Polymer Characterization

1. 2. 2.1 2.2 2.3 2.4 2.5 Polymer Properties and Characterization Methods The Single Macromolecule, Polymer Chain Configuration Conformation - models of polymer chains, end-to-end-distance, radius of gyration, concentration range, entanglement, rubber elasticity Constitution - Linear, Branched and Cross-linked Polymers The Statistical Character of Polymer Properties - molecular weight, chemical heterogeneity, tacticity The Polymer Solution - solubility of polymers, dilute polymer solution, the FLORY-HUGGINSeq., solubility parameter, - phase separation, theta-temperature

3 3.0 3.1

Determination of Molar Masses Overview Colligative Properties - thermodynamic relations 3.2 Vapor Pressure Osmosis 3.3 Membrane Osmosis (3.4 End group analysis) 4 4.1 4.2 4.3 Scattering Methods RAYLEIGH-Scattering - determination of weight-average molecular weight DEBYE-Scattering - determination of shape and size of macromolecules, the scattering function Dynamic Light Scattering - diffusion coefficient, hydrodynamic radius Ultracentrifuge

5.

6. Viscometry of Dilute Polymer Solution - KUHN-MARK-HOUWINK-eq., FLORY-FOX-eq.

7. 7.1

Molecular Weight Distribution General Characterization of Distribution Curves - mathematical formalism, types of m.w.d. 7.2 Separation effects and methods for polymer fractionation 7.3 Polymer-Chromatography - Fundamental, HPLC, SEC, equipment, application, detectors (7.4 Field-Flow-Fractionation) 8. Nonlinear Polymers 8.1 Branched Polymers - short chain branching - long chain branching 8.2 Cross-linked Polymers - mechanical properties - swelling

Copyright 2008 by Karl-Fr. Arndt Physical Chemistry of Polymers TU Dresden, D-01062 Dresden, Germany No part of this booklet (esp. figures!) may be reproduced or copied in any form or by any means without permission! Only for personal use!

1. Polymer Properties and Characterization Methods

Polymer solution: Polymer chains in dilute solutions are isolated and interact with each other only during brief times of encounter determination of structural parameters of single chains by measurements of the properties of a polymer solution:
molecular weight

osmometry (membrane, vapour) light scattering (static, dynamic) viscometry of dilute polymer solution ultracentrifugtion molecular weight distribution fractionation gel chromatography chemical heterogeneity special techniques of chromatography and fractionation (combined methods) chain length light scattering viscometry (hydrodynamic properties) diffusion coefficient dynamic light scattering shape of polymer chain scattering methods branching determination of typical dimensions of macromolecules LCB spectroscopy (number of end-groups) SCB swelling change of macroscopic dimension of a cross-linked polymer determination of cross-linking density

further aims of investigations of polymer solutions: solubility of polymers (thermodynamic of polymer solution, interaction polymer solvent) concentration range (dilute regime semi-dilute regime) polymer solution at high concentration

2.

The Single Macromolecule, Polymer Chain

2.1 Configuration Position and arrangement of atoms in a polymeric chain can be divided into two categories:
- Position fixed by chemical bonds (cis- or trans-isomers). This kind of order which can be changed only by disrupting chemical bondsand is known as configuration. - Structural differences originating from rotations around single bonds (various forms of polymer chains in solution); conformation

2.2 Conformation Freely Rotating Chain

C C C lCC: 0.154 nm (1.54 ) CCC (): 109.5

0.252 nm
2 h o, f = nCC lCC

1 cos 2 = 2 nCC lCC ~ M 1.0 1 + cos

Restricted Rotation

2 h o,r = nb lb

1 cos 1 + cos 1 + cos 1 cos = h o, f

: steric factor, hindrance parameter

cos =

0 exp(U ( ) / kT ) cos d 0 exp(U ( ) / kT ) d

ns = 7

Freely Jointed Chain

KUNH segment chain ns = number of segments ls ls = length of one segment; ls = f (chain stiffness)

h: end-to-end distance

3 w(x, y,z) dxdydz = 2 h o

Cartesian coordinates

3/ 2

3( x + y + z ) dx dy dz exp 2 h o

w(h): density function of distribution of h:

3 w( h) dh = 2 h o
3/ 2

3 h 4 h dh exp 2 h o

spherically symmetrical

Mean-Square Value:

h o = dh w( h)h = ns ls ~ M 1.0
0

*)

unperturbed (undisturbed) dimension (sum of all interactions = 0 ! see theta-condition) Contour length: maximum chain length hmax = ns ls hmax = nsls ~ M , for vinyl-polymer:
*)
0

hmax = nCC lcc(eff) = 2 (M/Mo) lcc(eff) = ns ls ns = 2 (M/Mo) (lcc(eff)/ls)

2 n ax

dx =

1 3...( 2 n 1) 2 n + 1 a n + 1/ 2

Radius of Gyration

s o =

1 2n

i j

2 rij =

1 n +1

si2
i

Characteristic Ratio C:
2 h o = ns ls2 = nCC lCC C n ; lim C n = C

Radius of gyration and characteristic chain dimension of different types of macromolecules:

Shape of macromolecule unperturbed coil random coil, good solvent thin rod, length L hard sphere, radius R *) disc, radius R ellipsoid *) Example:
r= R

Characteristic dimension Characteristic dimension radius of gyration molecular weight <h>o = 6 <r>o <h> = (2 +)(3 + ) <r> <L> = 12 <r> <R> = (5/3) <r> <R> = 2 <r> (a + b + c) = 5 <r> <h>o ~ M <h> ~ M 1 + L~M R~ M1/3 R ~ M1/2

< r > = r = 0

r 4r dr
r =0

r= R

4r dr

3 = R 5

2.3 Constitution
Branching long chain branching (LCB): < 10 C-atoms broader m.w.d. influences melt and solution properties short chain branching (SCB): 2...6 C-atoms influences properties in solid state (crystallinity, density) e.g. polyethylene: PE-HD (high-density): 1..10 SCB/1000 C-atoms PE-LD (low density): SCB + LCB PE-LLD (linear-low-density): copolymerisation with 1-olefins, 10...40 SCB/1000 C-atoms

other branched structures: hyperbranched polymers dendritic polymers Crosslinking elastomers (rubber) high-crosslinked polymers (e.g. epoxy-resin) interpenetrated networks

2.4 The Statistical Character of Polymer Properties Polydispersity and Mechanism of Polymerization
Formation of polymers from monomers is divided into two reaction classes: - step-growth (step polymerization, step polyaddition) polymerization - chain-growth (or addition) polymerization Distinction between these processes can be made on mechanistic grounds (dissimilar reaction kinetics): different distributions of species as a function of the extent of reaction different molecular weight distribution (m.w.d.) step growth reaction: 1 monomer + monomer, monomer + oligomer, monomer/oligomer + macromolecules, macromolecules + macromolecules (polycondensation : PA, PC ; polyaddition : PUR, EP) chain-growth reaction: 2 monomer + macromolecule (polymerization: PE, PVC, PP, other vinyl-polymers)

P n 2 T2 > T1

2 t

1 1 M

reaction time n = Zahl der Molekle

t1 <

t2 < t3 <

t4

Distributions and Statistical Weights

g = fraction distribution of a property Q moment of a distribution (general definition): frequencyg
discontinuous
Qg =

gi Qia 1 i a gi
i

cumulative-distribution g

g
continuous

Average Molecular Weights

Average Number, Mn Statistical Weight ni Definition

ni M i Mn = i ni
i

Alternative Form

wi i Mn = w i / Mi
i

Weight, Mw

wi

wi M i Mw = i wi
i

ni M i2 Mw = i ni M i
i

z-averaged, Mz

zi

zi M i Mz = i zi
i

wi M i2 Mw = i wi M i
i

Viscosity-average, wi M0

M =

i wi
i

wi M ia

1 a

Polydispersity and Mechanism of Polymerization

The width of a molecular mass distribution curve is characterized by the ratios of averages of molecular mass (polydispersity index, Q = Mw/Mn), combined with one absolute value of an average mass (Mw). Also (Q 1) = U is used, U = non-uniformity index (SCHULZsche Uneinheitlichkeit); U = (n/Mn)
= ( x ) f ( x ) dx ;
+
0

x f ( x ) dx
+

2 n=
+ 0

( M M n ) h( M ) dM ;

Mn =

M h( M ) dM
0

h( M ) dM =1

or: gw = (w/Mw) = Mz/Mw = 1 as a measure of polydispersity

The numerical value of Q is determined by the reaction mechanism of the polymerization and by the condtions (p, T..) under which it was carried out. Living Polymers Condensation polymers Addition polymers Anionic Group-transfer Step reaction of bifunctional monomers Radical addition Kationic addition Coordination-polym. (metal-organic complexes) Mw/Mn = 1.01.05 ~2 2 10 2 30 2 50 at the gel-point

Branched polymers Radical addition Network polymers Step-reaction of tri-, tetrafunctional monomers

2.5 Thermodynamics of Polymer Solutions

Notation: A = solvent; B = solute (polymer) in case of copolymers or multi-component systems: 1 = solvent; 2, 3polymer

Entropy of mixing: The Flory-Huggins theory (1)

Deviation of polymer solutions from ideal behavior is mainly due to low mixing entropy. This is the consequence of the range of difference in molecular dimensions between polymer and solvent.

Flory (1942) and Huggins (1942)

Calculation of Gm = G (A,B) - {G (A) + G (B)} H = 0 Gm = -T Sm lattice model transfer of the polymer chains from a pure, perfectly ordered state to a state of disorder

 mixing process of the flexible chains with solvent molecules Sm = S (NA, NB) - {S(NA) + S(NB)}

Sm

= -R (nA ln A + nB ln B)

A = volume fraction solvent = NA/K = nAVA/( nAVA + nBVB) B = volume fraction polymer = NB/K = nBVB/( nAVA + nBVB) Flory-Huggins theory (3); chemical potential A

= RT ln aA = RT (ln A + (1 - VA/VB) B) B = RT ln aB = RT (ln B + (1 VB/VA) A) A = f (M) !

VA/VB = [BMA/AMO] 1/P VA/VB ~ 1/P ~1/MB Enthalpy change of mixing

= RT nA B = Huggins interaction parameter

H

Gibbs enthalpy based on Flory-Huggins theory:

Gm

= RT (nA ln A + nB ln B + nA B )

Theta-temperature and Phase separation (1) critical point:

B,c = 1 1+ VB / VA ; c = 1 + 2 VA V + A VB 2 VB

Solubility Parameter
The strength of the intermolecular forces between the polymer molecules is equal to the cohesive energy density (CED), which is the molar energy of vaporization per unit volume. Since intermolecular interactions of solvent and solute must be overcome when a solute dissolves, CED values may be used to predict solubility. 1926, Hildebrand showed a relationship between solubility and the internal pressure of the solvent; 1931, Scatchard incorporated the CED concept into Hildebrands eq.

2 H V

(nonpolar solvent; H = heat of vaporization)

heat of mixing: Hm = VAB(A - B) = nAVAB (A - B)

Like dissolves like is not a quantitative expression! Problems: polymers with high crystallinity; polar polymers hydrogen-bonded solvents or polymers additional terms

The square root of cohesive energy density is called solubility parameter. It is widely used for correlating polymer solvent interactions. For the solubility of polymer P in solvent S (P - S) has to be small!

3. Determination of Molar Masses

3.0 Overview Method absolute Osmometry Isothermal distillation Ebullioscopy Cryoscopy Vapor pressure osmometry*) Scattering methods Ultracentrifugation relative Viscosity Size exclusion chromatography equivalent End group determination Molar mass average Mn Mn Mn Mn Mn Mw Mw, Mz M M n, M w , M z Range (g/mol) **) 104 < M < 106 M < 104 M < 104 M < 104 M < 104 M > 5 102 M > 102 M > 103 M < 106

Mn

M < 5 104

*) relative method due to experimental condition **) depends on experimental condition (solvent, polymer, equipment..) ***) parameter of Kuhn-Mark-Houwink equation were determined only in a small range of molar mass, KMH is not valid in low molar mass range.

3.1 Colligative properties:

cryoscopy: ebulliometry:
Tm = Tm,0 Tm =
2 RTm ,0 x B

H m

xB

Tb = Tb Tb,0 =

RTb2,0 x B H b

xB ;

xB c

MA MB

Relative Comparison of the Sensitivity of Various Colligative Properties*) Property Mn = 104 g/mol Mn = 105 g/mol Osmotic pressure (cm 30 3 solvent) Vapor pressure 8 x 10-3 8 x 10-4 lowering (cm Hg) Freezing point 5 x 10-3 5 x 10-4 depression (C) Boiling point 2.5 x 10-3 2.5 x 10-4 evaluation (C) *) 1% solution of polystyrene in benzene, 25C Mn = 106 g/mol 0.3 8 x 10-5 5 x 10-5 2.5 x 10-5

only vapor pressure osmometry is used in polymer (oligomer) characterization

3.2 Vapor Pressure Osmometry

Measurement
T = H b RTo2

Data evaluation
ln a A with FH equ.

1 T = + K A c e 2, v A c Mn
solv. solution

T/c

solvent

Ke = calibration constant; c = g/g; Mn > 103 g/mol: A2,v = A2,0

3.3 Osmotic Pressure

The measurement of osmotic pressure is the most important method for the determination of the number average molar mass Mn. Schematic representation of the osmotic pressure between solvent () and solution ()

Osmotic equation: Data evaluation:

cB

1 RT + B c B = RT + A2 c B Mn Mn

4. Scattering Methods
4.1 Rayleigh-Scattering
Lord RAYLEIGH (1842-1919):

Intensity of scattered light ~ (wave length)-4 We measure the reduced scattered intensity (RAYLEIGH I( ) r 2 R = R ( solution) - R ( solvent) ratio) R : I
o

primary radiation (incident beam)

angle of observation, r distance sample-detector, Io intensity of the Concentration fluctuations determine the intensity of the scattered light:
K cB 1 c 2 = ; = R T B + A 2 c B M R R T cB T 1 = R T + 2A 2 c B M cB T
2 n 2 4 2 n o c F( ) N L 4 B o

with K = optical constant:

K=

F(): polarization of the primary light and dependence of the effective scattering volume on the scattering angle (1/sin): 1 F( ) = (sin ) vertical pol.:
1 + cos 2 non-polarized: F( ) = 2 sin

cos 2 horizontal pol.: F( ) = sin

Light-scattering equation
monodisperse:

K cB 1 = + 2 A 2 c B + ...... R M

polydisperse:

K cB 1 = + 2 A 2 c B + ...... R M w

4.2 DEBYE-Scattering (M > 105 g/mol)

interference between the light scattered from various positions on the particle (intramolecular interference):

K cB 1 = + 2 A 2 c B + ...... R P ( ) M w
particle scattering function P(): P() = R()/R( = 0) sin(qrij ) 1 P( ) = 2 qrij N i j
P( ) = 1 Mw R K c B C 0

q scattering vector:

q =( 4 / )sin / 2 ; = o / n

For q rij << 1 (that means: small particles, all angles; or: large particles, small angles) follows:
1 1 P( ) =1- q 2 r 2 ; P( ) -1 =1+ q 2 r 2 3 3
Light-scattering equation, intramolecular interference

K cB 1 16 2 2 1+ r = 2 R ( , c B ) M w 3
R = 0; c = 0 R()c=0

sin / 2 + 2 A 2 c B Z
2

R (cB) =0

z-average of radius of gyration:

s2
Z

r2

wi Mi =
Mw

r2

Zimm-Plot

4.3 Dynamic Light Scattering Fundamental

Due to the Brownian motion of the scattering particles, a shift of the frequency of the scattered light occurs in analogy to the well-known Doppler effect of acoustic waves Light ~ 1015 Hz; : 105....107 Hz). In principle, the diffusion coefficient D of the particles may be obtained from an analysis of the line width of the spectral density profile of the scattered light intensity.

Hydrodynamic radius: kB T Rh = 6 A D

5. Ultracentrifugation
- absolute method - large scale of molar masses between 10 and 109 g/mol - besides the molar mass and molar mass distribution the AUC makes it possible to determine sedimenation coefficients, diffusion coefficients, and virial coefficients. Sedimentation velocity large angular velocities, Svedberg equation
friction force = centrifugal force buoyancy force
K f = Ks f df M B = x (1 A v B ) dt N L

with f = kBT/D

f = friction c. ; D = diffusion c. dx / dt and s = x s = sedimentation c.; s ~ Ma

MB =

RT s D 1 A v B

Svedberg-equ. Sedimentation equilibrium

cross-section q net-mass transport: dm/dt = dms/dt + dmD/dt

Diffusion
dmD/dt

Sedimentation
dms/dt

equilibrium: dm/dt = 0 !

c dm = q s cB x D B = 0 x dt
M

2 c B (x) = c B (x = x b ) exp B (1 A v B ) ( x x b ) cB s cB x = D x RT

xb = bottom

c B,2 MB = R Tln c B,1

[(1

2 v B ) x 2 2 x1

)] ;

concentration at two x-values

Experiments
Powerful tool, especially for complicated systems such as polyelectrolytes, polymers with microgels, heterogeneous polymers, and copolymers (sedimentation in a density gradient). ....60,000 rpm; equilibrium hours...2 days; multicell-rotors different detectors

6. Viscometry of Dilute Polymer Solution

Viscometry is the most widely utilized method for the characterization of polymer molecular mass since it provides the easiest and most rapid means of obtaining molecular massrelated data and requires a minimum amount of instrumentation. A most obvious characteristic of polymer solutions is their high viscosity, even when amount of added polymer is small.

left: velocity profile, flow through a tube right: velocity gradient in a macromolecule relatively to the center of mass: - - - - freely-draining; partially-draining

As a result of the velocity distribution the macromolecule rotates, and energy is dissipated (internal friction). The higher the internal friction in the fluid, the higher is the stress to maintain the velocity gradient. increase of viscosity

Measurement of viscosity:
HAGEN-POISEUILLE`s law:

r 4g h t = = A t ~ t 8l V
Hagenbach-correction, correction for contribution to kinetic energy:
B = A ; for t > 100 s no correction ; t t

experimental determination of B:

/t vs. 1/t

The limiting viscosity number (intrinsic viscosity):

[] = lim c

sp 1 0 = lim ; cB B 0

c B 0;

G 0,

laminar

Nomenclature of solution viscosity (IUPAC):

Viscosity ratio (relative viscosity): Specific viscosity: Viscosity number (reduced viscosity): Logarithmic viscosity number (inherent viscosity):
rel = 0 = t / t0
sp = rel 1= t t0 t0 red = sp cB inh = ln rel cB

Limiting viscosity number (STAUDINGER index, intrinsic viscosity): [] o = viscosity of solvent

Determination of the limiting viscosity:

SCHULZ-BLASCHKE: HUGGINS: KRAEMER: red = kSB []sp + [] red = kH [] cB + [] inh = kK [] cB + []

Limiting viscosity number and molecular weight KUHN-MARK-HOUWINK: [ ] = K M

rodlike molecule: random coil freely-draining limit : non-draining limit (theta conditions): sphere: disk:
a

a = 2 a = 0.6....0.9 a = 1 a = 0.5 a = 0 a = 0.5

Experimental:
Common solution viscometers: a) OSTWALD-viscometer b) UBBELOHDE-viscometer

PHILIPOFFs rule (empirical):

M =

[] =

wi

w i [ ]i

wi Mi wi
a

1/ a

FLORY-FOX eq. (r = <r>/<r>o)

[] = 6

3 2

0 , h r

r M

3 2

7.

Molecular Weight Distribution

7.1 General Characterization of Distribution Curves

h(M) density function of number frequency distribution H(M) density function of mass frequency distribution H(M) = M h(M) I(M) distribution function, frequently termed integral mmd (M = P M0; P = polymerization degree
M

I(M) =

H(M) dM

; H(M)=

dI(M) dM

molecular inhomogeneity, polydispersity

2 U= 2 n Pn = Pw Pn 1; 2 g w = 2 w Pw = Pz Pw 1

Distribution Functions:
SCHULZ-ZIMM (FLORY):

P 1 h(P) = exp ; Pn Pn
SCHULZ-ZIMM (FLORY):

1-parameter (Pn)

h(P)dP = 1
2-parameter (k,Pn)

( ) H(P) =
k Pn

k +1

k!

k P P exp ; P n
k

H(P)dP = 1
0

Evaluation of mean values: PH(P)dP k + 1 P 2 H(P) dP k + 2 Pw = = Pn ; Pz = = Pn k k H(P)dP P H(P) dP dH( P ) P(max): = 0 for P = Pn dP U = Pw/Pn 1 = 1/k
0

n ax

dx =

(n + 1) a n +1

; (n + 1) = n (n) ( = n! if n > 0; whole number)

POISSON-Distribution
h(P) =
P Pn exp( Pn ) P!Pn

Pw = 1+ Pn; U = 1/Pn

living polymerization WESSLAU-Distribution

ln P / P 2 1 o h(P)= exp I(lnPo) = 0.5; = (dI(P)/dP)P=Po P Pn = Poexp(-/4); Pw = Poexp(/4); 1

SCHULZ-ZIMM (FLORY): k = coupling constant, numerical value depends on termination reaction (radical polymerization)
k = 1 : disproportionation ( hydrogen abstraction from one growing chain by the radical end of another) two chains - unsaturated terminal unit - saturated chain end k = 2 : combination (formation of a -bond, when free radical sites collide, formation of one chain k = 1.5 : chain transfer to solvent molecules, monomers, polymerization regulators (no branches) or other polymer chain backbone branching

7.2 Separation Effects and Methods for Polymer Fractionation Separation effects
Thermodynamic properties precipitation fractionation
solubility fractionated extraction solubility fractionation with or without supporting materials with solvents/precipitation agents and/or temperature gradients in separation columns thin-layer chromatography (separating copolymers acc. to chemical heterogeneity) ultrazentrifugation field-flow-fractionation migration in an electrical electrophoresis field

Separation methods

adsorbability

Kinetic effects
diffusion and sedimentation

Particle size effects

size exclusion chromatography field-flow-fractionation

Combination of different separation effects! Experimental - Fractional Precipitation

Addition of nonsolvent (or precipitant) (continuously column fractionation, discontinuously fractionation flask) Elimination of solvent by evaporation (not common) Lowering the temperature of the system (ucst, or vice versa) (experiment is carried out in one solvent, volume of system is constant, control of fraction size can be adjusted more precisely)

- Fractional Solution
Fractionation by direct extraction (successive extraction of polymer with a series of solvents) Fractionation by film extraction

(FUCHS, 5-10 m film of the polymer is deposited onto an aluminum foil by dipping the foil into the polymer solution) Fractionation by coacervate extraction (coacervate = polymer-rich liquid phase; addition of a nonsolvent until essentially all of the polymer is in the coacervate, polymer-poor phase is removed and polymer in it is isolated, then extraction of the coacervate...)

- Fractionation by column elution

(polymer on a support, e.g. glass beads, gradient elution increasing content of solvent in the nonsolvent, additional temperature gradient)

- Turbidimetric Titration
fractional precipitation, a nonsolvent is slowly added to a dilute polymer solution, the polymer is precipitated selectively, the concentration of precipitated polymer is measured by optical methods (turbidity of the liquid phase) Applying the method to copolymers (block and graft copolymers): information is desired concerning the extent of copolymer formation and the amount of homopolymer present cloud point titration: cloud point depends on the chemical constitution

7.3 Separation effects in high performance liquid chromatography (HPLC) and size exclusion chromatography (SEC):
HPLC: energetic effects (enthalpic); interaction between the stationary phase and the molecules. HPLC utilizes columns that are intended to encourage adsorption and partition mechanism. Reversed phase columns: the packings are less polar than the mobile phase Binary, ternary...miscible mixtures of organic solvents and water are employed (isocratic elution: constant ratio; gradient elution: ratio vary with time)

HPLC is used to analyze small molecules (end-group), and copolymers

retention time ~ A + B lg M SEC: entropic effects, conformation of the macromolecules

retention time ~ A - B lg M Detector combinations and their application (SEC):

concentration concentration and size RI; UV; FTIR RI and viscosity copolymers molecular weigth distribution, long-chainbranching, constants of KMH molecular mass (absolute!), radius of gyration, microgels, association, separation process

RI and light-scattering

Calibration of SEC
Calibration with narrow standards: Ve = f (lg Mstandard) Ve = A B lg M
Problem: A, B = f (polymer, solvent, exp. condition) In the general case the lgM Ve dependence is not linear and can be

V = approximated by polynomials of the form: e

a (lgM)
i i= 0

(Calibration by using broad (polydisperse) standards with known molecularweight distribution is possible, but complicate. ) MWD of standards logarithmic normal distribution: maxima in their chromatograms can be related to M = (Mw Mn)1/2. hydrodynamic volume: Vh = [] M/2.5 Vh = molar volume of impenetrable spheres which would have the same frictional properties or enhance the viscosity to the same degree as the actual polymer in solution 1966 Benoit, Grubisic, Rempp: at constant Ve []x Mx = []PS MPS x indicate data of unknown polymer, PS indicate data of calibration standard With Kuhn-Mark-Houwink follows:

Universal Calibration:

lg M x =

K ,PS 1 + a ,PS 1 lg + lg M PS 1+ a ,x K ,x 1 + a ,x

MW of unknown sample can be calculated if K0,x and a0,x are known!

If K0,x and a0,x are not available, Mx can be derived from measurements performed with an SEC equipped with an online viscosity detector. []x,i Mx,i vs Ve,i is measured , equivalent to []PS,i MPS,i vs Ve,i

Mx,i

or: direct monitoring of MW by light-scattering detector!

Molecular Weight Distribution: w(M) = F(Ve) [dVe/dM]

7.4 Field-Flow-Fractionation
The separation takes place in a thin, open channel through which samples are transported by a laminar flow of liquid (1966 Giddings). The action of a field, applied perpendicular to the channel flow, causes a partitioning of the various components into regions of different flow velocities differential migration and separation. centrifugal fields for the characterization of colloidal materials; electrical fields for protein separation and purification; thermal gradient thermal FFF; hydraulic gradient flow FFF; In contrast to SEC: analysis in an open channel with defined dimension, formulation of rigorous theories for both retention and column dispersion! Retention Mechanism:
x x=w flow (v(x)) field

Side view of the FFF channel field perpendicular to separation axis (z)
z

x=0 parabolic velocity profile v(x): v(x) = 6 v

x x w w

Sample is exposed to the field minimization of potential energy steady state velocity U (proportional to the strength of interaction with the field). The migration is hindered by the channel wall formation of a layer with thickness l = D/U;
D = diffusion coefficient (back diffusion)

concentration distribution: c(x) = c(x=0) exp(-x/l);

l = thickness of the distribution of particles (fractionation, if lA lB)

with: U = F/f; D = kT/f

l = kT/F

F = force, f = friction coefficient

8. Nonlinear Polymers
8.1 Branched Polymers: comb-model star-model tree-model Structural parameters for describing branching structures:
- type of branching, e.g. star, comb - average number of branching-points per molecule, branching density or branching frequency - functionality of branching points - number of branching end points - average length of side branch and no-branched chain - distribution of branch lengths, non-branched chain segments, - average molecular weight and distribution of backbone chain
Influence of chain branching on polymer properties: SCB Crystallinity Density Melting point Dielectric constant Creep and fracture LCB Limiting viscosity Elution volume in SEC Sedimentation Virial coefficient Angular distribution of scattered light intensity Radius of gyration

short chain branching (SCB) long chain branching (LCB)

Determination of total number of branches: determination of the concentration of end-groups compared

with C-atoms in the backbone (CH3/ 1000 CH2); IR - Method (LDPE: absorption at 1378 cm-1) 1 -H nmr (LDPE: CH3 at 9.11 ppm; CH2 at 8.72 ppm) 13 -C nmr (side chains up to C6)

Specific methods for determination of SCB:

-C nmr spectrum; branch length and their concentration (e.g.LDPE: n-butyl: 67 %; n-pentyl: 12 %; n-ethyl: 8; n-hexyl and longer: 5 %) Degradation, scission of branches at branch points (PVAc: saponification of ester branch units and calculation of initial and final molecular weight) Radiolysis gas chromatography: analysis of the decomposition gases
13

Determination of LCB:
Branched molecules have a smaller coil dimension than a linear molecule of the same molecular weight. shrinking factor g < r > o ,br radius of gyration g o = < r > o ,lin M = M br lin

viscosity

< > o ,br R 3/ 2 = go = h 3 ; h = h ,br g o = R h ,lin < > o ,lin M br = M lin

b . experiments: g = g ; 0.5 b 15

Theoretical equations relating the shrinking factor (branching degree) and the number of branch points, were derived - by ZIMM and STOCKMAYER for randomly branched monodisperse and polydisperse polymers; - by OROFINO and BERRY for star-branched polymers.

Experimental background:

Viscosity
lg[]

Light scattering
<r>

lg M (--- branched polymer; ____ linear polymer)

lg M

8.2 Cross-linked Polymers

chemically cross-linked polymer interpenetrating network

physically cross-linked

f = functionality; = cross-linking density Mc = Molecular weight of the cross-linked chain = B/Mc

Rubber-Elasticity-Theory (RET):
A rubber represents an ensemble of polymer chains, each one running between two cross-links (junction points). It is necessary two assume correlation between the macroscopic dimension of the sample and the chain dimension (deformation model). no hindrance at deformation phantom-network Gaussian distribution of chain length; only change of entropy (U = 0); no volume change at deformation (Vdef = Vnondef; xyz = 1) affine deformation: the cross-link points are fixed within the sample; their displacement is linear in the macroscopic strain (other limit: free-fluctuating phantom network)
= ART 2

= stress (force/area non-deformed sample) = deformation ratio (x = xdef/xo; xo = non-deformed dimension) = memory-term (depends on polymer concentration at cross-linking, (dry state: = 1) A = microstructure factor; A = 1 affine deformation, A = (1 2/f) freefluctuating

Experimental Background:
a) compression of swollen sample b) stress-strain

Swelling, the FLORY-REHNER-eq.:

Two competing processes take place: - increase of entropy as a result of the introduction of solvent molecules - decrease of entropy of the network chain as a result of the dilation

Swelling degree: Q = Vswollen/Vnon-swollen = 1/(volume fraction polymer) or: Qm = (mpolymer + msolvent)/mpolymer (independent of T !)

FR: 1943, statistical theory, calculation of change of freeenergy or chemical potential of solvent due to swelling measurement of Q Mc;