324 Makromol. Chem., Macromol. Symp.

61,324-341 (1992)

CHARACTERIZATION OF POLYMER MOLECULAR MASS DISTRIBUTION

FROM RHEOLOGICAL MEASUREMENTS

M. Fleissner
Hoechst AG, D-6230 F r a n k f u r t / M 80

A b s t r a c t : V a r i o u s methods f o r t h e d e t e r m i n a t i o n o f molec-
u l a r mass d i s t r i b u t i o n f r o m r h e o l o g i c a l measurements o f
polymer m e l t s a r e i n t r o d u c e d . Shear v i s c o s i t y , e n t r a n c e
p r e s s u r e l o s s , r e c o v e r a b l e s h e a r , and i n p a r t i c u l a r t h e
dynamic v i s c o e l a s t i c i t y d a t a G ' and G " a r e d i s c u s s e d as
a n a l y t i c a l t o o l s t o e v a l u a t e t h e m o l e c u l a r mass d i s t r i b u -
t i o n . Well c h a r a c t e r i z e d samples and homologous s e r i e s o f
t h e polymers PS, PE-HD, PP, and PTFE were measured t o
check t h e methods. P r e c i s e and r e l i a b l e r e s u l t s can be
o b t a i n e d by c a l c u l a t i n g t h e m o l e c u l a r mass d i s t r i b u t i o n
f r o m t h e f r e q u e n c y dependence o f t h e s t o r a g e modulus.

INTRODUCTION

The c l a s s i c a l methods f o r the determination o f m o l e c u l a r mass

and m o l e c u l a r mass d i s t r i b u t i o n r e l y on measurements o f p o l y m e r s
i n d i l u t e solutions. An e s s e n t i a l f e a t u r e o f f l e x i b l e p o l y m e r s ,
however, the presence o f entanglement c o u p l i n g s creating net-
works with rubber-like properties, i s purposely suppressed in
d i l u t e solutions. T h i s v i s c o e l a s t i c b e h a v i o u r o f polymer m e l t s -
the rheological properties i n the undiluted state - strongly
depends on the structure of these entanglement networks and
hence r e f l e c t s v e r y s e n s i t i v e d f f e r e n c e s i n t h e m o l e c u l a r com-
position.

The i n f l u e n c e o f m o l e c u l a r mass d i s t r i b u t i o n on t h e r h e o l o g i c a l
p r o p e r t i e s o f polymers i s quite well understood today: but the
comprehension o f t h e o p p o s i t e problem, t h e e v a l u a t i o n o f molecu-
l a r mass d i s t r i b u t i o n from rheological measurements, has o n l y
recently l e f t t h e stage o f q u a l i t a t i v e p r e d i c t i o n s . The impetus
f o r many e x p e r i m e n t a l and t h e o r e t i c a l p a p e r s was t h e p r a c t i c a l
interest t o u n d e r s t a n d t h e r e l a t i o n s h i p between polymer struc-
ture (polymer s y n t h e s i s ) and p r o c e s s i n g b e h a v i o u r , as w e l l the
s c i e n t i f i c e f f o r t t o model t h e markedly v i s c o e l a s t i c c h a r a c t e r -
istics of polymer melts and to determine the interrelations
among the material functions. In addition, the necessity to
describe insoluble polymers - where classical methods fail -
s t i m u l a t e d research i n v e s t i g a t i n g t h e v i s c o e l a s t i c behaviour o f

0 1992 Huthig & Wepf Verlag, Basel CCC 0258-0322/92/$ 04.00

 325

t h e m e l t s t o determine t h e molecular mass (MM) and t h e molecular

mass d i s t r i b u t i o n (MMD).

DETERMINATION OF THE RELATIVE MOLECULAR MASS

The b e s t known r e l a t i o n between a rheological property and a

molecular q u a n t i t y i s t h e connection o f t h e shear v i s c o s i t y in
t h e l i n e a r v i s c o e l a s t i c range w i t h molecular mass. The r e l a t i o n
d e r i v e d by Bueche - zero shear v i s c o s i t y i s proportional t o the
3 . 5 t h power o f molecular mass - has been confirmed by experimen-
tation; n e a r l y w i t h o u t e x c e p t i o n a p r o p o r t i o n a l i t y t o t h e 3.4th
power i s found. I n addition, i t was e s t a b l i s h e d t h a t t h e mass
average of the molecular
mass distribution must be
i n s e r t e d as molecular mass,
independent o f t h e w i d t h and
the type of the distribu-
tions. Fig.1 illustrates
this relationship for a
homologous series of high
density polyethylenes and
polypropylenes with differ-
ent molecular masses and
molecular mass d i s t r i b u t i o n s
(3,2 I Mw/Mn 5 11). The com-
p a r i s o n PE - PP demonstrates
that the viscosity at com-
parable chain l engt h - MMpp
= 1,5*MMp~ - i s v e r y depend-
e n t on c h a i n f l e x i b i l i t y .
Fig.1 Zero shear v i s c o s i t y versus
molecular mass

RHEOLOGICAL CHARACTERIZATION OF POLYMER MELTS

In the following discussion of relations between rheological

p r o p e r t i e s and molecular p o l y d i s p e r s i t y , i t i s assumed t h a t t h e
reader i s f a m i l i a r w i t h r h e o l o g i c a l c h a r a c t e r i z a t i o n o f polymer
melts. I n t h i s treatment, t h e d e s c r i p t i o n o f t h e l i n e a r visco-
e l a s t i c behaviour i s based on t h e frequency dependencies o f t h e
s t o r a g e modulus G ' , the l o s s modulus G " , and t h e complex v i s -
326

cosity q*. The s t u d i e s o f molten polymers w i t h small amplitude

o s c i l l a t o r y shear deformations belong t o t h e c l a s s i c a l e x p e r i -
mental methods. I n t h e dynamic experiment, t h e components G ' and
G " o f t h e complex modulus c h a r a c t e r i z e t h e e l a s t i c and t h e v i s -
cous response o f the m a t e r i a l s (Ref.1). The a b s o l u t e value o f
t h e complex v i s c o s i t y lq*l i s a frequency-dependent dynamic v i s -
c o s i t y given by
/q*1 = (GI2 + G"2)1/2/w ,
where w i s c i r c u l a r frequency o f t h e o s c i l l a t i o n . I t i s o f prac-
t i c a l i n t e r e s t t h a t t h i s dynamic v i s c o s i t y a l l o w s one t o p r e d i c t
the steady-state shear viscosity. The empirical relationship
found by Cox and Merz ( R e f . 5 ) ,
q(j) = IQ*(w)I w = j ,
which we u t i l i z e d , j o i n s l i n e a r v i s c o e l a s t i c behaviour w i t h non-
l i n e a r rheology.

I t i s the practice i n industry t o characterize the rheological

behaviour f i r s t o f a l l by determining m a t e r i a l f u n c t i o n s o f non-
l i n e a r rheology. Among t h e v a r i o u s r h e o l o g i c a l f u n c t i o n s a v a i l -
able, we s h a l l examine t h e shear viscosity q , t h e recoverable
shear jr, and t h e entrance pressure l o s s pent t o e l u c i d a t e t h e
r e l a t i o n s h i p s . The shear v i s c o s i t y as a f u n c t i o n o f shear r a t e
o r shear s t r e s s i s a very b a s i c concept needing no e x p l a n a t i o n .
Capillary measurements a l l o w one to determine both t h e shear
viscosity and t h e pressure drop r e s u l t i n g from t h e rearrange-
ments o f t h e v e l o c i t y p r o f i l e a t t h e d i e entrance and a t t h e d i e
exit, known as Bagley-corrections. The flow in the entrance
region is mainly an extensional deformation because of the
severe r e d u c t i o n o f t h e c r o s s s e c t i o n from t h e r e s e r v o i r t o t h e
capillary, and t h e entrance pressure l o s s pent t h e r e f o r e meas-
ures t h e r a t i o o f extensional v i s c o s i t y t o shear v i s c o s i t y a t
t h e p a r t i c u l a r shear s t r e s s ( R e f . 2 , 3 ) .

The recoverable shear jr is a measure o f the elastic energy

stored during flow, which can be recovered upon removal of
stress. This quantity, determined i n shear creep experiments,
allows one to characterize the elastic behaviour of polymer
m e l t s (Ref. 2,4). The shear creep experiments may a l s o be used
t o measure v i s c o s i t i e s .
 327

CHARACTERIZATION OF MOLECULAR MASS DISTRIBUTION

BY M A T E R I A L FUNCTIONS OF NONLINEAR RHEOLOGY

The shear-thinning behaviour o f polymer melts - being obvious i n

plotting shear viscosity versus shear stress or shear rate -
c l e a r l y depends on molecular mass d i s t r i b u t i o n . Fig.2 shows the
s i m i l a r i t y o f form o f t h e v i s c o s i t y f u n c t i o n s a t i d e n t i c a l w i d th
o f molecular mass d i s t r i b u t i o n f o r a homologous s e r i e s o f h i g h
den s i ty polyethylenes (MM and MMD were analysed by gelpermeation
chromatography). The viscos-
i t y curves o f t h e samples o f
108, I I I I 1 d i f f e r e n t molecular mass can
be brought t o coincidence by
vertical shifting. In this
case, t h e sample o f h i g h e st
molecular mass polymerized
w i t h th e same c a t a l y t i c sys-
tem but at lower tempera-
ture, i s noticeably d i f f e r -
ent. The similarity of the
viscosity functions would
also become e vi d e n t if the
viscosity i s p l o t t e d versus
shear rate. The dependences
would then be flatter with
Schubspannung d [Pal shifts c a r r i e d out along a
diagonal with the slope -1
Fig.2 V i s c o s i t y curves o f PE-HD to obtain a master curve.
( d i f f e r e n t MM, constant MMD) Using t h e f i r s t description
we a r r i v e a t a reduced v i s -
c o s i t y f u n c t i o n by d i v i d i n g t he d i f f e r e n t v i s c o s i t y f u n c t i o n s by
the r e s p e c ti v e zero shear viscosities. Fi g.3 illustrates the
influence of MMD on t he shear-thinning behaviour p re se n ti ng
r e s u l t s on homologous s e r i e s and f r a c t i o n s o f PE-HD and making
use o f t h e reduced graphs (Ref.4,6). Nonlinear behaviour s t a r t s
the e a r l i e r , the broader t he molecular mass d i s t r i b u t i o n i s . In
addition, th e t o t a l reduct ion o f v i s c o s i t y i s the gre a ter, the
hig h e r th e p o l y d i s p e r s i t y i s . These wel l -estab l i sh e d relations
are t h e basis f o r a qualitative characterization o f molecular
d i s p e r s i t y i n i n d u s t r i a l practice. The s i m i l a r i t y o r d i s s i m i l a r -
i t y o f molecular mass d i s t r i b u t i o n s can q u i c k l y be checked. The
 2r100 . . . . . . . . . . ......., . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Fig.3
-_
.. - - - ---------. ----q--\'
. --. ~

..- \. , .... Influence o f the

\. \
\. \ --<,
molecular mass
\\
\ d i s t r i b u t i o n on
\, \ ~:
PE - HO \ \ t h e form o f t h e
\
'.\ v i s c o s i t y curves
~\
(homologous s e r i e s
: HW/H" - 1.3
--- : - and f r a c t i o n s o f
--:
M,/M,
H,/M, - 5.5
7.5
t
t
1. 0
1. 5
\\

\*\,
PE-HD)
-.... . . .... . . ..... . . . . . ..... . . . . .... . . ..... . . . ........
I I b I . . . . . . . . .. .. . . . ."8.
I

Schubspannung a [Pal 1x106

slope of the viscosity functions. in an appropriate range

of shear stress, i s a q u a l i t a t i v e measure o f the width o f the
distribution. I t i s a l s o a common p r a c t i c e t o use t h e r a t i o o f
m e l t f l o w indexes a t two l o a d l e v e l s t o determine t h e slope. The
shear-thinning behaviour can also be p r e d i c t e d by means o f a
v a r i e t y o f molecular t h e o r i e s , i n t h i s connection t h e papers and
reviews o f W . W . Graessley have t o be mentioned ( R e f . 7 ) . The com-
parison o f calculated viscosity functions (Fig.4) (where a l o g -
arithmic-normal d i s t r i b u t i o n was assumed ( R e f . 8 ) ) w i t h measured
viscosity curves (Fig.3) (where t h e samples l a r g e l y correspond
to logarithmic-normal distributions) supports the view that
half-quantitative p r e d i c t i o n s can a l s o be made by means o f such
measurements.

-l Fig.4

C a l c u l a t e d viscos-
i t y functions f o r
logarithmic-normal
distributions of
d i f f e r e n t width

(after
W.W. Graessley)
. . . . .. .. . . , . . . . , . . . . . ..., . . . . . . . . .

1*10-~ Rsduzlevte Schubspsnnung 1x101

 329

The molecular mass d i s t r i b u t i o n l l k e w i s e i n f l u e n c e s t h e e l a s t i c

behaviour o f polymer m e l t s , which i s w e l l s u i t e d f o r c h a r a c t e r -
i z a t i o n purposes. F i g . 5 and Fig.6 e x e m p l i f y t h a t h i g h molecular
mass fractions cause large changes in the elasticity of the
m e l t s . The a d d i t i o n o f 1% o f a component w i t h 15times t h e aver-
age molecular mass increases t h e zero shear v i s c o s i t y (qo) about

Fig.5

Influence o f high
molecular mass
fractions on the
viscoelastic
PE-HO behaviour

101 102 lo3 lo4 lo5 106

Schubapannung 0 [Pal

t h e expected amount, enhancing t h e s h e a r - t h i n n i n g behaviour, and

causing an e x t r a o r d i n a r y increase o f the r e c o v e r a b l e shear jr

(Fig.5). The recoverable shear i s proportional t o the applied

stress i n the linear viscoelastic range. The r a t i o o f t h e two
quantities, named t h e shear compliance Jeo, t heref ore describes
t h e e l a s t i c behaviour unambiguously. Fig.6 demonstrates t h a t a

Fig.6

Shear compliance Jeo for

blends of two HDPE-samples
of equal polydispersity but
\I of d i f f e r e n t molecular mass
( y 2 :weight f r a c t i o n o f the
2*10-~
0.0 v2 1.0
l o n g c h a i n component)

h i g h molecular mass t a i l o f t h e d i s t r i b u t i o n s t r o n g l y i n f l u e n c e s
t h e e l a s t i c behaviour. Fig.7 i l l u s t r a t e s , i n t h e same homologous
series previously presented in Fig.2, that the elastic prop-
e r t i e s a t i d e n t i c a l w i d t h o f MMD a r e independent o f t h e average
330

Fig.7
-.? 101
Ln
c
L
3
PE-HD - Serie
I 1 Independence o f the elastic
2 100 behaviour on the average
(0

or
L
molecular mass at constant
;c
10-1 molecular p o l y d i s p e r s i t y
I_(

or
3

D
: 10-2 (The r e s u l t s o f shear creep
W
3
4
measurements on samples o f a

low3 homologous s e r i e s can be r e -

3
101 102 103 lo4 105 presented by t h e same curve,
Schubspannung 0 [Pal
if M > 3*Mc )

molecular mass, i f t h e average molecular mass M i s a p p r e c i a b l y

greater than three times the critical molecular mass Mc (at
which entanglements s t a r t t o o c c u r ) . Very small d i f f e r e n c e s i n
the h i g h molecular mass t a i l of the distributions can be de-
t e c t e d i n t h i s manner.

In capillary rheometry, information about the molecular mass

d i s t r i b u t i o n can a d d i t i o n a l l y be deduced from entrance pressure
losses. Entrance pressure losses, which a r e simple t o determine,
depend on t h e molecular mass d i s t r i b u t i o n . T h i s i s because they
measure the ratio of extensional t o shear viscosity and t h i s
r a t i o i s dependent on molecular mass d i s t r i b u t i o n . F i g . 8 shows
t h e independence o f entrance pressure losses on t h e average mol-
ecular mass a t constant polydispersity. On c o n t r a s t , a s e r i e s
w i t h higher p o l y d i s p e r s i t y - Mw/Mn 2 13 - i s shown i n Fig.9,
where an increase i n t h e pressure losses w i t h decreasing viscos-
i t y i s observed. The comparison w i t h t h e reproduced curve o f t h e
model s e r i e s - cf. Fig.8 - makes i t obvious t h a t entrance pres-
sure losses increase w i t h p o l y d i s p e r s i t y , and i m p l i e s t h a t t h e
molecular mass d i s t r i b u t i o n widens w i t h decreasing average mol-
e c u l a r mass i n t h i s case.

These v a r i o u s rheological measurements, usually carried out t o

assess processing behaviour, p r o v i d e a means o f characterizing
molecular mass distributions. However, measurements of
 331

viscoelastic behaviour are

much b e t t e r suited t o ana-
l y s e t h e molecular mass d i s -
tribution. Automation of
t h e measuring techniques now
permits these measurements
to be run on a routine
b a s i s , and t h e methods, for-
merly reserved for basic
research, can be a p p l i e d as
an a n a l y t i c a l t o o l .

Fig.9

Capillary viscometry of a
HDPE-series, where poly-
dispersity i s changing w i t h
molecular mass

(The curve f o r t h e entrance

pressure loss from F i g . 8 i s
g i v e n i n comparison)

to4 Schubspannung 0 [Pal 5N1O5

332

DETERMINING MOLECULAR MASS DISTRIBUTION

FROM LINEAR VISCOELASTIC PROPERTIES

1 . A Measure o f P o l y d i s p e r s i t y
Molecular mass and molecular mass d i s t r i b u t i o n c o n t r o l t h e r e -
l a x a t i o n spectra a t long times. The i n f l u e n c e o f t h e molecular
composition i s revealed i n t h e dependences o f t h e storage modu-
lus G’ and t h e l o s s modulus G ” at low frequencies, i n t h e so-
c a l l e d t e r m i n a l zone. Such dynamic i n v e s t i g a t i o n o f m e l t s can be
carried out quickly and very reproducibly, as was mentioned
above. As an introduction to the problem, Fig.10 shows the

----.-.-- Fig.10

Storage modulus G ’
i n dependence o f
frequency

(PS-standards and
a commercial p o l y -
styrene)

1*101 --
1*10-~
. ..... u
circular f r e w e n c y
1

w 11/s1 1t104

frequency dependences o f t h e storage modulus G ’ f o r PS-standards

(Ref.9) having d i f f e r e n t molecular masses, and f o r a commercial
polystyrene. One n o t i c e s t h a t t h e storage modulus changes o n l y
slightly i n a broad frequency range f o r t h e h i g h molecular mass
standard. I n t h i s so-called p l a t e a u zone t h e short-range diffu-
s i o n a l motions o f t h e polymer segments a r e much f a s t e r than our
o b s e r v a t i o n times, and large-scale conformational changes re-
sulting i n translational motions a r e s t i l l greatly restricted.
The entanglement network behaves like a cosslinked rubber in
this frequency range. As the observation time is increased -
lower frequencies - more and more large-scale motions take
place, and molecular diffusion causes the storage modulus to
drop. The l i m i t i n g behaviour i n this terminal zone i s a quad-
ratic dependence on frequency. A higher polydispersity, for
example the commercial PS-sample, produces a more gradual
 333

change, and t h e descent o f t h e storage modulus extends over a

l a r g e r frequency range.

Upon examination of the loss modulus G " of the same samples

(Fig.ll), i t i s evident t h a t t he l o s s modulus passes through a

1*10=
Fi g. 11

-
a
I Loss modulus G"
L1 i n dependence o f
frequency

(The same samples

as i n Fig.10)

l"lO1
MO-~ c i r c u l a r frequency Y ii/a~ 1.10~

shallow minimum and i s smaller i n magnitude than G ' i n t h e pl a -

teau zone. The marked reduct ion o f t he chain r e l a x a t i o n ca p a b i l -
ity i n that range - a c h a r a c t e r i s t i c o f polymers - leads t o a
crossover o f th e storage and l o s s modulus (Fi g.12 ). The l o c a t i o n
o f th e crossover p o i n t on t he frequency and modulus a x i s gives
valuable i n fo r mat ion on molecular mass and molecular mass d i s -

Fig.12
1x106 , ,,...,., , .....,,, , ,,,,,,,, , ,,,,,,,, . , . ,,,,,,,, , ,,,,,,, , ,

The dependence o f
storage modulus G '
and
l o s s modulus G"
on frequency f o r
two standards and
th e commercial
po l ystyren e

Frequenz Y lrad/sl
334

MO’ . , . . ...., . . . , ...., , , , . ...., , , , . ...., . , . . ...., . . . . ..

Fig.13
E
-
a
I MMD 0’ Dependence of G’
m
and G “ on MM and
m
MMD: Shift of the
crossover p o i n t

tribution (Fig.12 and schematic drawing of Fig.13). Zeichner

extensively studied the relations for unimodal distributed
polypropylenes (Ref.10) and showed t h a t a p o l y d i s p e r s i t y index
PI, d e f i n e d as t h e i n v e r s e o f t h e crossover modulus, c o r r e l a t e s
very w e l l w i t h t h e p o l y d i s p e r s i t y r a t i o Mw/Mn, which i s u s u a l l y
determined by gelpermeation chromatography. Fig.14 demonstrates

F i g . 14
1x10~

C o r r e l a t i o n o f t h e rheo-
logical polydispersity
index P I w i t h Mw/Mn from
GPC-measurements f o r
PP-homopolymers
l o : G . R . Zeichnerl
I A : elgene Mess I ( p u b l i s h e d and own d a t a )
lXl0Q PI 1*10’

t h e good c o r r e l a t i o n o f t h e two p o l y d i s p e r s i t y r a t i o s . (The pub-

l i s h e d d a t a and our own measurements do n o t p e r f e c t l y c o i n c i d e .
b u t n e i t h e r t h e t y p e o f t h e d i s t r i b u t i o n s o f t h e samples nor t h e
calibrations of the gelpermeation chromatography (GPC) may
n e c e s s a r i l y agree.) We checked t h a t l i n e a r polyethylenes w i t h
unimodal distribution can be analysed in the same way. Even
small amounts o f b i m o d a l i t y , however, i n t e r f e r e w i t h t h e analy-
sis.
 335

2. Q u a n t i t a t i v e D e t e r m i n a t i o n o f MMD

A l l t h e i n f o r m a t i o n about MM and MMD i s contained i n t h e behav-

i o u r o f t h e s t o r a g e and t h e l o s s modulus i n t h e t e r m i n a l and t h e
p l a t e a u zone, and must be deconvoluted t o o b t a i n t h e molecular
mass d i s t r i b u t i o n . S. Wu has shown (Ref.11) that t h e dynamic
s t o r a g e modulus G'(w) approximately corresponds t o t h e cumulat-
i v e molecular mass d i s t r i b u t i o n . He assumes a l i n e a r m i x i n g r u l e
when m o d e l l i n g t h e s t o r a g e modulus as a sum o f t h e c o n t r i b u t i o n s
o f each species. I n Fig.15 t h e s t o r a g e moduli G'(w) o f two PS-
standards a r e compared w i t h t h a t o f a 1 : l - b l e n d (Ref.l2), show-
ing that a linear m i x i n g r u l e can o n l y be a f i r s t approxima-
tion. Note t h a t t h e p l a t e a u modulus o f t h e h i g h molecular mass
component i n t h e m i x t u r e does n o t come up t o h a l f o f t h e o r i g -
i n a l value! F o r concentrated polymer s o l u t i o n s t h e p l a t e a u mod-

Storage modulus
G'(w) f o r
two PS-standards
and t h e
1 : 1-blend

l"lO1 t . ....... . ....... . . ......

I I . . ...... , yY_ ...... , .......' . ......I
1 x 1 0 ~ ~ Frewenz w [rad/sl 1.10~

u l u s GNO e x h i b i t s a q u a d r a t i c dependence on c o n c e n t r a t i o n t o a
good approximation (Ref.13,1(S.502)). W. H. T u m i n e l l o ' s approach
i s based on t h i s q u a d r a t i c dependence (Ref.14); t h e method then
i s a b l e t o p r e d i c t as w e l l bimodal and more complex d i s t r i b u -
t i o n s from r h e o l o g i c a l measurements.

Tuminello assumes that at a particular frequency all chains

w i t h r e l a x a t i o n t i m e s g r e a t e r than t h e i n v e r s e o f t h e frequency
f u l l y c o n t r i b u t e t o t h e modulus o f t h e network, whereas c h a i n s
w i t h s h o r t e r r e l a x a t i o n t i m e s a r e a c t i n g as a nonentangling s o l -
vent. A d i s t i n c t i o n i s made between unrelaxed c h a i n s s t i l l f u l l y
entangled at the particular frequency and relaxed chains be-
336

having as a d i l u e n t . The r e l a x a t i o n f r e q u e n c i e s o f t h e i n d i v i d -
u a l chains a r e c o r r e l a t e d t o molecular mass by t h e well-estab-
lished power law relation (l/w const. * M3.4). The storage
modulus o f t h e monodisperse component t h e r e f o r e i s approximated
by a s t e p f u n c t i o n i n frequency. I t i s also postulated t h a t the
chains do n o t m u t u a l l y i n t e r f e r e .

For e v a l u a t i o n , a reduced modulus curve must be c o n s t r u c t e d by

d i v i d i n g t h e measured frequency dependence o f t h e storage mod-
u l u s G'(w) w i t h t h e p l a t e a u modulus GNO and drawing t h e square
root - conforming t o the blending r u l e (Fig.16). The reduced
modulus curve, (Gt/G~O)Om5 versus log(w), is then fitted

Fig.16

Reduced modulus
N
2- curve and
"2 f i t w i t h one
>
-
L1
tanh-function

hendelsObliches PS

0 0
1*10-~ Frequenz w [rad/sl

t o one o r two t a n h - f u n c t i o n s (the tanh-function resembles t h e

cumulative form o f a normal d i s t r i b u t i o n ) . A f t e r t r a n s f o r m a t i o n
o f t h e frequency s c a l e i n t o a molecular mass s c a l e t h e curve i s
e q u i v a l e n t t o a cumulative molecular mass d i s t r i b u t i o n . The d i f -
ferential molecular mass d i s t r i b u t i o n may then be e a s i l y op-
t a i n e d , which can d i s t i n g u i s h small d i f f e r e n c e s i n t h e d i s t r i b u -
tions. For our example, commercial polystyrene, t h e evaluated
averages agree w e l l w i t h those o f t h e GPC-analysis (cf. Tab.1).
The comparison o f t h e d i f f e r e n t i a l curves ( F i g . 1 7 ) demonstrates,
however, t h a t t h e r e i s o n l y a l i m i t e d coincidence. Fig.18 exemp-
l i f i e s t h a t even samples w i t h a q u i t e broad molecular mass d i s -
t r i b u t i o n may be p r o p e r l y analysed. The n e x t example ( F i g . 1 9 )
demonstrates t h a t i t i s a l s o p o s s i b l e t o separate bimodal d i s -
t r i b u t i ons .
 337

1.2 n , , , , . . . . ' ' " " "

- hande15ilbllCtleS PS . _ .GPC Fig.17

1.0

PE-HO
_ _ - : GPC
Fig.18
My = 17L
Mw/M,, - 7.2
D i f f e r e n t i a l MMD
plots for
a HDPE-sample
w i t h a b r o a d e r MMD

2.5

1 : 1 - Mischung z w e i e r P o l y s t y r o l - S t a n d a r d s

Fig.19

A n a l y s i s by
r h e o m e t r y a n d GPC
f o r a bimodal
mixture

1- - - : GPC-Messung. -: Pheometrische Analysel

 3. Application Examples

The efficiency o f this quantitative analytical method is illus-

trated by some examples, which are compiled in Tables 1 to 3.
The close coincidence of the calculated and the determined mass
averages in a broad range of molecular mass is above all due to
the accuracy of the shift rules f o r the relaxation times.

Polystyrol PTFE-Copolymer *
PS3 PS4 PS5 PSN7000 PPVEI PPVE2

126 299 768 345 109 176

98 224 556 129 61 87

1.29 1.33 1.38 265 1.8 20

125 290 750 336

112 271 670 137

1.05 1.07 1.07 25 1.7 - 1.8

Tab.1 Comparison of the number and mass averages f o r PS- and

PTFE-samples determined by both the rheological and the
classical method (GPC)
 339

PEX HD ---I
Mdmasse
kdmoll Serie I (MwlMn = 5.5) Serie I1 (MwlMn = 8)
1193 1236 1292 1395 1615 I1187 11.284 11445

Mq 93 122 165 245 450 88 156 297

.a, M" 82 m 139 m 434 7 9 1 3 3 2 7 0

+
L

0 Mw 100 135 174 280 556 106 176 374

Mn 2 6 3 5 4 0 W l C 6 I7 26 46
.c
a: M,/Mn 3.8 3.9 4.3 4.7 5.2 6.3 6.7 8.1

M" 87 167 282 486 130

hzy x)5 170

2
0 Mn
20

Mw!Mn 5.2 5.2

Tab.2 Comparison o f v a r i o u s averages determined by r h e o l o g i c a l

and c l a s s i c a l analyses f o r samples o f two HDPE-series

Tab.3

Molecular charac-
* * * *
* * Bc-Messungen * Rheolopie * terization by GPC
* * (Methode Tuminellol *
* * * * and rheometry of
0 Robe * Hv MUlHn * Hv HviM *
some PP-samDles
* * * *
* W.uD * 162 3.2 * 168 2.1 *
* * * *
* W.wF * 170 5.1 * 167 2.5 *
* * * *
* W.HD * (680) 7.1 * 819 2.7 * (filed to
* * * *
* W.W * 573 8.0 * 692 3.0 * increasing
* * * *
* W.TF 366 10.7 * 356 4.1 * polydispersity)
*
I(
* * *
340

UNSOLVED PROBLEMS AND CONCLUSIONS

Comparing t h e MMD values o f t h e PP-samples shown i n Tab.3, one

w i l l be aware t h a t t h e r a t h e r good correspondence i n t h e case o f
t h e p o l y e t h y l e n e w i t h broad d i s t r i b u t i o n s i s due t o a f a v o u r a b l e
fact. The c a l c u l a t e d d i s t r i b u t i o n s are, i n general, t o o narrow.
This i s an expected result, because t h e r e l a x a t i o n time o f a
molecule i s considerably changed by blending. The l o n g molecules
behave i n t h e m i x t u r e as i f they were s h o r t e r , and t h e s h o r t
chains a c t as i f they were longer. Thus t h e w i d t h o f t h e d i s -
tribution of r e l a x a t i o n times i s significantly reduced i n the
blend. This e f f e c t becomes e v i d e n t for broader distributions.
The present understanding o f t h e r e l a t i o n s h i p between r e l a x a t i o n
s p e c t r a and molecular mass d i s t r i b u t i o n s i s l i m i t e d t o e m p i r i c a l
relations ("blending rules"). In our investigations we have
noticed, i n a d d i t i o n , t h a t t h e narrowing o f t h e r e l a x a t i o n spec-
t r a i s dependent on c h a i n f l e x i b i l i t y . Polyethylene i s a marked-
ly more f l e x i b l e c h a i n than polypropylene, the difference in
chain r i g i d i t y d i s t i n c t l y i n f l u e n c e s t h e narrowing o f t h e r e l a x -
ation spectra. A provisional remedy against this shortcoming
c o u l d be t o stretch the calculated d i s t r i b u t i o n by an a f f i n e
t r a n s f o r m a t i o n ( c f . Ref.15).

I hope t o have given you a review o f t h e d e t e r m i n a t i o n o f t h e

molecular mass d i s t r i b u t i o n f o r l i n e a r polymers from r h e o l o g i c a l
measurements. Remember that the approach of determination of
molecular mass d i s t r i b u t i o n from l i n e a r v i s c o e l a s t i c m e l t prop-
erties i s a f f e c t e d by t h e approximations and by t h e unsolved
problem o f how t o handle t h e narrowing o f t h e r e l a x a t i o n spec-
tra. Despite t h i s , t h e r e s u l t s and t h e degree o f quantitative
agreement obtained a r e remarkable. Rheological methodology i s o f
h i g h a value i f r e l a t i v e answers a r e s u f f i c i e n t , what i s o f t e n
t h e case i n i n d u s t r i a l p r a c t i c e . I n a d d i t i o n , i n s o l u b l e o r poor-
l y soluble polymers can be analysed i n t h i s way, and rheology
can be applied even where alternative methods are available
because o f i t s small t i m e requirements.
 341

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