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Effect of phase transition on swelling and mechanical behavior of synthetic hydrogels

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Responsive Gels: Volume Transitions I

Part of the book series: Advances in Polymer Science ((POLYMER,volume 109))

Abstract

The effect of the concentration of the charge, its polarity, and position in the side chain together with the effect of amount of diluent and crosslinker at network formation on the appearance and the extent of the first-order phase transition in the swollen ionized polyacrylamide gels in water-acetone mixtures and in ionized poly (N,N′-diethylacrylamide) gels in water is summarized. The results of the swelling, photoelastic, and mechanical behavior together with small-angle neutron scattering, direct-current conductivity and dielectric measurements of these hydrogels in the collapse region are presented and it is shown that a jumpwise volume change at the transition correlates with jumpwise changes in the equilibrium modulus, the stress-optical coefficient, both components of the complex permittivity and modulus, and in the conductivity. The chains were found to have the form of a Gaussian coil in the expanded state and a compact globular structure in the collapsed state. The theory describing the swelling equilibria in polyelectrolyte networks is analyzed and it is shown that experimental swelling behavior of polyacrylamide gels at the collapse can be described by this theory if the correction factor for the effective degree of ionization is introduced.

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Abbreviations

A:

deformational-optical function

A :

front factor

a:

acetone content in a water-acetone mixture

C:

stress-optical coefficient

c:

concentration of co-ions

D:

dielectric constant of the medium

D :

sample diameter

e:

unit charge

ΔF:

change in Gibbs free energy

f:

force

fe :

average functionality of the junction

f-:

activity coefficient of co-ions

G:

shear modulus

G*:

complex shear modulus

h:

chain end-to-end distance

\(\overline {h_0^2 }\) :

mean-square end-to-end distance

i:

degree of ionization

I:

intensity of electric current

k:

Boltzmann constant

M0 :

molar mass of the monomer

n:

number of statistical segments in the chain

ng :

refractive index of the gel

nj :

number of mols of the j-th type ions in the gel

NA :

Avogadro constant

p:

external pressure

P:

swelling pressure

q:

scattering vector

r:

number of equivalent segments of the macromolecule

R:

gas constant

ℛ:

resistance

s:

number of monomeric units in the statistical segment

S 0 :

initial cross-section of the sample

t:

time

T:

temperature

U:

voltage

ΔU:

activation energy

V:

volume of the sample

V1 :

molar volume of the solvent

x1, x2 :

numbers of moles of the solvent and of the polymer

X:

swelling ratio

Z:

degree of polymerization of the chain

Δα :

optical anisotropy of the statistical segment

Δ:

extent of the collapse

κ:

inverse Debye radius

ρ:

density

ϕ 2 :

volume fraction of the polymer in the swollen gel

ϕ 0 :

volume fraction of the polymer at network formation

φ:

correction factor

Φi :

contribution to the swelling pressure Eq. (1)

\(\bar \chi\) :

Flory-Huggins interaction parameter

χc:

critical interaction parameter at the collapse

λ:

compression

Λ:

elongation

σ:

stress

dΣ(q)/dΩ:

differential effective scattering cross-section per unit volume of the sample

νd :

concentration of chains

〈α 20 〉:

dilatation factor

ω:

frequency

ε*:

complex permittivity

τ:

relaxation time

Θ:

scattering angle

SANS:

small-angle neutron scattering

PAAm:

polyacrylamide

PDEAAm:

poly(N,N′-diethylacrylamide)

MBAAm:

N,N′-methylenebisacrylamide

MNa:

sodium methacrylate

TEMED:

N,N′-tetramethylethylenediamine

I:

N,N,N-trimethyl-N-2-methacryloxyethylammonium chloride (salt I)

II:

N,N,N-trimethyl-N-4-methacryloxybutylammonium chloride (salt II)

III:

N,N,N-dimethyl-N-methoxycarbonylmethyl-N-2-methacryloyloxyethylammonium chloride (salt III)

IV:

N,N,N-dimethyl-N-butoxycarbonylmethyl-N-2-methacryloyloxyethylammonium chloride (salt IV)

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Authors and Affiliations

  1. Institute of Macromolecular Chemistry, Czechoslovak Academy of Sciences, 162 06, Prague 6, CSFR

    M. Ilavský

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K. Dušek

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© 1993 Springer-Verlag

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Ilavský, M. (1993). Effect of phase transition on swelling and mechanical behavior of synthetic hydrogels. In: Dušek, K. (eds) Responsive Gels: Volume Transitions I. Advances in Polymer Science, vol 109. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-56791-7_4

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  • DOI: https://doi.org/10.1007/3-540-56791-7_4

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  • Print ISBN: 978-3-540-56791-2

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