Understanding the Mechanical

Properties of Filled Polyolefins

J M Adams, C D Paynter & S Ritchie

Introduction
Polylefins are the most
used polymers today

Flexural Modulus

Filled grades

Polymer

Market %

PE

32

PP

19

PVC

16

PUR

PS

PET

PA

PC

Other

10

Use of a variety of
virgin polyolefin types
and additives generates
wide property envelope
Impact Strength

Green implications

Background
Inorganic fillers affect composite properties:
Increase:

It Depends:

Density
Thermal conductivity
Electrical conductivity
Stiffness

Permeability

Inorganic fillers for

functionality, not cost
Polyme
r
PE
PP

$/litre

Filler

Filler (kt)

$/litre

0.70 Fine
0.79 Ultrafine

2.80
14.50

Fillers are expensive but also:

Remember the compounding cost!

Decrease:
Thermal expansion
Warpage
Surface finish
Colour
Tensile strength
Flammability
1972

1987

2002

35

200

60

282

854

1200

Kaolin

24

24

24

Silica

13

Talc

80

160

ATH
Asbestos
Carbonate

Filler Particles

Talc

Kaolin

Calcium Carbonate

Bentonite

1 m

Youngs Modulus (GPa)

Stiffness 1 Basic Data

7

mica

talc

kaolin
4

calcium
carbonate

3
2
1
0
0

10

20

Filler Loading (wt %)

30

40

50

Stiffness - 2
What is the origin of the different stiffening
effects shown by different fillers?
Could be:
Aspect Ratio (Ec =Ef..MRF + Em(1-); MRF= f(AR))
Delamination in processing (increasing AR)
Particle alignment in processing (increasing MRF)
Relative stiffness of filler particles
Interfacial properties
(Induced) polymer morphology

Stiffness 3 Aspect Ratio

6.5

40 wt% filled PP

Flexural Modulus (GPa)

6.0
5.5

talc
kaolin

5.0
4.5
4.0
3.5

So, Aspect ratio is important.

BUT it is not the only factor.

3.0
0

20

40

60

80

Particle Aspect Ratio

100

120

140

Stiffness 4 Effects during Processing

Delamination during processing does NOT happen. Trial with PP filled
(40 wt%) with talc. AR before compounding/moulding = 29, and 27 afterwards.
Talc-filled
FTIR Orientation vs Depth

Intensity Ratio

talc

Orientation effects are

the SAME for different
platey fillers.
kaolin
0

Kaolin-filled

2
Depth (mm)

Stiffness 5 Modelling for Filler Modulus

(Padawar & Beecher: Ec=Ef..MRF + Em(1-)

6.5

40 wt% filled PP

Flexural Modulus (GPa)

6.0

T
O
T

5.5

Ef = 35 GPa
talc

5.0

kaolin

4.5

Ef = 20 GPa

4.0

O
T

3.5

Particle stiffness seems important.

BUT, is this the (full) answer?

3.0
0

20

40

60

Particle Aspect Ratio

80

100

120

140

Stiffness 6 Interfacial Properties

PP 40 wt% filled with kaolin

The chemistry of the interface

does make a difference, BUT the
reasons are not crystal clear.

With 3-APS +
Polybond

With Polybond

With 3-APS

With PC1A/PC1B

With PC1A

2.5

With AHT

3.5

untreated

Flexural Modulus (GPa)

4.5

Stiffness 7 Polymer Microstructure

We know that
for unfilled PP the
polymer microstructure
is critical to performance.
Spherulite

Transcrystalline
Region near
Nucleating surface

Transcrystalline

Spherulitic

Youngs Modulus (GPa)

1.09

0.67

Tensile Yield Strength (MPa)

25.0

18.6

Elongation to Break (%)

>300

Failure Energy (kJ m2)

28.0

28.5

Optical
Micrographs
Spherulitic
Stucture
in unfilled PP

Stiffness 8- Nucleation
Modelling the shape of the DSC crystallisation curve => Nucleation Properties

Sample

tm (min)

Number of
nucleating sites per
SA of filler Nf (x 106
m-2)

Unfilled PP

12.2

PP + Calcium
Carbonate

3.2

65

PP + Stearic
Acid coated
Calcium
Carbonate

3.4

PP + Talc

0.9

Heat output

20 wt% filled PP crystallised at 135 oC

tm

temperature

Nf = NA1.5(filled) NA1.5(unfilled)

60
NA = [23 (ro /t)2 tm2]-1

1300

AND we know that fillers

affect the crystallisation
of the polymer (Example 1).

Stiffness 9 Polymer Morphology

Untreated Mineral
Transcrystallisation
Nucleation and crystal
growth in PP much reduced
by modification of the
mineral surface

Residual Spherulitic Growth

AND we know that fillers
affect the crystallisation of
the polymer (Example 2).

Surface Treated with 3-APS

Stiffness 10 Crystallinity
Sample

% Crystallinity %
(DSC)
Crystallinity
(IR)

Crystallinity
Index
(XRD)

-phase
Orientation
Index (XRD)

-phase
Index
(XRD)

Unfilled PP

60

68

3.7

0.88

0.05

PP + 40 wt%
Calcium
carbonate

59

66

3.6

0.80

0.07

PP + 40 wt%
Stearate
coated
calcium
carbonate

60

68

4.0

0.83

0.12

PP + 40 wt%
Talc

55

11.5

0.92

0.02

AND we know that fillers affect the

crystallisation of the polymer (Example 3).

Stiffness 11 - Summary
Composite stiffness is determined by:
Filler loading
Stiffness of the filler
Aspect Ratio of the filler
Important effects from:
(i) nucleation/crystallisation properties of fillers
(ii) surface treatment which modifies these properties

Everyone knows that fillers that

give high stiffness have poor impact

properties

Impact strength

Everyone knows that this

is a result of the high
stresses at the edges
of a high AR inclusion
(Higher AR = sharper edges)

Falling Wt Impact Strength (J)

Stiffness - Flex Modulus

Impact 1 - Background

Talc and clay filled PP

10

x
x

x
x
x

x
x
x

40

80

Aspect Ratio

120

160

Charpy Notched Impact Strength (kJm-2)

Impact 2 Key Information - 1

Talc

30

Calcium Carbonate
Coated

20

10

Uncoated
0
0

10

20

30

40

Filler Loading (wt%)

50

10

20

30

40

Filler Loading (wt%)

At loadings from 10-50 wt%, coated carbonate gives notched IS > unfilled.
Below 20 wt% loading talc gives notched IS = unfilled, but declines thereafter.
Even with excellent dispersion given by twin screw compounder, uncoated
carbonate (low AR) performs as poorly as talc (which has high AR).

50

Falling Weight Impact Strength (J)

Impact 3 Key Information - 2

Talc

15

Calcium Carbonate
Coated

10

Uncoated
0
0

10

20

30

40

Filler Loading (wt%)

50

10

20

At loadings from 10-50 wt%:

coated carbonate gives un-notched IS >> unfilled.
uncoated carbonate gives un-notched IS = unfilled.
talc gives un-notched IS = 2* unfilled.

30

40

50

Filler Loading (wt%)

Impact 4 Important Factors

Particle shape High AR = sharp edges => stress foci

Poor Particle Dispersion => aggregates => Griffith flaws

Crystallisation & Microstructure

Mechanics of crack propagation

Poor dispersion

BUT REMEMBER that THE MOST IMPORTANT FACT is that

PROPERTIES CAN IMPROVE when you add filler particles!

-phase index - B

0.25

Crystallinity index - C

80

Distance from the gate (mm)

-phase orientation index - A

Impact 5 Unfilled PP
0.7

220 oC
250 oC
280 oC

0.5
0

80

Distance from the gate (mm)

Measured IS as a function of sample

distance from the gate and T.

2.2

Deduced that High IS corresponds to:

Low crystallinity
High -phase content
Low -phase alignment
0

80

Distance from the gate (mm)

Question:
Does this translate to the filled case?

Impact 6 Nucleation/Crystallisation

Falling Weight Impact Strength (J)

We do have data that demonstrate the importance of nucleation

and crystallisation in determining the impact performance of filled
polyolefins. Data for Polypropylene is given below.
12

Coated Carbonate
Uncoated Carbonate
Unfilled PP

120

124

128

132

136

Temperature of onset of crystallisation (oC)

1. Crystallisation does determine Impact Strength.

2. Unfilled point is NOT on the line
=> Mechanism for good impact performance is different in filled and unfilled cases.

Impact 7 Fracture Mechanics

plastic zone
radius rp

Umes-Uke = G (b w Z)
Z is a function of (a/w)
b
a

(a)

crack length

Fail energy (J)

bwZ (mm2)

Sample

Notched IS
(kJ/m2)

Gc
(kJ/m2)

rp
(mm)

Unfilled PP

11.51.0

3.2

0.08

Carbonate filled

9.52.0

3.1

0.26

Coated
carbonate filled

13.04.5

5.0

0.31

Filled materials have:

- higher Gc values
- much bigger plastic (deformation) zones

Impact 8 Critical Ligament Theory

FW Impact Strength (J)

Izod Impact Energy (J/m)

Bartczaks Critical Thickness

0.1 m

1 m

Interparticle Ligament Thickness

10 m

0.1 m

1 m
0.6 m particles
0.75 m particles
0.9 m particles

We found no
critical ligament thickness

10 m

Impact - 9 Instrumented Charpy Impact Test

Striker
Piezoelectric load cell
Generalised curve
250

Load (N)

200
150

Post peak energy

ie
plastic or ductile
region

GT

100
50

GIC

0
0.0

1.1

2.2

GPP
3.3

4.4

Displacement (mm)

Impact - 10 -Total energy results

Perpendicular

G1G2G3G4G5 G6

Flow direction + molecular orientation

30
25

GT kJ/m2

20
15
10

Impact performance is
very dependent upon:
- flow & molecular orientation
- position in the mould
especially for filled materials.

5
0
perpendicular

G1
g1

G2
g2

G3
g3

G4
g4

G5
g5

G6
g6

flow orientation and position in mould

neat

5 vol%
5%
cc

10 vol%
10%
cc

30
vol%
30%cc

20
vol%
20%cc

25
vol%
25%cc

Impact 11 - Thin orientated injection moulded samples (G1)

250
25%-g1
5%-g1

5 vol% filler

load (N)

200

25 vol% filler

150
ductile

100
50
0
0.0

2.0
brittle

4.0

6.0

displacement (mm)

More highly filled system has the highest impact strength.

The initiation energy remains constant BUT
the post-peak energy absorption is increased by the increased filler volume.

Impact - 12 - Impact properties as a function of flow orientation

250
25 vol% filler (Perpendicular)
25%-g1

load (N)

200

25%-perpendicular
25 vol% filler (G1)

150
100
ductile

50
brittle

0
4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0

displacement (mm)

We see large differences between samples having different orientation:

-the initiation of the crack is the same
- but we lose almost all of the post-peak toughness when the flow and
molecular orientation is perpendicular to the direction of fracture.

Impact 13 - Fracture Surface

PP - 5 vol% Calcium Carbonate

PP 25 vol% Calcium Carbonate

The more ductile deformation in the 25% filled case can clearly be seen.

Impact - 14 - SEM of the stress whitened plastc deformation

zone - microtomed surface perpendicular to the crack face
under the fracture surface
PP 20 vol% Calcium Carbonate

400 m under
fracture surface
Voiding/cavitation does
not extend this far into
The bulk.

100 m under
fracture surface
Voiding still present.
Cavitation extends ~ 130 m
into the bulk, allowing plastic
deformation and dissipation
of energy.

Directly under
fracture surface
Large scale voiding

Final Summary
Composite stiffness critical properties:

Filler Loading
Stiffness of the filler
Aspect Ratio of the filler

(i) nucleation/crystallisation properties of fillers

(ii) surface treatment which modifies these properties

Impact Performance governed by:

Filler loading
Processing conditions, which determine:
(i) filler dispersion
(ii) geometric/orientation effects

Aspect Ratio of the filler

(i) nucleation/crystallisation properties of fillers

(ii) surface treatment which modifies these properties

Degree of plastic flow, determined by filler size and loading, and

by the interparticle ligament geometry

Acknowledgements
Imerys Minerals Ltd
- Phil McGenity
- Andy Riley
- Mike Hancock
EU Interreg MNAA
Universities of Exeter & Bristol - MCSW