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Thermodynamic study of non-solvent/dimethyl sulfoxide/polyacrylonitrile ternary systems: effects of the non-solvent species

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Abstract

In order to investigate the effects of the non-solvent species on the formation mechanism of polyacrylonitrile (PAN) fiber in wet spinning, theoretical ternary phase diagrams of water/DMSO/PAN and ethanol/DMSO/PAN systems were constructed based on the extended Flory–Huggins theory. The cloud-points of dilute PAN solutions of the two systems were determined by titration method and those of concentrated PAN solutions from Boom’s linearized cloud-point correlation. Binary interaction parameters were calculated and optimized to construct the theoretical phase diagram. The obtained diagrams were used to investigate the effects of the non-solvent species on the formation of PAN fibers. If the non-solvent water is replaced with ethanol, the meta-stable two-phase region in the ternary phase diagram increases. This favors the de-mixing of the filament via nucleation and growth mechanism during the coagulation process, resulting in homogenous dense PAN fibers with low porosity.

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Abbreviations

a, b, a 0, a 1, a 2, a 3, a 4, α:

Constants

w 1 :

Mass fraction of non-solvent

w 2 :

Mass fraction of solvent

w 3 :

Mass fraction of polymer

g 12 :

Concentration-dependent binary interaction parameter between non-solvent and solvent

g 23 :

Binary interaction parameter between solvent and polymer

g 13 :

Binary interaction parameter between non-solvent and polymer

ΔG m :

Gibbs free energy of mixing

ΔG E :

Excess Gibbs free energy of mixing

n 1 :

Molar fraction of non-solvent

n 2 :

Molar fraction of solvent

R :

Gas constant

T :

Absolute temperature

Λ12, Λ21 :

Wilson parameter

ϕ1 :

Volume fraction of non-solvent

ϕ2 :

Volume fraction of solvent

ϕ3 :

Volume fraction of polymer

V 1 :

Molar volume of non-solvent

V 2 :

Molar volume of solvent

λ12 = λ21 :

Interaction energy parameter between non-solvent and solvent

λ22 :

Interaction energy parameter between solvent and solvent

λ11 :

Interaction energy parameter between non-solvent and non-solvent

γ1 :

Activity coefficient of non-solvent

γ2 :

Activity coefficient of solvent

δ1,d :

Dispersion force component of the solubility parameter of non-solvent

δ1,p :

Polar force component of the solubility parameter of non-solvent

δ1,h :

Hydrogen bond component of the solubility parameter of non-solvent

δ3,d :

Dispersion force component of the solubility parameter of polymer

δ3,p :

Polar force component of the solubility parameter of polymer

δ3,h :

Hydrogen bond component of the solubility parameter of polymer

Δμ1 :

Difference between the chemical potential of non-solvent in the mixture and the pure state

Δμ2 :

Difference between the chemical potential of solvent in the mixture and the pure state

Δμ3 :

Difference between the chemical potential of polymer in the mixture and the pure state

Δμ1,A :

Difference between the chemical potential of non-solvent in polymer-rich phase and the pure state

Δμ2,A :

Difference between the chemical potential of solvent in polymer-rich phase and the pure state

Δμ3,A :

Difference between the chemical potential of polymer in polymer-rich phase and the pure state

Δμ1,B :

Difference between the chemical potential of non-solvent in polymer-poor phase and the pure state

Δμ2,B :

Difference between the chemical potential of solvent in polymer-poor phase and the pure state

Δμ3,B :

Difference between the chemical potential of polymer in polymer-poor phase and the pure state

ϕ1,A :

Volume fraction of non-solvent in polymer-rich phase

ϕ2,A :

Volume fraction of solvent in polymer-rich phase

ϕ3,A :

Volume fraction of polymer in polymer-rich phase

ϕ1,B :

Volume fraction of non-solvent in polymer-poor phase

ϕ2,B :

Volume fraction of solvent in polymer-poor phase

ϕ3,B :

Volume fraction of polymer in polymer-poor phase

\( G_{22} \) :

\( \frac{{\partial^{2} \Updelta G_{\text{m}} }}{{\partial (\phi_{2} )^{2} }} \)

\( G_{33} \) :

\( \frac{{\partial^{2} \Updelta G_{\text{m}} }}{{\partial (\phi_{3} )^{2} }} \)

\( G_{23} \) :

\( \frac{{\partial^{2} \Updelta G_{\text{m}} }}{{\partial \phi_{2} \partial \phi_{3} }} \)

\( G_{222} \) :

\( \frac{{\partial^{3} \Updelta G_{\text{m}} }}{{\partial (\phi_{2} )^{3} }} \)

\( G_{223} \) :

\( \frac{{\partial^{3} \Updelta G_{\text{m}} }}{{\partial (\phi_{2} )^{2} \partial \phi_{3} }} \)

\( G_{233} \) :

\( \frac{{\partial^{3} \Updelta G_{\text{m}} }}{{\partial \phi_{2} \partial (\phi_{3} )^{2} }} \)

u 1 :

ϕ1/(ϕ1 + ϕ2)

u 2 :

ϕ2/(ϕ1 + ϕ2)

PAN:

Polyacrylonitrile

DMSO:

Dimethyl sulfoxide

LCP:

Linearized cloud-point

NG:

Nucleation and growth

SD:

Spinodal decomposition

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Acknowledgments

The authors gratefully acknowledge the financial support from the Science and Technology Commission of Shanghai Municipality (07QA14001) and National 973 Project (2006CB605302 and 2006CB605303).

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Authors and Affiliations

  1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Material Science and Engineering, Chemical Fibers Research Institute, Donghua University, Shanghai, 201620, People’s Republic of China

    Jian Zhang, Youwei Zhang & Jiongxin Zhao

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  1. Jian Zhang
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  2. Youwei Zhang
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  3. Jiongxin Zhao
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Correspondence to Youwei Zhang or Jiongxin Zhao.

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Zhang, J., Zhang, Y. & Zhao, J. Thermodynamic study of non-solvent/dimethyl sulfoxide/polyacrylonitrile ternary systems: effects of the non-solvent species. Polym. Bull. 67, 1073–1089 (2011). https://doi.org/10.1007/s00289-011-0525-9

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