, Sulfates, and even Selenites done by FTIR/ATR [15]. In any of these cases peak bands shift around 1300 to 1400 cm-1 as opposed as the accepted 890 and 790 cm-1. This may be due to the absorption of those components [14, 17]. However, extensive literature can be found on Goethite recognition by traditional FTIR [13]. The expected Iron oxide forms to be present in a steam line are: Magnetite (Fe3O4), Maghemite (-Fe2O3), Hematite (-Fe2O3), Lepidocrite (-FeOOH), and Goethite (-FeOOH) [2, 3].

UIS Ingenieras, Volumen 7, No. 2, pags. 211 - 214, Diciembre 2008; Facultad de Ingenieras Fisicomecnicas, UIS

212 2. DESCRIPTION
To compare patterns between the FTIR methods, Goethite was picked because its very distinctive and sharp peaks. Cornell R. and Schwertmann U. [2] provide with a list of very easily and identifiable characteristics of Goethite, while using FTIR, being 790 and 890 cm-1 absorption bands with sharp peaks in a defined shape. Such spectrum is of public domain and can be found in free databases online. The advantage of using FTIR over other characterization techniques, such as commonly used XRD (which is based on Bragg`s law), is that the lattice value for Magnetite (0.8396 nm) [11] is too close to the one of Maghemite (0.835 nm ) [12] delivering a 2 angle for both forms almost impossible to distinguish to the not highly trained eye [1]. The transition between Magnetite to Maghemite could tell the user the beginning of an unsustainable oxidation process [4, 5]. Nowadays, such process can be slowed down and identified by common and novel techniques used in the power industry such as the ones described in [6, 7, 8]. The problem that may arise from using standard FTIR may be the relative difficulty - when compared to ATRto make samples. The difference in the applied pressure to the samples may induce changes in final readings, and the necessity of storing expensive KBr in humidity and temperature controlled environment. The aim of this work is to establish the feasibility of establishing a more frequent condition monitoring for the condensate line as opposed as the habitual 18 months scheduled-outage at TXUs Comanche Peak Steam Nuclear Electric Station (CPNSES) in Glennrose, Texas. If more frequent data is available, a trend analysis could be done to forecast when a component would reach an allowed minimum thickness thus scheduling its replacement without interfering day-to-day energy production.

Jorge Diaz, Haritha Namduri Several 13 mm KBr pellets were made at 2000 psi, and FTIR in transmittance mode was run on the final product using a Perkin Elmer 1750 machine and Spectrum 1.3 as data treatment software. Also, the mixture was tested in a FTIR Nicolet machine in reflectance mode and Omnic was used to process data. To test the recognizition of Goethite on paper filters, the product was impregnated in 0.4 m Nucleopore (polymer based) and 0.45 m Milipore (cellulose based) filters, and screened in ATR in a Nicolet machine. One must notice the similar mesh size for both filters used. These filters are commercial grade, normally used in steam traps, and were provided by the Water Chemistry group at TXUs Comanche Peak Electric Steam Nuclear Station in Glennrose, TX.

4. RESULTS AND DISCUSSION

FTIR in reflectance mode (ATR) was able to identify the characteristics peaks of Goethite present in commercial filters (polymer and cellulose based), whereas FTIR in transmittance mode did not show the difference between Goethite and the filters material. Figure 1 shows the obtained spectra for the prepared oxide done by FTIR in transmittance mode in KBr pellets. One can see absorption peaks at 890 and around 790 cm 1. These values, plus the characteristic form of the spectra, were conclusive factors showing the presence of Goethite. This was done to test the preparation methodology.

3 .METHODOLOGY
Goethite was prepared according to a recipe observed in [3] in the following manner: 180 g of Iron III nitrate of 99,9 % purity and 25 g of NaOH of 99,8 % purity in a 1 M solution were mixed, stirred for 3 days, and NaOH pellets were added until the mix reached a pH of 12. After that, the solution was aged for 3 more days at 55 C, then it was washed and separated in a high-speed centrifuge at 7500 RPM, the final mix was dried at 30 C for 1 day.

Figure 1. FTIR spectra of prepared Goethite run on FTIR transmittance mode

Goethite Recognition by ATR on Filter Papers Figures 2a and 2b show clean commercial filters. Even though both filters are made out of dissimilar materials (2a: 0.45 m Millipore and 2b 0.4 m Nucleopore), they showed similar peaks around 830 and 760 cm-1. Those peaks were what apparently produced an overlap and did not allow the identification of Goethite under these conditions.

213

Figure 3a. ATR spectra for Cellulose based filter (0.45 m)

Figure 2a. ATR spectra for Milipore filter (0.45 m)

Figure 3b. ATR spectra for Polymer based filter (0.45 m)

5. CONCLUSIONS
FTIR in reflectance mode was able to identify the characteristic Goethite`s deep shape smeared on commercial papers and polymer filters. The characteristic form for Goethite remains present in the final spectra. However, the 790 cm-1 peak shifted to around 800 cm-1 which cannot be conclusive about ATR not being able to identify Goethite.

Figure 2b. ATR spectra for Nucleopore filter (0.4 m) Figures 3a and 3b show the result of FTIR in reflectance mode for the mentioned filters that were smeared with Goethite. Clearly one can see the representative value peaks and the form of Goethite in both spectra. Cellulose based filter (3a) shows peaks at 890 and 804 cm-1 and Polymer filter (3b) based shows peaks at 887 and 815 cm-1.

6. ACKNOWLEDGEMENTS
The author wants to thank the Water Chemistry group at the Comanche Peak Electric Steam Nuclear Power Plant for providing the filters. Also, wants to recognize the help of the personnel at the molecular Biology laboratory at the University of North Texas who helped doing the Goethite centrifuging. Finally to Dr. H. Namduri, and Dr. S. Nasrazadani who worked all along this idea.

214 7. REFERENCES
[1] Cornell R., and Schwertmann. U., The Iron Oxides, Weinheim Ed., New York City, 1996. [2] Fellers B., Stevens J., and Nichols G.. TXU Electric, Strategic Elements of Steam Cycle Chemistry Control Practices at TXUs Comanche Peak Steam Nuclear Electric Station, CPSENS June 2001. [3] Nasrazadani. S. The application of infrared spectroscopy to a study of phosphoric and tannic acids interactions with Magnetite (Fe3O4), Goethite (-FEOOH) and Lepidocrocite (-FeOOH). Corrosion Science, Vol. 39, 1997 [4] Nasrazadani. S., and Raman. A. Application of IR Spectra to Study the Rust Systems, Corrosion Science Vol. 34. 1993 [5] Nasrazadani. S., and Raman. A. Morphology of Oxide Phases in the Scales Formed on Steels. Prac Met Vol. 28. 1991 [6] Namduri H. Characterization of iron oxide deposits formed at Comanche Peak Steam Nuclear Electric Station (CPSENS). Master of Science thesis. University of North Texas 2002 [7] Diaz J. G.Effect of Amines as Corrosion Inhibitors for a Low Carbon Steel in Power Industry. Master of Science thesis. University of North Texas 2004 [8] Miksic B, and Miller R. H. Fundamental Principles of Corrosion Protection with Vapor Phase Inhibitors. 5th European Symposium of Corrosion Inhibitors. Italy 1980 [9] Brundle C., Evans C., and Wilson S. Encyclopedia of Materials Characterization. Butterworth-Heinemman, Stoneham. MA. 1992 [10] Mirabella F.M., Principles, Theory, and Practice of Internal Reflection Spectroscopy. F.M. Mirabella, Jr., Marcel Dekker, Inc. NY. 1993 [11] Ismail M.G., Yoshimura M., Somita S. Synthesis of Magnetite Using Ilmenite under Hydrothermal Conditions. Materials Science Letters, Vol 4, 1985. [12] Randrianantoandro N., Mercierb A. M, Hervieuc M., y Grenchea J. M., Direct Phase Transformation from Hematite to Maghemite during High Energy Ball

Jorge Diaz, Haritha Namduri Milling. Materials Letters Vol. 47-3, 2001 [13] Ruan H. D., Frost R. L., Kloprogge J. T., Duong L., Infrared spectroscopy of Goethite dehydroxylation: III. FT-IR microscopy of in situ study of the thermal transformation of Goethite to Hematite. Spectrochimica Acta, Vol. 58, No. 5, 15 March 2002, pp. 967-981 [14] Lackovic K., Angove M. J., Wells J. D., and Johnson B. B. Modeling the adsorption of Cd(II) onto goethite in the presence of citric acid, Journal of Colloid and Interface Science Vol. 269-1, 1 January 2004, pp 37-45. [15] Prasad, P. S. R. y otros, In situ FTIR study on the dehydration of natural Goethite, Journal of Asian Earth Sciences, Vol. 27-4, September 2006, pp. 503-511 [16] Wijnjaa H., and Schulthessb C.P., Carbonate Adsorption Mechanism on Goethite Studied with ATR FTIR, DRIFT, and Proton Coadsorption Measurements, Soil Science Society of America Journal, Vol. 65, 2001, pp.324-330 [17] Rustad J. R., and Zarzycki P, Calculation of sitespecific carbon-isotope fractionation in pedogenic oxide minerals, PNSA, Vol. 105 No. 30, July 29 2008, pp 10297-10801

8. CURRICULUM
Jorge Guillermo Diaz, Ingeniero Mecnico UIS (1999), Magister en Ingeniera de University of North Texas (2004), Denton, Texas. Se ha desempeado como ingeniero de proyectos para SPM Flow Control, Fort Worth, TX (2005) e Industrias INAL, Bucaramanga, COL (2007-2008) y como diseador mecnico para SIEMENS Energy & Automation, Grand Praire TX (2006-2007). Actualmente se desempea como docente tiempo completo de la Universidad Santo Tomas Bucaramanga. Haritha Namduri, Ingeniera Mecnica de Chaitany Bharathi Institute of Technology, Hydarabad, India (2001), Magister en Ingeniera (2003) y Doctora en Ciencia de materiales (2006) de University of North Texas, Denton, Texas. Ha trabajado como Ingeniero de investigacin y desarrollo para Square-D, Iowa. Actualmente se desempea como consultor de corrosin para ELK Engineering Associates, Inc en Fort Worth, TX