Polymer Solutions and Blends

Why do some things mix and others dont?.

A Phase Separated System !

The Gibbs Free Energy

The second law

S! !! total! > 0!
Remove Barrier !

S! S! S! system! +! !! surroundings! !! total! =!!! ! ! !! !Q ! system Hs !ystem! S! !! surroundings! =!-! T! =! -! T!

Heat !

!! S! ! !S! -!T! total!=! !! H! -! T! !! S! ! !S! !G ! !=!-!T! H! -! T! total!=! !!

Would !!Stotal! be > 0 ?!

The Free Energy of Mixing

Polymer + Solvent For Mixing ! Mix !

! S! !! total! > 0! Gmix< ! 0! !!

The Mean Field Assumption

Each molecule is assumed to be acted upon by a potential that is an average taken over all the interactions in the system, rather than one determined by local composition . This allows us to treat the entropy and enthalpy changes upon mixing as separate and additive quantities. We will start by treating the entropy.

The Entropy of Mixing

First examine the simplest possible problem, mixing spherical molecules of equal size. If we can figure out the total number of ways all the molecules can be arranged, ", then we can use Boltzmanns equation;

S = k ln "
to calculate the entropy. But where on earth do you even start on a problem like this, when you have the jumbled up, randomly arranged mess that is the liquid state ?

The Entropy of Mixing

Lattice Model !

The Entropy of Mixing Small Molecules of Equal Size

If we start with nA molecules of type A and nB molecules of type B, then also assume that there are no holes on the lattice*, then there are just n0 = nA + nB lattice sites. Now we take all the molecules off the lattice and put them back on randomly one at a time, not caring, at this point, if its an A or a B. How many ways are there to put the first molecule on the lattice? A. nA B. nB C. n0

*This is equivalent to assuming that there is no free volume, or the fluid is incompressible.

The Entropy of Mixing Small Molecules of Equal Size

How many ways are there of putting two molecules on the lattice?

The Entropy of Mixing Small Molecules of Equal Size

There are n0 - 1 arrangements of the second molecule with first molecule placed here !
It must be (n0)(n0 - 1). OK, how many ways can you put 3 molecules back on the lattice? - youve got it, (n0)(n0 - 1) )(n0 - 2). So, the number of ways of putting all n0 molecules back on the lattice is, (n0)(n0 - 1) )(n0 - 2) (n0 - 3) - - - - (3)(2)(1). or n0 factorial, n0!

Another n0 - 1 arrangements with first molecule now placed here !

The Entropy of Mixing Small Molecules of Equal Size

Do we get a new distinguishable arrangement if we let these two molecules switch positions? !

The Entropy of Mixing Small Molecules of Equal Size

(nA + nB )! "= nA!nB! S = k ln" - !Sm = k(nA ln xA + nB ln xB) nA xA = nA + nB nB xB = nA + nB

ln(nA!) = nA ln nA - nA, etc

The Entropy of Mixing Small Molecules of Equal Size

Molecules !

- !Sm = k(nA ln xA + nB ln xB)

Moles !

- !Sm = R(nA ln xA + nB ln xB)

The Entropy of Mixing Molecules of Different Size

The Entropy of Mixing a Polymer and a Solvent

Model -the polymer is a chain of connected segments, each equal in size to a solvent molecule. !

The Entropy of Mixing a Polymer and a Solvent

A much more complex problem. Florys result;

- !Sm = R(nA ln # A + nB ln #$B )

where #A and #B are the volume fractions of the A and B components (say solvent and polymer), respectively. This is often called the combinatorial entropy of mixing.

The Entropy of Mixing

- !Sm = (n ln x + n ln x ) A A B B R
Regular Solution Theory !

- !Sm = (nA ln # A + nB ln #$B ) R

Flory - Huggins Theory !

Mole Fraction and Volume Fraction

The mole fraction of polymer is;

np! 1 $ xp! = = !!! np! + ns! 76

The volume fraction is;

#p =

np mVs! 25 $ = !!! np mVs + nsVs 100

The Entropy of Mixing

- !Sm = k(25 ln0.25 +75 ln0.75)!

- !Sm = k(1 ln0.25 +75 ln0.75)!

The Entropy of Mixing

The small entropy of mixing polymers is more seen if we express it on a per mole of lattice sites basis (i.e. divide by the number of moles of lattice sites = V/Vr)

- !Sm Vr = Vr [nA ln# A + nB ln #B ] R V V

Using

nAVr nAmAVr # A = = V VmA mA

nBVr nBmBVr # B = = V VmB mB

%# ( # S V S ! ! m r m == ' A ln# A + B ln # B* mB ' * R V R & mA )

The Enthalpy of Mixing

Increasing Interaction Strength! Non Polar
! ! ! !
Highly Polar

Dispersion Forces Dipole/dipole Interactions Hydrogen Bonding Coulombic Interactions

} !

Focus on dispersion and weak polar forces !

Nearest Neighbor Assumption

I can feel these guys !

But not these !

Interaction energy
! A ! A ! A ! A ! A ! B ! B ! B ! B ! B ! B ! A ! A
Let the attractive interaction energy between a pair of small A molecules be +AA. If we assume that we can simply add the interactions between all pairs, then we can say that the interaction of a chosen A molecule with all its nearest neighbors is z+AA, where z is the number of nearest neighbors.

! A

! B ! B

Do the same for the B molecules

Change in Interaction Energy

! A ! A ! B ! B
What we really want, however, is the change in energy on going from the pure to the mixed state. In order to calculate this we first consider the change in energy when we replace interactions between a pair of A molecules, AA, and pairs of B molecules, BB, with AB pairs. The energy change per AB pair is given by;

! B

! A

! B

! A ! % AB 1 = % AB - [% AA + % BB ] 2

The Heat of Mixing

! A ! A ! B ! A ! A ! B
Now all we have to do is multiply this by the number of AB pairs

! A ! B

! Hm = nAB !% AB
Then

! Hm = nA # B [z!% AB ]

Probability that a B is next to a chosen A is #B !

The Flory &$ Parameter

Flory defined the following interaction parameter, ,, which he made dimensionless by dividing by kT;

z!% AB &= kT
The heat of mixing is then simply

! Hm = kT [nA# B &]

The Flory-Huggins Equation

! Gm = ! Hm - T!Sm = kT [ nA# B& + nA ln # A + nB ln # B] ! Gm = nA ln# A + nB ln # B + nA# B& RT

Cohesive Energy Density

! A ! A ! A ! A ! A ! A ! B ! B ! B ! B ! B ! B ! B ! A ! A ! ! nA !E ! vap !! z! %!AA! CA ! A!=! =! V! 2V !A !!

Evap ! ! nB !! !! z! %!BB! CB ! B!=! =! V! 2V !B !!

! B

Cohesive Energy Density

! A ! A ! A ! B ! A ! A

! A

! A

CA ! B! =!?!
0! .! 5! 0! .! 5! CA ! B! =!CA ! A! CB ! B! 0.! ! 5! 0.! ! 5! 2! E ! ~ ! ( ! 2 C ! ! C ! C ! ) ! ( ! C ! C ! !! -! AB!-! AA!-! BB! =! AA! -! BB! )!

Solubility Parameters
'!A! =! C! !
0. 5 AA

!! !

0.! ! 5! C ! '!B! =! BB!

2! E ! ~ ! ( ! ) ! !! '!A!-!'!B! 2! ! ! =!(!nA ! !+!nB !! )! Vm !# ( ! ) ! !!Hm ! # ! ' ! ! ' ! ! A! B! A! B!

Vr 2 ' ' [ A B] RT Vr 2 & - 0.34 + [' A - ' B ] RT

& -

The Phase Behaviour of Polymer Solutions and Blends

Example of a phase separated or immiscible system !

One Condition for Mixing !

S! !! total! > 0! Gmix< ! 0! !!

The Phase Behaviour of Polymer Solutions and Blends

! G 'm ! Gm Vr # A #A ln ln # B + # A# B& = = #A + mA RT RT V mA Vr 2 & [' A - ' B ] RT
Polymer Blends ! Always Positive !

! G 'm ! Gm Vr # A # ln# A + A ln # B + # A# B& = = mA RT RT V mA

Small !

Positive !

Phase Behaviour
Single Phase

Vr 2 ' ' & [ A B] RT

(Miscible Mixture)

& = a+ b T

Temperature

Phase Separated (Immiscible) Composition

Phase Behaviour
!G ! 0 ! B2 ! xB1 ! xB2 ! 0 !

Q ! B1 ! Q* !

xB !

!G1 !

!G2 !

!Gtotal = !GQ = !G1 + !G2

Phase Behaviour
!G ! 0 ! B2 ! xB1 ! xB2 ! 0 !

Q ! B1 ! Q* !

xB !

!GQ* ! !GQ* < !GQ

The Chemical Potential and the Conditions for Phase Separation

!G ! 0 ! xB1 ! Q* ! B1 ! Q ! xB2 ! 0 !

B2 ! xB !

!G1 !

!G2 !

The Chemical Potential and the Conditions for Phase Separation

!G !

% (!G ( ' * = ' & (xB * ) xB1

or

% (! G ( ' * ' & (xB * ) xB 2 % (! G ( ' * ' & (nB * ) nB 2

2 B

0 !

xB1 !

xB2 !

0 !

% (!G ( ' * = ' & (nB * ) nB1

1 B

B1 ! B2 ! xB !

! = !

The Chemical Potential

2 ! 1 = ! B B

Composition B1

2 ! 1 = ! A A

Composition B2

The Flory-Huggins Chemical Potential

Composition B1

! Gm = ns ln# s + np ln # p + ns # p & RT % 1( 2 ! s ln( ) 1 - # p + * 1 - *# p + # p & = & M) RT

Composition B2

!G !

Phase Diagrams
B1 ! B2 ! xB !
2 ! 1 = ! s s

Temperature

UCST

Composition

More Phase Behaviour

!G ! 0 !

xB1 !
! S1 ! C

xB2 ! S2 ! B2 ! xB !

0 !

B1 !

!G !
! 0 ! B1 ! S1

0 ! S2 !

The Binodal and Spinodal

( !G =0 2 (xB
At the UCST we also have
2

B2 ! xB !

Temperature

UCST Binodal

( !G =0 3 (xB

Spinodal

Composition

The Conditions for Forming a Miscible Mixture

Temperature Single Phase

Phase Separated

Composition

We can now summarize our conditions for forming a single phase or miscible mixture; a) The free energy change on mixing should be negative. b) The second derivative of the free energy of mixing should be positive (which means a point of inflection on the free energy curve has not been reached and it is concave upwards across the composition range).

The Critical Value of

2 '

,.

Temperature

1 1 ( ( !Gm / RT ) = + - 2& = 0 2 # m # m A A B B (# A Tc! 1 1 ( (!Gm / RT ) =- 2 + 2 = 0 3 # A mA # B mB (#A

3 '

[#p]c$

Composition

% ( 1 1 &c = '1 + * 1/ 2 2' mp * & )

The Critical Value of

2 '

- Blends ,.

1 1 ( ( !Gm / RT ) = + - 2& = 0 2 # m # m A A B B (# A 1 1 ( (!Gm / RT ) =- 2 + 2 = 0 3 # A mA # B mB (#A [# A ]c = m

1 /2 B 3 '

mA1 / 2 + mB1 / 2
2

1% 1 1 ( &c = ' 1 / 2 + 1/ 2 * 2' mB * & mA )

The Critical Value of the Solubility Parameter Difference for Polymer Solutions
UCST Upper Critical Solution Temperature Temperature

% ( 1 1 &c = '1 + * 1/ 2 2' mp * & )

&c ~ 1 / 2
2 & c = 0.34 + Vr [' p - ' s ]c = 0.5 RT

[' p - ' s ] - 1
Composition

A Comparison of Theory and Experiment

20 15

T (0 C)

10 5 0 -5

Experimental! Data points! Flory - Huggins! Theory!

!
-10 0.00

0.05

0.10

Volume Fraction of Polymer

0.15

Values of ,. for Solutions of $Polystyrene in Cyclohexane

1.4!

1.2!

1.0!

& = &1 + &2 # p + &3# p 2 + - - - - -

0.8!

0.6!

FLORY - HUGGINS
0.4! 0.0! 0.2! 0.4! 0.6! 0.8! 1.0!

VOLUME FRACTION OF POLYMER!

The Lower Critical Solution Temperature

Phase Separated

Temperature

LCST - Lower Critical Solution Temperature Single Phase

Composition

The Lower Critical Solution Temperature

Temperature (C)

190

4800 10,300

140 100

19,800
50 0 -50 0.1

10,300 4800
0.2 0.3

Polymer volume fraction

The Lower Critical Solution Temperature

Phase Separated

Temperature

LCST - Lower Critical Solution Temperature UCST - Upper Critical Solution Temperature

An aside is in order here. The fact that the lower critical solution temperature is at a higher temperature than the upper critical solution temperature can be a bit confusing. The word lower in LCST is chosen to mean at the bottom (lowest temperature) of a two phase region, while the word upper in UCST designates the top of a two phase region.

Phase Separated

Composition

Some Limitations of the Flory - Huggins Theory

1. Based on a lattice model that uses various approximations in the counting process! ! 2. Ignores "free volume and only accounts for combinatorial entropy! ! 3. Assumes random mixing of chains in calculating the entropy and segments in calculating the enthalpy! ! 4. Only applies to non - polar molecules! ! 5. Does not Apply to Dilute Solutions! ! !

Dilute Solutions
!There is an intermolecular excluded volume effect in a good solvent (meaning & << 0.5, the critical value).! ! !There is also an intramolecular excluded volume effect, again in a good solvent, such that the chain expands its dimensions! relative to the usual end-to-end distance found in concentrated solutions or the melt. ! ! !The chain expansion varies with &, hence temperature, and there is a temperature, the theta temperature, where the chain again becomes ideal, or can be described by Gaussian statistics. ! ! !

The Theta Temperature

At high temperatures

%1 ) ~m ' &2
5 0. 5

( #p &* + + - - - - - ) 3 ~m
0. 6

Temperature

2 0 .5

~)m

0 .5

At the * temperature

1 &+ 2 R
2 0 .5

~m

0 .5