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Measuring the Mutual Diffusion Coefficient for Dodecyl Acrylate in Low Molecular Weight Poly(dodecyl acrylate) with Laser Line Deflection (Wiener's Method) and the Fluorescence of Pyrene

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Daniel Antrim,^† Patrick Bunton,^‡ Lydia Lee Lewis,^§ Brian D. Zoltowski,^† and John A. Pojman*^†

Department of Chemistry and Biochemistry, The University of Southern Mississippi, Hattiesburg, Missisippi 39406, Department of Physics, William Jewell College, 500 College Hill, Liberty, Missouri 64068, and Department of Chemistry, Millsaps College, Jackson, Mississippi 39210

J. Phys. Chem. B, 2005, 109 (23), pp 11842–11849

DOI: 10.1021/jp0502609

Publication Date (Web): May 18, 2005

Section:

Physical Properties of Synthetic High Polymers

Abstract

Diffusion of small molecules into glassy polymers is quite complicated and almost always non-Fickian. Little work has been done with the diffusion of low molecular weight polymers that are liquids at room temperature (such as poly(dodecyl acrylate)) into their miscible monomers. We have studied three molecular weights under 20 000 to determine if poly(dodecyl acrylate) diffusion into dodecyl acrylate could be treated with Fick's law and if so to determine the values of the diffusion coefficients. We compare two methods for measuring the diffusion of dodecyl acrylate into poly(dodecyl acrylate): We used laser line deflection (Wiener's method) and improved upon the method from published reports. We also used the dependence of pyrene's fluorescence on the viscosity to measure the concentration distribution, and thus to extract the diffusion coefficient. After an initial relaxation period, diffusion in all cases followed Fick's law with a single concentration-independent diffusion coefficient. Comparison of the diffusion coefficients obtained by both methods yielded the same order of magnitude for the diffusion coefficients (10^-7 cm²/s) and showed the same trend in the dependence on the average molecular weight of the polymer (a decrease in the diffusion coefficient with an increase in the molecular weight).

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This article has been cited by 2 ACS Journal articles (2 most recent appear below).

Evidence for the Existence of an Effective Interfacial Tension between Miscible Fluids. 2. Dodecyl Acrylate−Poly(dodecyl acrylate) in a Spinning Drop Tensiometer
Brian Zoltowski, Yuri Chekanov, Jonathan Masere, John A Pojman, and Vitaly Volpert
Langmuir2007 23 (10), 5522-5531
- Evidence for the Existence of an Effective Interfacial Tension between Miscible Fluids. 2. Dodecyl Acrylate−Poly(dodecyl acrylate) in a Spinning Drop Tensiometer
  Brian Zoltowski, Yuri Chekanov, Jonathan Masere, John A Pojman, and Vitaly Volpert
  Langmuir2007 23 (10), 5522-5531
  We studied drops of dodecyl acrylate in poly(dodecyl acrylate) (molecular weight of 25 000) in a spinning drop tensiometer to determine whether an effective interfacial tension (EIT) existed between these two miscible fluids. We found convincing evidence. ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Evidence for the Existence of an Effective Interfacial Tension between Miscible Fluids: Isobutyric Acid−Water and 1-Butanol−Water in a Spinning-Drop Tensiometer
John A. Pojman, Colin Whitmore, Maria Liria Turco Liveri, Renato Lombardo, Jolanta Marszalek, Rosie Parker, and Brian Zoltowski
Langmuir2006 22 (6), 2569-2577
- Evidence for the Existence of an Effective Interfacial Tension between Miscible Fluids: Isobutyric Acid−Water and 1-Butanol−Water in a Spinning-Drop Tensiometer
  John A. Pojman, Colin Whitmore, Maria Liria Turco Liveri, Renato Lombardo, Jolanta Marszalek, Rosie Parker, and Brian Zoltowski
  Langmuir2006 22 (6), 2569-2577
  We report definitive evidence for an effective interfacial tension between two types of miscible fluids using spinning-drop tensiometry (SDT). Isobutyric acid (IBA) and water have an upper critical solution temperature (UCST) of 26.3 °C. We created a drop ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links