Dispersion of Fillers

R. H. Schuster
Consultant to LANXESS /German Rubber Institute

12 Jornadas Latino-Americanas de Caucho

Buenos Aires 23/24 Sept. 2013
 Dispersion through mechanical mixing

Pelletizing
Broken
CB Fluffy Pellets
Aggregates Macro-dispersion
Agglomerates 1-3 mm
≥ 1 µm

Preheated Feedstock:
Air Oil

"Onion
Refractory
1650 °C 915 m/sec skinning"

Natural Gas H2O

Micro-dispersion
< 1 µm
50-500 nm Dispersed
Aggregates
CB Manufacturing
 Mixing Diagram

Dispersion
and
Distribution

Filler
Incorporation
 Micro-dispersion → Large Interface
Macro-dispersion Micro-dispersion

Matrix

Interface

Particles

Segment Density
Interface:
Matrix
increases by dispersion
determines Phase Bonding Distance from
Reinforcement solid particle

Specific Properties in the interface

 Theoretical Aspects
Elongational Flow

(Shear Flow)

FC = ν F H FH = cη π Ra2 τ xy / γ
Cohesive Strength Hydrodynamic Force

νF = Contact points
H = Interaction Force ν F Hγ
Fc
FH
=
=
Cohesive Force
Hydrodynamic Force
(η τ ) x z krit >
c π Ra2
τxz = Shear rate
η = Viscosity
Ra = Radius of Agglomerate
γ = Interfacial Tension
Methods to evaluate Filler Dispersion

Direct methods:
microscopical detection of particles
particle size distribution,
interparticle distance.

Indirect methods:
evaluation through a
physical property related to
filler dispersion
Filler Dispersion – scale dependent Phenomenon
What is the adequate Ruler ?
Micro-dispersion Macro-dispersion
10-9 10-8 10-7 10-6 10-5 10-4 10-3 m

“Particle” (?)
Aggregates
Agglomerates
Undispersed Pellet Fragments
Defects (?)
AFM -TEM

Mechanical Surface Roughness

Optical Roughness

AC and DC Electrical Measurements

 Dispersion Index Analysis (DIAS)
Principle:Vertical Light Reflection on Razor Blade Cuts
DI = 61,3 %

Poor Dispersion

n
f ∑A
i =1
part .,i
DI = 78,5 %

DI =1 −
n Agraph c
Good Dispersion

DI Dispersion Index
n

∑A
i =1
part .,i Sum of Particle Area Computer aided evaluation
Data bank
Agraph Observed Area Quantitative Comparison
n Number of Micrographs Rapid Method
f Solid Content of Agglomerates
Off-line Measurement
c Volume Fraction of Filler
 Mechanical Roughness
Surface Profilometer
-2µ diamond tip stylus
X-Y-Z positioner

Ra=<Z-Za>
Z – altitude of a point 1.2
Za- average altitude of
the surface 1.0

Micro-roughness,Ra
0.8

0.6

0.4

0.2
0 300 600
Mixing Time [sec.]
Gerspacher
 Atomic Force Microscopy (AFM)

Simple sample preparation Good Dispersion Poor Dispersion

DI = 61,3 % DI = 78,5 %
Magnification variable
Qualitative ranking
Quantitative data rather difficult

Small Magnification:
Agglomerates
High Magnification:
Aggregates /Primary Particles

Th. Alshuth & R. H.Schuster KGK (1992)

 AFM Analysis of Micro - dispersion

(a) (b)
AFM "phase" image (a) and binary image (b).

Definition of neighbour aggregates Illustration of the "dilatation" method

according to their common borders
J.-B. Donnet, KGK (2006)
Transmission Electron Microscopy (TEM)
Incident
Electron Beam
Auger Electrons E0 Back scattered
E<10 eV Electrons
X-Ray Secondary
0<hv<E0 Electrons
Light E=20-50 eV
0<hv<einige eV
Sample
CB N330
φ = 0.188
Inelastic Elastic
scattered scattered tm = 125 s
Electrons Elektrons
E0- E' E0

Aggregate Radius (nm)

Agglomerates/ Aggregates are
isolated from the uncured mix B. Oppermann & R. H. Schuster (1994)

Size and Shape Analysis by TEM

 TEM-Microdispersion of Silica

Silica/ SSBR (55V; 25S)

20 phr

a) Silica/ Silane/SSBR (55V; 25S)

20 phr
b) Silica/Silane/SSBR (25V; 25S)
X-Ray Computer Tomography

3D Micro-CT of an NR
Voxcel Size 9 µm

Non-destructive detection of large undispersed particles

that acts as flaws and can initiate premature cracks
 Dispersion / Percolation Concept

Filler-Network Filler-Network
percolated Unpercolated percolated

Poor Dispersion Good Dispersion Good Dispersion

Large Agglomerates Small Agglomerates
(Aggregates?)
Electrical Conductivity of Filler-Networks
Micro-dispersion by Volume Resistivity
Electrical Percolation Threshold

Ω cm]
LOG (Volume Resistivity) [
E-EpP-T

Percolation

Conducting
Insulating

Carbon Black Loading [p hr]

Larger Electrical Percolation Threshold(phr)

→ Better Dispersion
Intensive Mixing shifts the Percolation Threshold
to higher Concentrations
Influences on Filler Macro-Dispersion
Process Parameters
- Mixing time
- Rotor Speed
- Cooling
 Influence of mixing conditions
(Visible light reflection DIAS)
The Macro-dispersion
tends to a limiting
plateau value.

The plateau value depends

on the mixing conditions
DI and the mixing efficiency.
(%)
The level of dispersion
can be increased after
cooling by remixing
(i.e. on a two-roll mill)

Mixing Time Rotor Speed

(min) (rpm)
Mixing time and Rotor Speed
demonstrate similar graded
influences
Effect of an increasing E-spec on CB Dispersion
Specific energy 120 180 240 Wh/kg
Mooney viscosity 54 47 42
 TEM-Analysis of Micro-dispersion
120 s 360 s

Frequency %
125 s

Aggregate Radius
Aggregate Radius
0.20
Mixing time
Frequency [%] 6 min

4 min
0.15 2 min

Indication that at longer mixing times 0.10

Micro-dispersion is going on (!)

0.05

Method not applicable for routine work

0.00
0 0.05 0.10 0.15
2
Aggregate area [µm ]

B. Oppermann & R. H. Schuster (1994)

 Influence of mixer cooling
Efficient cooling of the
DI
internal Mixer increases
Filler Dispersion,
while Filler Incorporation
is prolonged
Cooling water temp.

Is the increase of
filler Macro-Dispersion spec. energy
in the region of 90-99%
of any importance

Macro-dispersion tends to a limiting value

 Influence of mixing conditions
Dispersion (Summary)

Dispersion

Dispersion
Mixing time Nr. of revolutions Ram Pressure

Dispersion
Dispersion

Cooling
Filling factor
Influences on Filler Macro-Dispersion
Polymer
-Chain Length
-Chemical Nature

Filler
-Surface Specific Area
-Structure
-Surface Activity
 Influence of the Polymer
Chain length of the rubber Chemical nature of the rubber
Viscosity 100
SBR(15;23)
DI DI [%]
[%] 90
80
80
M (NR) NR
w
40 230.000 g/mol 70
590.000 g/mol
0 60
50 20 40 60 80 100
30
CB [phr] CB [phr]

Macro-dispersion is improved by:

- Long polymer chains.
- Entanglements transmit shear forces.
- Chain segments with good interactions
with the active sites of the filler surface
V.Peterseim and R.H. Schuster RCT (1994)
Influence of the Polymer Microstructure
Vinyl Content
SSBR/CB N234 (50phr)
100
Dispersion Coefficiient, D (%)

75

Symbol Polymer 1,2-Vinyl Styrene M

W
50 wt.% wt.% g/mol

L-SBR 0825 < 7.5 25 163000

L-SBR 2525 25 25 206600
25
L-SBR 5025 50 25 203600
L-SBR 5525 55 25 167400

0
0 120 240 360 480 600 720
Mixing time, t [s]
U. Skodzaj & R.H. Schuster DIK (2001)
 Influence of the Molecular Weight
SSBR/Silica (70phr)
100
Dispersion Coefficiient, D (%)

75
Symbol 1,2-Vinyl Styrene M
W
wt.% wt.% g/mol

28.5 24.9 81200

50
29.3 24.9 131200
29.8 24.6 223400

25
0 200 400 600 800 1000 1200
Mixing time, t [s]

U. Skodzaj & R.H. Schuster DIK (2001)

Influence of the Molecular Weight Distribution
SSBR/Silica (70phr)
100
Vinyl Styrene M (M / M )
W W n
Dispersion Coefficiient, D (%)

wt.% wt.% g/mol

90 29.8 24.6 223400 1.43

25.0 25.0 206600 2.12

80

75

70

Dichtefunktion φ / -
50

60
25

0
1,0E+04 1,0E+05 1,0E+06 1,0E+07

Molmasse Mw / gmol-1

50
0 200 400 600 800 1000 1200
Mixing time, t [s]
U. Skodzaj & R.H. Schuster DIK (2001)
 Influence of the Polymer microstructure

SBR/prec. Silica

Macro-dispersion is improved
by side groups:
Styrene > Vinyl
Pellet breakdown is influenced
by polymer dynamics.
Long chain relaxation
facilitate pellet breakdown

U. Skodzaj & R.H. Schuster DIK (2001)

 Tensile of CB Aggregates

More resistance to break

shear and to erosion
poor dispesion at constant
mixing time
LS-CB
Number of contacts
per aggregate

shear
Less resistance to break
and to erosion
good dispesion at constant
mixing time

HS-CB
 Influence of CB Structure
Better
Dispersion Kinetics Dispersion
DI 4,0
N 326

ln (UCB)
3,0

N 347
2,0
SBR 1500
2 4 6 8
Mixing time (min)
Mixing time (s)

High structure CB
disperse better
shorter mixing times
- less filler-filler contacts per Aggregate
-Energy reduction
incorporation is slower
Higher Dispersion
- filling the larger void volume is more
- better Product Quality
time consuming
 AFM Analysis of Aggregate Distance
Distance (nm)
400
Average "B-B" distances between
300 275 aggregates
167
CB N330 at different loading
200
101
100 65

0
5 10 30 50
Loading (phr)

150
109 107
Distance (nm)

100 91

Average "B-B" distances of CB

50
aggregates
Influence of CB structure (50 phr)
0
N326 N330 N347
Influence of mixing time and Silica type
100
SSBR (50V; 25S)/prec. Silica
Dispersion Coefficient, D (%)

75

50
Silica DBP N-SA
70 phr ml/100g m2/g

25 K2 176 177
K1 203 132
HD 176 177
0
0 100 200 300 400 500 600 700
Mixing time t / s

U. Skodzaj & R.H. Schuster DIK (2001)

 Influence of Structure and
Surface Specific Area

The decrease of particle size leads SBR 1712

140 60/37,5 CB/Oil
to poor dispersion
The increase in void volume 85 90

Spec.Surface Area
of the aggregates leads 100
to better filler dispersion
80 95
60
75

20

65 85 105 125
DBP[ml/100g]
HS CB exhibit less contacts
Points of identical macro-dispersion
with neighboring aggregates
Better Dispersion form a contour line
 Influence of Oil Addition
DI(%) SBR 1500
Competition between mineral 100 60 phr N 326
oil components and the polymer
10
for active sites on 90
25
40
the filler surface. 10

80
25

70 40

60
1000 2000 3000
3
Mixing energy[MJ/m]
Better Dispersion is achieved Oil after CB 0
if the oil is added after the Oil together with CB 100
filler incorporation
Influence of CB Aggregate Size on Percolation
(Micro-dispersion)
Electrical Percolation Threshold
Ω cm]

log(Vol. Resistivity) [Ωcm]

14
LOG (Volume Resistivity) [

12 Aggregate size
E-
Ep P-T
10 Ep
Percolation

Conducting
Insulating

8 Percolated
Compound
Resistivity
6 Range
0 20 40 60 80
Carbon Black Loading [p hr] CB loading [phr]
M. Gerspacher (1998)

Electrical Percolation Threshold (EPT)

is a measure of Filler Micro-dispersion
EPT is a function of:
Filler-Network Formation
- CB aggregate size
- surface activity
 Influence of Polymer on CB Percolation
(Micro-dispersion)

Electrical Percolation Threshold depends

on both: the polymer and the filler
SB R (35)

δ [J/c m3] 1/2

Interaction Potential of the Polymer
18
Saturated Rubbers (IIR, EPDM) SB R ( 23,5)
demonstate percolation at SBR (18)

low concentrations 17 Functionalization

Interaggregate interactions NR
are favoured 16
EPDM

Unsaturation and specifically

interacting groups (styrene) 15
30 40 50
increase percolation threshold Φ c CB [ phr]

Functionalization of the R.H.Schuster (1998)

rubber improve further the

polymer-filler interaction
New teqniques for Filler Dispersion
Masterbatch Technology

Rubber Filler Composites (RFC)

Cabot Elastomer Composites (CEC)

 Rubber-Filler-Composites (RFC)
CB Fluffy

Co-Precipitation Drying RFC SEM

0,5 mm
Silica

Rubber-Emulsion
Waste water

M. Bogun, R. Uphus, U. Görl, R. H. Schuster, KGK 2003

 Cabot Elastomer Composite (CEC)
CB Fluffy

Elongational Flow / co-Precipitation CEC

NR-Latex

No Pellet Fragments

Micro-dispersion !!

Cut growth Resistance

X50 X50 Abrasion Resistance
X50

Batch Mixing CEC

N134 (50 phr) N134 (50 phr)
4-stage 2-stage

M.-J. Wang KGK 2007

Filler Distribution
in
Rubber Blends
 Reasons for Rubber Blending

Improved Processability

Property Combinations
Polarity
Degree of Saturation
New Properties

Blending of Rubbers with different

Polarity creates problems for
- mixing
- vulcanization
- filler distribution
Filler – Polymer Affinity
Adsorption of chains on the filler surface
Chain length
Temperature

Equal Distribution
Preferential Distribution
Morphologies of two Phase Rubber Blends

NBR/SBR
Filler Partition depends on Mixing

(EPDM + CB) + SBR (SBR + CB) + EPDM

Masterbatch Mixing can control filler location

Filler Distribution: TEM Evaluation (I)

80:20

NR

CIIR

CIIR-NR

80:20
Partition of CB in CIIR/NR
CIIR: light Phase
NR: gray Phase

CIIR-EPDM
Filler Distribution: TEM Evaluation (II)

NBR

EPDM

EPDM/NBR EPDM/NBR
Coarse Morphology Silanized Silica
partitioned at interface