Viscosity of entangled polymer melts

log(const.)

entanglements are also reflected

in the molar-mass dependence
of the viscosity:

unentangled chains:
< : = 1

log(const.M)
From Strobl, The Physics of Polymers

entanglement regime:
> : = 3.2 3.6
1

Time-temperature superposition principle

Often, measurement of
mechanical properties
only possible in
certain frequency and
temperature range.

Construction of complete relaxation curve possible

using the time-temperature superposition principle.
This corresponds to shifting the curves measured
at different temperatures along the log()-axis.

The principle follows from

the fact that all relaxation processes
(terminal flow, transition between rubbery and glassy region)
have the same temperature dependence
The friction between the segments determines both processes.
or
, = ,
, log = , log + log
is the shift factor.

Williams-Landel-Ferry
(WLF) equation

1
=
+ 2

ln(aT)

: reference temperature (can be any temperature)

1 , 2 : coefficients

WLF law holds in the

temperature range above
the glass transition temperature,
i.e. between and ~ + 70

0
Tref

T [K]

Vogel-Fulcher-Tammann (VFT) law

=

+2

is equivalent to

= 0 exp

VFT law describes viscosity

in the temperature region
above the glass transition
temperature

From Strobl, The Physics of Polymers.

Data from Plazek et al., Macromolecules
1992.
5

1
ln = ln + ln = ln
+ 2
1 + 2 1 2
= ln
+ 2

add c1c2 and

subtract it again

1 2
= ln 1 +
+ 2
identify 2

= 0 exp

and

= 1 2

at temperatures far above :

VFT law results in Arrhenius law

7.6 Rubber elasticity

strong stretching possible

(several times
its original length)
deformation fully reversible

Types of networks
chemically connected networks,
e.g. vulcanized poly(1,4-isoprene)
(car tire), Goodyear 1839
lightly crosslinked,
i.e. long polymer strands
between cross-links

Sx

Sx
Sx

Sx

another example:
chemically cross-linked
polyelectrolytes:
superabsorbers

another example:
thermo- or pH-responsive polymer networks
macroscopic shrinkage of gel and water releas
valves in microfluidics, drug release

water-soluble

water-insoluble

T. Tanaka et al.

: crosslinker
9

thermoreversible networks:
network is dissolved upon heating
reshaping is possible

triblock copolymers
with hard PS end blocks
and soft PB or PI middle blocks:
Kraton
used for adhesives (e.g. wound draps)

polymer with hydrophobic end blocks

(poly(propylene oxide)) and
hydrophilic middle block (poly(ethylene oxide))
in aqueous solution: polymeric hydrogel
Pluronics from BASF, used for cosmetics

10

Gelatine:

collagen

heating breaking of bonds

H-bonds
bonds between polar/charged amino acids
van der Waals bonds

gelatine:
network points
are triple helices

cooling
partial reformation
of bonds
11