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This study explores the high-frequency dynamics and visco-elastic properties of the PEG+H2O system using Brillouin light scattering. The results provide insights into the relaxation processes and temperature analysis of the system.
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High-Frequency Dynamics in PEG+H2O System Mikołaj Pochylski Adam Mickiewicz University (UAM) Department of Physics, Poznań, Poland
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Outline • PolyEthylene Glycol – PEG • Brillouin Light Scattering • Relaxation process • – Visco–elasticity • –Relaxation functions • Results for PEG+H2O system: • – Temperature analysis • – Frequency analysis • – Comparison with dielectric results
PolyEthylene Glycol - PEG OH-(CH2-CH2-O)n-H PEG600(n=13)
PolyEthylene Glycol - PEG • General properties: • Non-toxic, flexible,hydrophilic (amphiphilic) • Application examples: • Separation, purification and fusion of biomolecules and cells, • Hydrophilic moiety in nonionic surfactants, • Matrix for ion conducting polymer electrolytes, • Coating of implants and ship hulls • ... Industry fields: Biomedical, Pharmaceutical, Cosmetics, Textile, Paints, Food ...
PolyEthylene Glycol - PEG hydroxyl group ether group
– density fluctuations Dynamic structure factor (shape of the spectrum) – Dielectric constant fluctuations Light scattering
Light scattering Linearized hydrodynamic equations for viscous fluid FT
Spectrum of scattered light Intensity Frequency
Brillouin Light Scattering Brillouin Frequency Shift
Acoustical parameters: Hypersound velocity - vB Normalized attenuation coefficient - /f2 Brillouin Light Scattering Brillouin Shift: (velocity of soundwave) Scattering Wave Vector: Brillouin Linewidth (HWHM): (attenuation of soundwave) Kinematic longitudinal viscosity Brillouin Spectroscopy: extension of Ultrasonic Spectroscopy for GHz frequencies
Brillouin Light Scattering Longitudinal Modulus, M: Describes mechanical response of a medium (induced stress) subjected to longitudinal deformation
Acoustical parameters: Hypersound velocity - vB Normalized attenuation coefficient - /f2 Brillouin Light Scattering Complex longitudinal modulus components: Accumulation modulus – M’ Loss modulus – M”
– Relaxation time Visco-elasticity
Peak condition Relaxation Debye relaxation function
B , B vB, /f2 M’ , M” Results – PEG600 Brillouin spectra for pure PEG600 at different temperatures Normalized intensity Frequency shift [GHz]
Debye relaxation function Temeprature dependence of relaxation time: • Vogel-Fulcher-Tamman • Arrhenius Maisano, G., et al.,Mol. Phys. 1993, 78, 421 Results – PEG600
Relaxation in complex liquids Arrhenius Vogel-Fulcher-Tamman
Results Temperature experiment for PEG400 solutions
Havriliak-Negami Debye Cole-Cole Cole-Davidson Results Temperature experiment for PEG400 solutions Havriliak-Negami function
Results Temperature experiment for PEG400 solutions Cole-Cole function Vogel-Fulcher-Tamman
Brillouin Light Scattering Full Spectrum Analysis Dynamic structure factor Havriliak-Negami function
Poor quality of fit: presence of the distribution of relaxation times • More complicated relaxation function is needed Full Spectrum Analysis – PEG600 Debye relaxation
Full Spectrum Analysis – PEG600 Cole-Davidson relaxation function
Havriliak-Negami Debye relaxation Full Spectrum Analysis – PEG400 • Modulus expressed in terms of the Longitudinal Compliance, J(Havriliak-Negami function) • and taken directly from dielectric experiment T. Sato, et al.,J. Chem. Phys. 1998, 108, 4138
Relaxation times vs PEG concentration comparison with Dielectric Spectroscopy results [1] M. Pochylski et al., J.Phys. Chem. B2006, 110, 20533 [2] T. Sato et al, J.Chem.Phys.1998, 108, 4138 [3] N. Shinyashiki et al, J.Chem.Phys.1990, 93, 760 [4] C.H. Wang et al., J. Non-Cryst. Solids1991, 131, 970. [5] T. Noudou et al., Jpn. J. Appl. Phys.1996, 35, 2944.
PEG282, x’=0.42 DVFT = 7.6 PEG400, x’=0.50 DVFT = 7.2 Relaxation times vs Temperature comparison with Dielectric Spectroscopy results [1] Murthy, S.S.N. et al., J. Phys. Chem. B 2000, 104, 6955 [2] Sudo, S. et al., J. Chem. Phys. 2004, 121, 7332
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