Qualitative and Semiquantitative Determination of Bromine in Hybrid Hydroxyurethanes-Poly(dimethylsiloxane) Films Containing Phosphotungstates ([PW12O40]3-)
In this study, the complex hybrid materials based on hybrid poly(dimethylsiloxane)-derived hydroxyurethanes films (PDMSUr-PWA) containing phosphotungstic acid (H3PW12O40/PWA) and Bromine were analyzed by laboratory XRF (EDXRF, WDXRF), Synchrotron Radiation Micro X-ray Fluorescence (SR-μXRF), and Volumetric analysis, in order to correlate the distribution patterns and composition of Bromine with their respective properties and potential applications. Recently, the characterization and analysis of PDMSUr-PWA films (without consider Bromine) was reported in order to correlate structure, compositions and properties. SR-μXRF maps provide indicatives of the possible inter-elemental interactions Bromine-Silicon-Tungsten. There is segregation of Bromine at surface and through the thickness of PDMSUr-PWA films. These films possess hydrophobicity and non-hygroscopic properties, which makes potential candidates for high-performance adhesives, corrosion-resistant coatings of steel and titanium alloys surfaces in different media. The presence of Bromine (element provided from tetraethylammonium bromide in previous steps of elaboration of PDMSUr-PWA films) could contribute with their corresponding adhesive, thermal-insulator, and anti-corrosive properties. Functional materials as PDMSUr-PWA films present easy processing, excellent toughness and durability. Nowadays, Polyurethane (PU) coatings are very useful in many sectors due to their excellent mechanical properties. Nonetheless, one limitation is their thermal stability, which can be improved by insertion of poly(dimethylsiloxane) (PDMS) segments. The interesting properties of PDMS are of significance for applications as adhesives and at the aerospace industry. The films containing 1%, 35%, 40-50% PWA are candidates as anticorrosive coatings and as inert materials under the presence of polar chemical reagents, based on the significant Bromine presence at surface. The films containing 25% and 55% PWA would be suitable for thermal insulators, based on the significant Bromine presence at thickness. PDMSUr-PWA films can constitute systems for the storage of energy based on the synergy of their potential applications as Proton exchange membrane fuel cells (PEMFCs) and also as H2-Br2 multiple micro-fuel cells. PEMFCs have great attention in scientific and industrial fields based on energetic and environmental aspects mainly. PEMFCs based on PDMSUr-PWA films could exhibit high chemical and mechanical stabilities. The hydrogen bromine (H2-Br2) electrochemical systems constitute promising candidates as generation and storage devices of energy due to their high energy capacities and conversion efficiencies, as also their low costs. More in depth studies are necessary in order to analyze the different chemical forms of Bromine present (atomic, ionic and/or molecular) in the three-dimensional network constituted by silicates and phosphotungstates, as also the characterization of their local chemical and electrochemical environment.
Orlando Elguera Ysnaga,
Qualitative and Semiquantitative Determination of Bromine in Hybrid Hydroxyurethanes-Poly(dimethylsiloxane) Films Containing Phosphotungstates ([PW12O40]3-), Engineering Physics.
Vol. 4, No. 2,
2020, pp. 19-36.
L. Zhai, H. Li. “Polyoxometalate–Polymer Hybrid Materials as Proton Exchange Membranes for Fuel Cell Applications”. Molecules. 2019, 24 (19): 3425.
K. Tsuru, S. Hayakawa, A. Osaka, and J. Ritchie. “Medical Applications of Hybrid Materials” and “Electronic and Electrochemical Applications of Hybrid Materials”. In Guido Kickelbick editor. Hybrid Materials Synthesis, Characterization, and Applications. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co., 2007. Chapter 8 and Chapter 10, Pp. 323-335, and 401-402.
L. Wang, Q. Ji, T. Glass, T. Ward, et al. “Synthesis and Characterization of Organosiloxane Modified Segmented Polyether Polyurethanes”. Polymer. 2000. 41: 5083–5093.
M. Pergal, J. Dzunuzovic, R. Poreba, D. Micic, et al. “Surface and Thermomechanical Characterization of Polyurethane Networks Based on Poly(Dimethylsiloxane) and Hyperbranched Polyester”. Exp. Polym. Lett. 2013. 7 (10): 806–820.
J. Cabrera, M. Ruiz, M. Fascio, N. D’Accorso, R. Mincheva, P. Dubois, L. Lizarraga and R. Negri. “Increased Surface Roughness in Polydimethylsiloxane Films by Physical and Chemical Methods”. Polymers 2017. 9 (331): 1-15.
M. Planes, C. Le Coz, A. Soum, S. Carlotti, V. Rejsek-Riba, S. Lewandowski, S. Remaury, S Solé. “Polydimethylsiloxane/Additive Systems for Thermal and Ultraviolet Stability in Geostationary Environment”. Journal of Spacecraft and Rockets. 2016. 53 (6): 1-6.
E. Maaskant, K. Tempelman, N. Benes. “Hyper-cross-linked thin polydimethylsiloxane films”. European Polymer Journal, 2018. 109: 214-221.
J. Vega, S. Madrigal, J. Martínez. “Thermoplastic Polyurethanes-Fumed Silica Composites: Influence of NCO/OH in the Study of Thermal and Rheological Properties and Morphological Characteristics”. In: A. Zaki, E. Sonbati editors. Thermoplastic–Composite Materials. Croatia: Intech, 2012. Pp. 11–25.
K. Rossi Flores de Aguiar. Síntese de Hidroxiuretana-Poli(dimetilsiloxano) com Diferentes Terminações de Cadeia via Fixação de CO2: Síntese, Caracterizações e Aplicações. [Doctor of Science in Analytical and Inorganic Chemistry, Thesis]. Instituto de Química de São Carlos. São Carlos, São Paulo-Brasil: Universidade de São Paulo (IQSC-USP), 2015. Unpublished.
K. R. Aguiar, V. G. Santos, M. Eberlin, K. Rischka, et al. “Efficient Greensynthesis of Bis(Cyclic Carbonate) Poly(Dimethylsiloxane) Derivative Using CO2 Addition: A Novel Precursor for Synthesis of Urethanes”. RSC Adv. 2014. 4 (46): 24334–24343.
K. M. F. Rossi de Aguiar, E. P. Ferreira-Neto, S. Blunk, J. F. Schneider, et al. “Hybrid Urethanesil Coatings for Inorganic Surfaces Produced by Isocyanate-Free and Sol-Gel Routes: Synthesis and Characterization”. RSC Adv. 2016. 6 (23): 19160–19172.
K. M. F. Rossi de Aguiar, U. Specht, J. Maass, D. Salz, C. Picon, M. Noeske, K. Rischka and U. P. Rodrigues-Filho. “Surface modification by physical treatments on biomedical grade metals to improve adhesion for bonding hybrid non-isocyanate urethanes”. RSC Adv. 2016. 6 (53): 47203–47211.
P. Ferreira, A. Carvalho, T. R. Correia, B. P. Antunes, I. J. Correia, P. Alves. “Functionalization of polydimethylsiloxane membranes to be used in the production of voice prostheses”. Science and Technology of Advanced Materials. 2013. 14 (5): 055006.
Y. Liu, Y. Lu, A. Haragirimana, I. Buregeya, N. Li, Z. Hu, S. Chen. “Immobilized phosphotungstic acid for the construction of proton exchange nanocomposite membranes with excellent stability and fuel cell performance”. International Journal of Hydrogen Energy. 2020. 45 (35): 17782-17794.
Y. Zhou, J. Yang, H. Su, J. Zeng, S. Ping-Jiang, W. Goddard. “Insight into Proton Transfer in Phosphotungstic Acid Functionalized Mesoporous Silica-Based Proton Exchange Membrane Fuel Cells”. Journal of the American Chemical Society. 2014. 136 (13): 4954-4964.
K. Saadi, P. Nanikashvili, Z. Tatus-Portnoy, S. Hardisty, V. Shokhen, M. Zysler, D. Zitoun. “Crossover-Tolerant Coated Platinum Catalysts in Hydrogen/Bromine Redox Flow Battery”. Journal of Power Sources. 2019. 422: 84-91.
K. Höhne, G. Starbeck. Hydrogen/Bromine Cell. U.S. Patent: 4,520,081. Filed: 1983. Issued 1985.
Novel bromine battery: Small-scale demo, large-scale promise. Spring 2014 issue of Energy Futures. https://energy.mit.edu/wp-content/uploads/2016/06/MITEI-Energy-Futures-Spring-2014.pdf [accessed 28 July 2020].
R. Savinell, S. Fritts. Theoretical and Experimental Flow Cell Studies of a Hydrogen-Bromine Fuel Cell, Part 1. [Chemical Engineering M.S. Thesis]. University of Akron, Akron, Ohio, United States, 1986. Pp. 1–8, 16-24.
H. Kreutzer, V. Yarlagadda, T. Van Nguyen. “Performance Evaluation of a Regenerative Hydrogen-Bromine Fuel Cell”. Journal of The Electrochemical Society. 2012. 159 (7): F331-F337.
T. Van Nguyen, V. Yarlagadda, G. Lin, G. Weng, C. Ying, V. Li, K Chan. “Comparison of Acid and Alkaline Hydrogen-Bromine Fuel Cell Systems”. ECS Transactions- Electrochemical Society. 2014. 58 (37): 29-35.
T. Nguyen, V. Yarlagadda, D. Konwar, K. Chan. “359395 Alkaline-Based Hydrogen-Bromine Fuel Cell”. 2014. AIChE Annual Meeting. https://www.aiche.org/conferences/aiche-annual-meeting/2014/proceeding/paper/304d-alkaline-based-hydrogen-bromine-fuel-cell-1 [accessed 28 July 2020].
W. Glass, G. Boyle. “Performance of Hydrogen-Bromine Fuel Cells”. In: Fuel Cell Systems, George J. Young, Henry R. Linden. Advances in Chemistry-American Chemical Society. 1969. 47 (15): 203-220.
Elestor Electricity Storage. “The choice for hydrogen and bromine”. https://www.elestor.nl/technology-the-elestor-solution/ [accessed 28 July 2020].
Energy storage for the grid & Transportation. Introduction to Hydrogen/Bromine regenerative fuel cells. LAS 493 Special Topics in Energy and Sustainability. https://las493energy.wordpress.com/2017/09/25/introduction-to-hydrogenbromine-regenerative-fuel-cells/ [accessed 28 July 2020].
O. Elguera, K. Rossi de Aguiar, C. Zamboni, W. Polito, U. P. Rodrigues-Filho. “Qualitative and Semiquantitative Determination of the Atomic and Molecular Tungsten Distributions in Hybrid Hydroxyurethanes–Poly(dimethylsiloxane) Films Containing Phosphotungstates ([PW12O40]3–)”. Applied Spectroscopy. 2020. 0 (0) 1–15.
C. Furl, C. Mathieu, T. Roberts. Washington State Department of Ecology. Evaluation of XRF as a Screening Tool for Metals and PBDEs in Children’s Products and Consumer Goods. United States of America, 2012. Pp. 30-35.
A. Takeda, S. Yamasaki, H. Tsukada, Y. Takaku, S. Hisamatsu, N. Tsuchiya. “Determination of total contents of bromine, iodine and several trace elements in soil by polarizing energy dispersive X-ray fluorescence spectrometry”. Journal Soil Science and Plant Nutrition/Soil Chemistry and Soil Mineralogy. 2011. 57 (1): 19-28.
M. Ziegler, T. Jilbert, G. De Lange, L. Lourens, G. Reichart. “Bromine counts from XRF scanning as an estimate of the marine organic carbon content of sediment cores”. Geochemistry, Geophysics, Geosystems. 2008. 9 (5).
A. Jinsung, J. Hyeyeon, B. Jo-Ri, Y. Hye-On, S. Jungju. “Feasibility of wavelength dispersive X-ray fluorescence spectrometry for a simplified analysis of bromine in water samples with the aid of a strong anion exchange disk”. Spectrochimica Acta. Part B, Atomic Spectroscopy. 2014. 91: 1–4.
Y. Tateishi, T. Hashimoto, K. Ushiyama, N. Sakai, I. Baba, T. Nagayama. “Simple analytical method of bromine in fruits and grain products with wavelength dispersive X-ray fluorescence spectrometer”. Journal of the Food Hygienic Society of Japan (Shokuhin Eiseigaku Zasshi). 2010. 51 (2): 53-7.
G. Pashkova, T. Aisueva, A. Finkelshtein, E. Ivanov, A. Shchetnikov. “Analytical approaches for determination of bromine in sediment core samples by X-ray fluorescence spectrometry”. Talanta. 2016. 160: 375-380.
I. Mantouvalou, T. Wolff, O. Hahn, I. Rabin, L. Lühl, M. Pagels, W. Malzer, B. Kanngiesser. “3D Micro-XRF for Cultural Heritage Objects: New Analysis Strategies for the Investigation of the Dead Sea Scrolls”. Analytical Chemistry. 2011.83 (16): 6308–6315.
A. Leri, S. Myneni. “Natural organobromine in terrestrial ecosystems”. Geochimica et Cosmochimica Acta. 2012. 77: 1-10.
G. Suzuk, A. Kida, S. Sakai, H. Takigami. “Existence State of Bromine as an Indicator of the Source of Brominated Flame Retardants in Indoor Dust”. Environ. Sci. Technol. 2009. 43 (5): 1437–1442.
S. Kutterolf, T. Hansteen, A. Freundt, H. Wehrmann, K Appel, K. Krüger, W. Pérez. “Bromine and chlorine emissions from Plinian eruptions along the Central American Volcanic Arc: From source to atmosphere”. Earth and Planetary Science Letters. 2015. 429 234-246.
C. Pérez, M. Radtke, H. Sánchez, H. Tolentino, et al. “Synchrotron Radiation X-ray Fluorescence at the LNLS: Beamline Instrumentation and Experiments”. X-ray Spectrom. 1999. 28 (5): 320–326.
V. Solé, E. Papillon, M. Cotte, Ph. Walter, J. Susini. “A Multiplatform Code for the Analysis of Energy-Dispersive X-ray Fluorescence Spectra”. Spectrochim. Acta, Part B. 1999. 62 (1): 63–68.
PyMca. “PyMca X-ray Fluorescence Toolkit Home Page”. http://pymca.sourceforge.net/documentation.html. [accessed 28 July 2020].
O. A. Elguera Ysnaga. Métodos de Análise de Materiais Híbridos: Um Estudo Comparativo Entre Fluorescência de Raios-X Com Detecção Dispersiva em Energia Usando Fonte Tradicional e Luz Síncrotron. [Doctor of Science in Analytical and Inorganic Chemistry, Thesis]. Instituto de Química de São Carlos. São Carlos, São Paulo-Brasil: Universidade de São Paulo (IQSC-USP), 2015. Pp. 249–301. Unpublished.
W. Schöniger, “Analytical Procedures for the Flask Combustion Method”. In: Pergamon Press. Proceedings of the International Symposium on Microchemistry, Basle, Switzerland. Sandoz Ltd, 1958. Pp. 93-95.
H. Zhao-sheng, Q. Wen-qiang, K. Cheng-you. “Synthesis and properties of triethoxysilane-terminated anionic polyurethane and its waterborne dispersions”. Journal of Polymer Research. 2015. 22 (6): 111.
D. Li, F. Wang, X. Yu, J. Wang, Q. Liu, P. Yang, Y. He, Y. Wang, M. Zhang. “Anticorrosion organic coating with layered double hydroxide loaded with corrosion inhibitor of tungstate”. Progress in Organic Coatings. 2011.71 (3): 302-309.
S. Oleinik, Y. Kuznetsov, A. Vartapetyan, “Corrosion Inhibition of Steel in Lithium Bromide Brines”. Protection of Metals. 2003. 39 (1): 12-18.
J, Datta, C. Bhattacharya, S. Bandyopadhyay. “Influence of Cl–1, Br–1, NO3–1 and SO4-2 ions on the corrosion behaviour of 6061 Al alloy”. Bulletin of Materials Science. 2005. 28 (3): 253–258.
J. Hernandez, R. García-Alamilla, G. Sandoval-Robles, J. Melo-Banda, L. García-Serrano. “Effect of the addition of phosphotungstic acid on the thermal stability of zirconium oxide”. DYNA. 2014. 81: 107-114.
Q. Tu, J. Wang, R. Liu, J. He, Y. Zhang, S. Shen, J. Xu, J. Liu, M. Yuan, J. Wang. “Antifouling properties of poly(dimethylsiloxane) surfaces modified with quaternized poly (dimethylaminoethyl methacrylate)”. Colloids and Surfaces B: Biointerfaces. 2013.102: 361–370.
L. Zheng-hong, H. Teng-yun. “Synthesis and characterization of poly(dimethylsiloxane)-block- poly (2,2,3,3,4,4,4-heptafluorobutyl methacrylate) diblock copolymers with low surface energy prepared by atom transfer radical polymerization”. Reactive and Functional Polymers. 2008. 68 (5): 931–942.
https://webbook.nist.gov/cgi/cbook.cgi?ID=C10035106&Mask=80#IR-Spec. [accessed 28 July 2020].
I. Kozhevnikov. “Catalysis by heteropoly acids and multicomponent polyoxometalates in liquid-phase reactions”. Chemical Reviews. 1998. 98 (1): 171-198.
A. Yaroslavtsev, D. Gorbatchev. “Proton mobility in the solid inorganic hydrates of acids and acid salts”. Journal of Molecular Structure. 1997. 416 (1–3): 63-67.
J. Keggin. “The structure and formula of 12-phosphotungstic acid”. Proceedings of the Royal Society of London. Series A. 1934. 144 (851): 75–100.
M. de Oliveira, U. P. Rodrigues-Filho, J. Schneider. “Thermal Transformations and Proton Species in 12-Phosphotungstic Acid Hexahydrate Studied by 1H and 31P Solid-State Nuclear Magnetic Resonance”. The Journal of Physical Chemistry C. 2014. 118 (22): 11573-11583.
M. Suss, K. Conforti, L. Gilson, C. Buie, M. Bazant. “Membraneless flow battery leveraging flow-through heterogeneous porous media for improved power density and reduced crossover”. RSC Adv. 2016 (6): 100209-100213.
W. Braff, M. Bazant, C. Buie. “Membrane-less hydrogen bromine flow battery”. Nature Communications 2013. 4 (1): 2346.
A. Passchier, J. Christian, N. Gregory. “The ultraviolet-visible absorption spectrum of bromine between room temperature and 440°C”. Journal of Physical Chemistry. 1967. 71 (4): 937-942.
D. Zehavi, J. Rabani. “The Oxidation of Aqueous Bromide Ions by Hydroxyl Radicals. A Pulse Radiolytic Investigation”. Journal of Physical Chemistry. 1972. 76 (3): 312–319.
Quantification of Bromide by APHA 4500 Method: Phenol Red Colorimetric Method https://www.perkinelmer.com/lab-solutions/resources/docs/APP-Quantification-of-Bromide-by-APHA-4500-using-LAMBDA-465-012208A_01.pdf. [accessed 02 November 2020].
K. Nakamoto. Infrared and Raman Spectra of Inorganic and Coordination Compounds Part A: Theory and Applications in Inorganic Chemistry. New Jersey: John Wiley & Sons, 2009. Pp. 13, 155, 164, 166, 170, 172.
E. Plyler. “Infrared Spectrum of Hydrobromic Acid”. Journal of Research of the National Bureau of Standards-A. Physics and Chemistry. 1960. 64 (5): 377-379.
W. Feng, T. Zhang, J. Liu, R. Lu, Y. Zhao, J. Yao. “Ultrasound-induced change of microstructure and photochromic properties of PAM thin films containing a polyoxometalate”. Journal of Materials Research. 2003. 18 (03): 709-713. (2003).
P. Abramov, A. Rogachev, M. Mikhailov, A. Virovets, E. Peresypkina, M. Sokolov, V. Fedin, “Hexanuclear chloride and bromide tungsten clusters and their derivatives”. Russian Journal of Coordination Chemistry. 2014. 40 (5): 259–267.
Crystal Maker® Software. “Elements, Atomic Radii and the Periodic Radii”.2020. http://crystalmaker.com/support/tutorials/atomic-radii/index.html [accessed 28 July 2020].