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Entangled polymers
Role of entropy in rubber elasticity.
February 07
Lecture 6
Paramagnetism
Spin systems
Some atoms in salts have a permanent
magnetic moment.
Example: Gd2(SO4) 3.8H2O, where the Gd3+
ions have a spin moment, S=7/2.
General case:
Angular-momentum, quantum number, J, gives
paramagnetic moment
g B [J ( J + 1)]
12
1<Land
1<Land factor<2
factor<2
Bohr
Bohr magneton
magneton ==e
2me
= m J g B ,
J mJ J
J=3
-3 -2
February 07
-1 m +1 +2
J
H
Lecture 6
+3
Spin paramagnetism
Simplest system: a spin-paramagnet.
In this case there is no orbital, angular
momentum so J=S. Since S=, there are only 2
values of mJ.
Only two energy levels to consider, with energy
+/-B.
B
mJ = -1/2
+1/2
i exp( U B kT )
=
i
February 07
exp( U B kT )
i
Lecture 6
Curies Law
Spin paramagnetism
There are 2 states and, hence, 2 terms in each
summation.
Average moment, at temperature, T.
= {e ( B kT ) e ( B kT ) } {e ( B kT ) + e ( B kT ) }
= tanh (B kT )
tanh(B/kT)
-2
-1
2
B/kT
high-T,
low-B limit
2 kT
February 07
Curies
Curies Law
Law
Lecture 6
Paramagnetic salts
Experiment
Curves at different temperatures and fields
scale to lie on the curve given by Curies Law.
3+,, S=7/2
Gd
Gd3+
S=7/2
3+,, S=5/2
Fe
Fe3+
S=5/2
<>/
<>/BB
3+,, S=3/2
Cr
Cr3+
S=3/2
B/T
B/T (Tesla
(Tesla KK-1-1))
Waldram Theory of Thermodynamics Ch 15, p187
February 07
Lecture 6
Pierre Curie
and Magnetism
Curies Law
The subject of Pierre Curies doctoral thesis,
1895, the same year as his marriage to Marie.
Lecture 6
Z = exp(B ) + exp( B )
ln(Z ) = B + ln (1 + exp( 2 B ))
= ln Z
= B tanh( B / kT )
Heat Capacity
B
C=
=k
sech 2 (B kT )
T
kT
February 07
Lecture 6
Entropic contribution to
elasticity
Classical treatment:
Any stretched string (metal or rubber)
dU =
dU =
dQ
T dS
+
+
dW
f dl
AA
S
S
=T
dT + T
+ f dl
T l
l T
U
dT
T l
February 07
Lecture 6
U
dl
l T
8
Maxwell relation
Classical analysis continued
Need to relate entropy and tension.
From previous results, differentiating gives
U
S
=T
T l
T l
U
S
=T
+f
l T
l T
2U
2S
=T
lT
lT
2 x
2x
=
yz zy
2U
2 S S
f
=T
+
+
Tl
Tl l T T
2S
2 S S
f
T
=T
+
+
lT
Tl l T T l
We have derived a Maxwell relation, which
connects the entropy to measurable quantites.
f
S
=
T l
l T
February 07
Lecture 6
BB
f (l , T ) =
U
S
T
l T
l T
Direct
Direct contribution
contribution to
to
internal
internal energy.
energy.
For
For example
example through
through
the
the stretching
stretching of
of
intermolecular
intermolecular bonds.
bonds.
Entropic
Entropic contribution.
contribution.
For
For example
example through
through
the
the ordering
ordering of
of
intermolecular
intermolecular bonds
bonds
Using B we get
U
f
f (l , T ) =
+T
T l
l T
Metal wire:
Elastic modulus: (T) = o(1+(T-To)).
Unstretched length: lo(T) = loo(1+(T-To)).
and are ~10-5.
T f
<< 1
f T l
Lecture 6
10
Rubber elasticity
Rubber:
Generally have large elastic strain.
In simple cases
f (l , T ) AT (l lo )
f
f
T
From which,
T l
constants
constants
U
f
f (l , T ) =
+T
l T
T l
f
S
T
T
T l
l T
d Q = dU f d l
T d S = Cl d T AT (l lo ) d l
T
1
S = Cl ln
A(l lo )2
To
2
Lecture 6
11
Rubber elasticity
1-D statistical model
Take molecules to have 2N links, of length, a.
Each link points right or left.
dS
1 dS
= T
dl
2a d r
kT
r
r
=
ln 1 +
ln 1
2a
N
N
kTr 2kT l
=
Na
a lmax
f = T
Expand
Expand lns
lns for
for small
small r/N
r/N
Note:
Note: TT and
and ll dependence
dependence
February 07
Lecture 6
12
Elasticity in rubber
Molecular model
Without strain
With strain
Experiment
X-ray diffraction from un-strained and strained
samples of rubber.
Lecture 6
13