Qualitative and Semiquantitative Determination of the Atomic and Molecular Tungsten Distributions in Hybrid Hydroxyurethanes–Poly(dimethylsiloxane) Films Containing Phosphotungstates ([PW 12 O 40 ] 3– )
Restricted accessResearch articleFirst published online December, 2020
Qualitative and Semiquantitative Determination of the Atomic and Molecular Tungsten Distributions in Hybrid Hydroxyurethanes–Poly(dimethylsiloxane) Films Containing Phosphotungstates ([PW 12 O 40 ] 3– )
In this study, hybrid poly(dimethylsiloxane)-derived hydroxyurethanes films (PDMSUr-PWA) containing phosphotungstic acid (H3PW12O40/PWA) were characterized using field emission gun scanning electron microscopy (FEG-SEM), in attenuated total reflectance Fourier transform mid-infrared mode (ATR FT-MIR), and analyzed using synchrotron radiation micro-X-ray fluorescence (SR-μXRF), synchrotron radiation grazing incidence X-ray fluorescence (SR-GIXRF), laser-induced breakdown spectroscopy (LIBS), and instrumental neutron activation analysis (NAA) in order to correlate the distribution patterns of tungsten and properties of PDMSUr-PWA films. PDMS constitute elastomers with good mechanical, thermal, and chemical (hydrophobicity/non-hygroscopy) resistance. Currently, products based on urethanes (e.g., polyurethanes) are widely used in many applications as plastics, fiber-reinforced polymers, high-performance adhesives, corrosion-resistant coatings, photochromic films, among others. The possibility to combine inorganic and organic components can produce a hybrid material with unique properties. PWA has an important role as agent against the corrosion of steel surfaces in different media, besides exhibiting amazing catalytic and photochromic properties in these films. PWA kept its structure inside of these hybrid films through interactions between the organic matrix of PDMSUr and silanol from the inorganic part (organically modified silica), as was shown using ATR FT-MIR spectra. The FEG-SEM/SR-μXRF/wide-angle X-ray scattering (WAXS)/X-ray diffraction (XRD)/energy dispersive X-ray results proved the presence of PWA in the composition of domains of PDMSUr-PWA films. At PWA concentrations higher than 50 wt%/wt, tungsten segregation across the thickness is predominant, while that at PWA concentrations lower than 35 wt%/wt, tungsten segregation at surface is predominant. Inhomogeneities in the tungsten distribution patterns (at micrometric and millimetric level) may play an important role in the mechanical properties of these films (elastic modulus and hardness).
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.
2.
G. Oertel. Polyurethane Handbook. Munich: Hanser Publishers, 1985. Pp. 7–116.
3.
W. Hui, W. Qingsong, H. Jia-Jia, et al. “Study on the Pyrolytic Behaviors and Kinetics of Rigid Polyurethane Foams”. Procedia Eng. 2013. 52. 377–385.
4.
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]. São Paulo-Brasil: Universidade de São Paulo (IQSC-USP), 2015.
SweilehB.Al-HiariY.KailaniM., et al.“Synthesis and Characterization of Polycarbonates by Melt Phase Interchange Reactions of Alkylene and Arylene Diacetates with Alkylene and Arylene Diphenyl Dicarbonates”. Molecules. 2010. 15(5): 3661–3682.
7.
O. Figovsky, L. Shapolov, N. Blank. Cyclocarbonate Groups Containing Hydroxyamine Oligomers from Epoxycyclocarbonates. US Patent 6 407198 B1. 2002.
8.
ArestaM.DibenedettoA.AngeliniA.“Catalysis for the Valorization of Exhaust Carbon: from CO2 to Chemicals, Materials, and Fuels. Technological Use of CO2”. Chem. Rev. 2014. 114: 1709–1742.
9.
WangL.JiQ.GlassT., et al.“Synthesis and Characterization of Organosiloxane Modified Segmented Polyether Polyurethanes”. Polymer. 2000. 41: 5083–5093.
10.
PergalM.DzunuzovicJ.PorebaR., et al.“Surface and Thermomechanical Characterization of Polyurethane Networks Based on Poly(Dimethylsiloxane) and Hyperbranched Polyester”. Exp. Polym. Lett. 2013. 7(10): 806–820.
11.
SollierE.MurrayC.MaoddiaP., et al.“Rapid Prototyping Polymers for Microfluidic Devices and High-Pressure Injections”. Lab Chip. 2011. 11: 3752–3765.
12.
AguiarK.R.SantosV.G.EberlinM., 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.
13.
Rossi de AguiarK.M.F.Ferreira-NetoE.P.BlunkS., 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.
14.
Peña-AlonsoR.RubioF.RubioJ.“The Role of Γ-Aminopropyltriethoxysilane (Γ-APS) on Thermal Stability of TEOS-PDMS Ormosils”. J. Sol-Gel Sci. Technol. 2005. 36(1): 77–85.
15.
MosaJ.DuránA.AparicioM.“Epoxy-Polystyrene-Silica Sol-Gel Membranes with High Proton Conductivity by Combination of Sulfonation and Tungstophosphoric Acid Doping”. J. Membr. Sci. 2010. 361(1–2): 135–142.
16.
PivaR.RochaM.PivaD., et al.“Acidic Dressing Based on Agarose/Cs2.5H0.5PW12O40 Nanocomposite for Infection Control in Wound Care”. ACS Appl. Mater. Interfaces. 2018. 10(37): 30963–30972.
P. Willmott. “Synchrotron Physics”. In: Introduction to Synchrotron Radiation: Techniques and Applications. Chichester, UK: John Wiley and Sons, 2011. Chap. 3, Pp. 39–86.
19.
K. Janssens, F. Adams, A. Rindbly. Microscopic X-ray Fluorescence Analysis. Chichester, UK: John Wiley and Sons, Ltd., 2000.
20.
PattersonB.HavrillaG.SchoonoverJ.“Elemental and Molecular Characterization of Aged Polydimethylsiloxane Foams”. Appl. Spectrosc. 2006. 60(10): 1103–1110.
21.
PattersonB.HavrillaG.“Confocal Micro X-ray Fluorescence a New Paradigm in 3D Elemental Imaging for Materials Characterization”. Microsc. Microanal. 2008. 14(S2): 1088–1089.
22.
AdamsF.“Synchrotron X-ray Fluorescence Analysis in Environmental and Earth Sciences”. EPJ Web Conf. 2010. 9: 165–180.
23.
A. Balerna, S. Mobilio. “Introduction to Synchrotron Radiation”. In: S. Mobilio, F. Boscherini, C. Meneghini, editors. Synchrotron Radiation: Basics, Methods and Applications. Berlin, Germany: Springer-Berlin, 2015. Pp. 3–28.
SitepuH.KopylovaM.QuirtD., et al.“Synchrotron Micro-X-ray Fluorescence Analysis of Natural Diamonds: First Steps in Identification of Mineral Inclusions In Situ”. Am. Mineral. 2005. 90: 1740–1747.
27.
Ferreira-NetoE.UllahS.Elguera YsnagaO., et al.“Zn2+ Doped Ormosil–Phosphotungstate Hybrid Films with Enhanced Photochromic Response”. J. Sol-Gel Sci. Technol. 2014. 72(2): 290–300.
28.
FerreiraF.AmaralT.Elguera YsnagaO., et al.“Structure–Property Relationship of New Polymide–Organically Modified Silicate–Phosphotungstic Acid Hybrid Material System”. J. Mater. Sci. 2016. 51: 4815–4824.
29.
B. Kanngiesser, M. Haschke. “Methodological Developments and Applications. Micro X-ray Fluorescence Spectroscopy”. In: B. Beckhoff, B. Kanngiesser, N. Langhoff, et al., editors. Handbook of Practical X-ray Fluorescence Analysis. Berlin, Heidelberg: Springer-Verlag, 2006, Chap. 7, Pp. 433–553.
30.
A. Markowicz. “X-ray Physics”. In: R. Van Grieken, A. Markowicz, editors. Handbook of X-ray Spectrometry. New York: Marcel Dekker, 2002. Pp. 1–38.
31.
AingingerH.WobrauschekP.“A Method for Quantitative X-ray Fluorescence Analysis in Nanogram Region”. Nucl. Instrum. Methods. 1974. 114(1): 157–158.
32.
KawaiJ.HayashiK.AmanoH., et al.“Surface Analysis of Si/W Multilayer Using Total Reflection X-ray Photoelectron Spectroscopy”. J. Electron Spectrosc. Relat. Phenom. 1998. 88–91: 787–791.
33.
GonçalvesL.Ferreira-NetoE.UllahS., et al.“Enhanced Photochromic Response of Ormosil–Phosphotungstate Nanocomposite Coatings Doped with TiO2 Nanoparticles”. J. Sol-Gel Sci. Technol. 2015. 76(2): 386–394.
34.
SanceyL.Motto-RosV.KotbS., et al.“Laser-Induced Breakdown Spectroscopy: A New Approach for Nanoparticle’s Mapping and Quantification in Organ Tissue”. J. Visualized Exp. 2014. 88: 51353.
35.
PinonV.MateoM.GinesN.“Laser-Induced Breakdown Spectroscopy for Chemical Mapping of Materials”. Appl. Spectrosc. Rev. 2013. 48(5): 357–383.
36.
PeruchiL.NunesL.Arantes de CarvalhoG., et al.“Determination of Inorganic Nutrients in Wheat Flour by Laser-Induced Breakdown Spectroscopy and Energy Dispersive X-ray Fluorescence Spectrometry”. Spectrochim. Acta, Part B. 2014. 100: 129–136.
NadkarniR.HaldarB.“Sub-Stoichiometric Determination of Tungsten by Neutron Activation Analysis”. J. Radioanal. Chem. 1971. 8(1): 45–51.
39.
RajurkarN.ZinjadD.“Instrumental Neutron Activation Analysis of Tungsten in Various Steel Samples”. J. Radioanal. Chem. 1988. 127(5): 333–340.
40.
SrivastavaS.BhaisareS.WaghD., et al.“Analysis of Tungsten in Low Grade Ores and Geological Samples”. Bull. Mater. Sci. 1996. 19(2): 331–343.
41.
MorrisonS.BeckC.BowenJ., et al.“Determination of Tungsten in Geochemical Reference Material Basalt Columbia River 2 by Radiochemical Neutron Activation Analysis and Inductively Coupled Plasma Mass Spectrometry”. J. Radioanal. Nucl. Chem. 2017. 311(1): 749–754.
42.
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]. São Carlos, São Paulo-Brasil: Universidade de São Paulo (IQSC-USP), 2015. Pp. 249–301.
43.
PérezC.RadtkeM.SánchezH., et al.“Synchrotron Radiation X-ray Fluorescence at the LNLS: Beamline Instrumentation and Experiments”. X-ray Spectrom. 1999. 28(5): 320–326.
44.
SoléV.PapillonE.CotteM., et al.“A Multiplatform Code for the Analysis of Energy-Dispersive X-ray Fluorescence Spectra”. Spectrochim. Acta, Part B. 1999. 62(1): 63–68.
L. Nunes. Estratégias Quimiométricas Para Análise de Plantas Por Espectrometria de Emissão Óptica Com Plasma Induzido por Laser. [Doctor of Science in Analytical Chemistry, Thesis]. São Carlos, São Paulo-Brasil: Universidade Federal de São Carlos, 2010.
47.
P. Gouffon. Manual Do Programa IDEFIX. São Paulo, Brazil: Instituto de Física da Universidade de São Paulo (IFUSP), 1987.
48.
ŠtangarU.L.GrošeljN.OrelB., et al.“Structure of and Interactions Between P/Siwa Keggin Nanocrystals Dispersed in an Organically Modified Electrolyte Membrane”. Chem. Mater. 2000. 12(12): 3745–3753.
49.
VudayagiriS.JunkerM.SkovA.“Factors Affecting the Surface and Release Properties of Thin Polydimethylsiloxane Films”. Polymer J. 2013. 45: 871–878.
50.
KrólP.KrólB.“Surface Free Energy of Polyurethane Coatings with Improved Hydrophobicity”. Colloid Polym. Sci. 2012. 290(10): 879–893.
51.
H.A. Liebhafsky, H.G. Pfeiffer, E.H. Winslow, et al. X-ray Absorption and Emission in Analytical Chemistry: Spectrochemical Analysis with X-rays. New York: John Wiley and Sons, 1960.
52.
V.R. Hoffmann. G.J. Miller. Solids and Surfaces: A Chemist’s View on Bonding in Extended Structures. New York: VCH Publishers, 1989.
53.
DeodharG.“Some Investigations in Rontgen Spectra Part II. X-ray Spectra and Chemical Combination. Sulphur”. Proc. R. Soc. A. 1931. 131(818): 647–658.
54.
A. Meisel, G. Leonhardt, R. Szargan. “X-Ray Spectroscopic Studies of the Band Structure of Solids”. In: R. Gomer, editor. X-ray Spectra and Chemical Binding. Springer Series in Chemical Physics. Berlin: Springer-Verlag, 1989. Vol.37, Chap. 2, Pp.36–55.
55.
A. Compton, S. Allison. X-rays in Theory and Experiment. Chicago: D. Van Nostrand Company, Inc., 1967.
56.
WetterbladT.“Die Kβ1-Linien von Natrium, Magnesium und Aluminium und die Abhängigkeit ihrer Wellenlängen von der Chemischen Bindung”. Z. Phys. 1927. 42(8): 603–610.
57.
S.S. Mao. “Laser Ablation: Fundamentals and Applications”. Presented at: Lawrence Berkeley National Laboratory, University of California at Berkeley; July 20, 2004.
58.
S.J. Rehse. “Laser-Induced Breakdown Spectroscopy (LIBS). Principles of and Recent Advances in Laser Micro/Nano Manufacturing Processes”. Presented at: Principles of and Recent Advances in Laser Micro/Nano Manufacturing Processes. Evanston, Illinois; June 1–4, 2010.
59.
PopaA.SascaV.KissE., et al.“Studies in Structural Characterization of Silica-Heteropolyacids Composites Prepared by Sol-Gel Method”. Mat. Chem. Phys. 2010. 119(3): 465–470.
60.
D. Pito, I. Matos, I. Fonseca, et al. “Methoxylation of α-Pinene Over Heteropolyacids Immobilized in Silica”. Appl. Catal., A. 2010. 373: 140–146.
61.
K.-V. Peinemann, S. Pereira Nunes. Membranes for Energy Conversion. Weinheim, Germany: Wiley-VCH Verlag GmbH, 2008.
62.
ZhangW.ZhaoQ.LiuT., et al.“Phosphotungstic Acid Immobilized on Amine-Grafted Graphene Oxide as Acid/Base Bifunctional Catalyst for One-Pot Tandem Reaction”. Ind. Eng. Chem. Res. 2014. 53(4): 1437–1441.
63.
WangX.HuangY.LinZ., et al.“Phosphotungstic Acid Encapsulated in the Meso-Cages of Amine-Functionalized Metal-Organic Frameworks for Catalytic Oxidative Desulfurization”. Dalton Trans. 2014. 43(31): 11950–11958.
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