Polymer – Filler Interaction

Polymer-Filler Interface
Surface Activity
Surface Modification

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

12 Jornadas Latino-Americanas de Caucho

Buenos Aires 23/24 Sept. 2013
 Requirements for Filler Dispersion

Elongational Flow

Shear Flow

Cohesive Strength Hydrodynamic Force

cη π Ra2 τ xy
FC = ν F H FH =
γ
γF = Contact points per Aggregate

γνF H
H = Interaction Force
Fc = Cohesive Force
FH = Hydrodynamic Force
τxz = Shear rate
η = Viscosity
(η τ ) x z crit >
c π Ra
2
Ra = Radius of Agglomerate
γ = Interfacial Tension
Dispersion is the result of opposite interactions
during the Mixing Process
Interaggregate
Interaction
Strong Interaggregate Interactions
caused by cohesive forces (ν x H)
Insufficient Polymer Adsorption
Poor Wetting of the Filler surface
Insufficient Phase Adhesion
Polymer-Filler
Interaction
Weak Interaggregate Interactions
caused by reduced surface activity (H)
and contacts per aggregate ν
Good Wetting and
Strong Phase Adhesion due to
Polymer Adsorption or Chemical Bonds
Material Parameters that support
CB Dispersion

Polymer Chain length (viscosity)

Polymer Nature
double Bonds
functional Groups

Low surface activity

Low surface specific area
High Structure/Porosity
 Nature of Polymer-Filler Interaction
Physisorption
Interactions between polymer segments and active sites
on filler surface.
S S S

- chemical nature of the polymer

- surface activity of filler

S SS
- specific surface area of filler

HO OH

Chemisorption Si O OH

Si
OR
O Si

-Chemical reaction between Si

O
OH
Polymer and Filler HO
Si O
OH

- Functionalized polymers
or surfaces with functional groups
are required
ABTB_Sao Leopoldo
 Competitive Adsorption of Polymers (I)
Influence of the Chain Length

5,2
Number of Contacts per Chain νc Mw [10 -3 g/mol]

222 52 22
νc = P 1/ 2

Frisch & Eirich (1952) t = 0h

t = 0,5h

t = 1h

t = 3h
Long Chains are adsorbed first
They can replace short chains t = 24h

from the Filler surface.

Polyisoprene / N330
Driving Force is the Adsorption Cyclohexane at RT
Energy per chain

Bussmann & Schuster (1993)

 Competitive Adsorption of Polymers (II)
Influence of the Chemical Nature

Poly-isoprene Polystyrene Poly-isoprene Polystyrene

Mw 200,000 g/mol Mw 10,000 g/mol Mw 200,000 g/mol Mw 10,000 g/mol

Energetical beneficial
before Adsorption after Adsorption Interactions: Styrene-CB

The stronger interactions of the styrene groups

overcompensates the the chain length of IR

Preferential polymer-filler interactions

Adsorption of Polymer in Rubber Compounds
Bound Rubber
Rubber Matrix
Rubber –Filler
Interface
Filler Particles

Polymer-Filler Contact Area

Ψ = φρS φ- volume fraction of the filler
ρ-density of the polymer
S- surface specific area

Interface Properties Bound Rubber:

- amount of polymer that is
-Higher density strong bonded and cannot
-Reduced chain mobility be extracted by good solvents
-Reduced transport processes R filled − R extr
BR =
R filled
Dimensions of the interface ?
Indication for good
Polymer-Filler Interaction
Influence of surface spec. area and temperature
on Bound Rubber Content
40 40

35 35
N121
SBR + N330
30 N234 30
N375 N110

Bound Rubber [%]

Bound Rubber [%]

N339 N242
25 25
N220
N330

20 20
N326
N683 N539

15 N550 15
N660

10 N765 10
N762

5 5

0 0
0 20 40 60 80 100 120 140 160 20 30 40 50 60 70 80 90 100 110
2
CTAB [m /g] Temperatur [°C]

Bound rubber results from physical adsorption of chains

 Interfacial Effects: Chain Mobility
Normal H-NMR T2 –Relaxation
1
Mobility

Segment NBR/Filler
density T2, F 1.0
(Packing)
T2, 0
0.9
MMT
Matrix
0.8
CNT
Distance from
Hindered filler surface 0.7
Mobility
40 µs - 50 ms
90° 180° AQ 0.6
0.02 0.04 0.06 0.08 0.10 0.12
τ τ

φ
3 µs 6 µs t

( )
− tT
M = Mt0e 2
M = M 1 − e
− T1
t
t
Lower T2Relaxation Time
M z = M 0 (1 − exp
xy
(− ) M xy = M 0 exp (− )
z 0
T1 T 2
→ reduced Chain Mobility
M = Mxy

180°
Effect is caused by the amount of
Chains in the Rubber – Filler Interface
Indication for good filler dispersion
 Interfacial Effects: Equilibrium Swelling
Normal
Swelling

Segment
density
(Packing) qr , F  φ 
= 1 − m  
qr , 0 1−φ 
Matrix

Distance from
Hindered filler surface
Swelling

The effect depends on:

Degree of Swelling Q

2,0

→surface specific area

1,5 →surface activity
→state of dispersion
CNTs vol. %
1,0 Basis →polymer nature
0,27
NBR/CNT 0,8
1,33
MEK 25°C
0,5 2,1
3,1 Direct expression of
4,1
0 10 20 30 40 50
Rubber-Filler Interaction
√t (min 1/2) with potential for applications
 How to improve Polymer-Filler Interaction ?

Polymer Filler
Optimizing MW and MWD Optimized or new types of fillers

Optimizing chemical composition Taylor made Surface Activity

Functionalization of the Polymer Functionalization of the Filler Surface

 Polymeranalogue Reactions

- Mw and MWD not changed

- Concentation of functional groups small
- Chain Dynamics should be maintained

Epoxidation
M. Jacobi et al. KGK (2003, 2007, 2009)

Addition on double Bonds

Methatesis reactions on double Bonds

Cross-Coupling Reactions
 Copolymerization with new Monomers

- Mw and MWD can be changed

- Position of the functional groups
random or defined (end-functionalization)
- Concentation of functional groups variable
- Chain Dynamics should be maintained

X-Z
Functionalization Li X
end-functionalization
of SSBR and Li-BR X
A. Halasa & Hsu DKT (2006) X
M-X + monomer
X X
X In chain functionalization

Use of functional Monomers

in E-Polymerisation
G. Thielen DKT (2009)
S. Thiele DKT (2012) Polar groups In co-monomers

Comonomers in IIR
p-Br-Styrene
W. Waddell RCT (1993)
 Optimizing Properties of CB

Increasing the structure of CB

120
EB 1 Tailored ASD
EB 2

(ml/100g)
Preheated Air Feedstock: Oil
N 121 EB 3
110

COAN [ml/100g]
Refractory
Natural Gas 1650 °C 915 m/sec
Alkali Metal Additive

COAN
Reaction Time
100 N 234 N 134
0.3 to 1.0 sec
Quench water

90
100 110 120 130 140 150 160
2
STSA [m /g]

2
Spec. Surface Area (m /g)
Higher Structure leads to M. Heinz, R. Friehmelt, M. Borm, KGK (2011)
→better Dispersion
→larger Polymer-Filler Interface
→less Filler Networking
 Tayloring Surface Activity

Through Process Parameters

Physical or Chemical Treatment
Functionalization
Silanisation of Silica
Influence of Annealing on CB surface activity

Heat treatment
Inert atmosphere
2500-2700 °C

10 nm 4.4 nm
Influence of Graphitization on Gas Adsorption
TEM Primary particle (nm) N2 -spec. Surface (m2/g)
28 110

100
26
90
24
80
22
70

20 60

Original Graphitized Original Graphitized

M. Gerspacher, RCT (1998)

N2 Adsorption → Interaction potential of graphitic sites is reduced

Strong adsorption sites are no more present
Graphitized CB has no reinforcing effects
 Site Energy Distribution Function for CB
C2H4/N220
0,2
Fraction [%]
0,02

0,16 III I II III IV

I
0,01
0,12
N115 69 13 15 3
IV
N220 84 7 7 2
f(Q) [mol/kJ]

0,08 0
20 30 40
N220g 99 - <1 <1
0,04
II
III IV N550 93 6 1 <1
0
0 10 20 30 40 50
Q [kJ/mol]
I II III IV Energy [kJ/mol]
I II III IV
N115 15 19 24 31
N220 16 19 24 32
Graphitic Crystallit N220g 17 - 25 29
I III
Layers sp2 Edges
N550 15 21 26 32
II Polymorphic IV Slit Shaped
3
Carbon sp (?) Cavities (A. Schroeder & R. H. Schuster ,1999)
 Implementation of SiO2 nanoparticles in CB
Carbon Silica Dual Phase Filler

Perturbation of CB Section A-A

microstructure by
Implementation of
SiO2 nanoparticles

Size and concentration of CSDPF 2000

CB microcrystallites
is reduced.

Less graphitic structures

rystallite edges and
Slits on the surface CSDPF 4000

M. –J-Wang KGK 2006

 Surface Modification of CB
Chemical Treatment with Physical Treatment with
reactive species Atmospheric Plasma
Radical generators: (Air, N2/NH3 Q)
Diazonium Salts (N. Tricas & R.H. Schuster KGK (2008)

(M. J. Wang KGK 1995) Filler

AIBN and Peroxides
ZDMC
(Müller & Schuster 1998)
Plasma

Medium energy sites remain for

Filler – Matrix Interactions
II

III IV
Surface modified CB
High energy Sites
reduced by
Surface Treatment
 Plasma Modified CB
< < <

Nitrogen Plasma Air Plasma

HO N
N

H
+
N
Bound Rubber

Incorporation of Treated CB
N-Structures
In the Lattice of CB Untreated CB Treated CB

Hydrophilic CB
Good interactions
With polar Rubbers

Untreated CB

N. Tricas, R. H. Schuster, KGK (2006)

 Precipitated Silica
Manufacturing
Sodium Silicate Solution
Acid / Metal Salt Solution
Silo

Distribution
Filter
Granulator
Reactio Dryer
n
Tank Silo

Mil
l
Distribution
Homogeni -
zation Special surface Chemistry:
Polar Silanole Groups
Hidrophilic surface
Strong Inter-particle interactions
100
a: NBR (12;35)
KBr-Pressed piece
By „Hydrogen Bonds“
------ b: NBR (12;35) + Silica
standardized Extinction

....... Difference (b-a)

CN

80

Poor interactions with

HO

60

non-polar Rubbers
CN

40

20
EPDM, NR, BR, SBR
-1

-1
2249 cm

2237 cm

Good interactions with

0
2280 2260 2240
- 1
2220 2200 polar Rubbers: NBR, HNBR
Wave number (cm )
 Silanization of Precipitated Silica

The reaction of Silanole Groups Silanes are used for

with ethers lead Hydrophobization and coupling
to hydrophobization
The polar surface is transformed
into a non-polar surface.

Interaggregate Interactions are

reduced in number and strength

Better Dispersion
Silanization: Reaction Scheme

Primary Reaction Secondary Reaction

Formation of ether bonds Water is consumed stoechiometrically
Si-O-Si Formation of ROH !
Traces of water required Surface is shielded by a
Formation of ROH ! hydrophobic layer
Surface becomes less
hydrophilic
Monofunctional Silanes
BR NBR
Dynasylan 
PTEO Si

OCTEO 83,7 % 91,2 %

Si-C3

9216
92,7 % 98,7 %

Si-C8
Alkyl Chain shields the
92,2 % 98,2 %
polar surface
Effectivness is given by
the length of the alkyl chain
Bi-functional Silanes

Silica Polymer
coupling coupling
 Micro-dispersion of silanized Silica

a) SSBR(50V; 25S)
Si (20phr) Silane

b) SSBR(25V; 25S)
Si (20phr)Silane

Particle Size Distribution

Silica Distribution in NBR/BR Blends

Silica Si + PTEO 1/3

Si + PTEO 1 Si + OCTEO 1
 Site Energy Distribution on Silica Surface
OH
Silica
HO
Si O OH
Si Silica(dehydroxylated)
Si
OH
0,16
Si
OH Silica + Si-C3
OH

HO
Si
OH
O
Silica + Si-C8
0,12
HO
Si
OH
O OH
Si-C3
OR
Si

Si
O Si
O
OH
0,08 Si-O-Si
HO
Si
OH
O
Silanole Groups
0,04
HO
Si
OH
O OH
OR
Si-C8 Roughness/Pores (?)
Si
O Si
O
Si
OH
Si O 0
HO OH
5 15 25 35 45
Q, kJ/mol

Silanization: high energy sites are reduced

low energy site region shifted to lower values
Interparticle Interaction is reduced by silanization
Effects of Filler Dispersion
on
Rheological Properties
 Influence on Mooney Viscosity
SBR/CB

Dispersion vs. time and rotor speed Viscosity vs. time and rotor speed
 Influence of Silanization of silica
Mooney Viscosity

Efficient Silanization leads

to better Silica Dispersion.

Better Dispersion leads to

less filler-filler contacts
and reduced Viscosity
 Influence of mixing time on
viscoelastic properties of uncured compounds
(SBR/Silica)
1,0E+07 Mixing time
Storage Modulus G' [Pa]

t=150s
t=180s
t=210s
t=240s
t=300s
t=360s
1,0E+06 t=420s
t=600s
t=700s

1,0E+05
1,0E-01 1,0E+00 1,0E+01 1,0E+02 1,0E+03
Strain Amplitude γ (%)

With increasing Mixing time the stiffness of the

uncured coumpound decreases
 Influence of Batch to Batch variations on on
viscoelastic properties of uncured compounds

Variations in quality of mixes can be

caused by different states of dispersion
Influence of designed aggregate size distribution
0.240

[ - ] (80°C)
EB 3
N 234

δ 60°C δ
N 134

tan
MDR tan
0.190
N 121 EB 2

MDR
Increased „Structure“ (OAN) leads EB 1

to better dispersion.
0.140
Designed aggregate size distribution 110 120 130 140 150
STSA [m 2/g]
can improve viscoelastic compound 2
properties Spec. Surface Area (m /g)
120
EB 1 Tailored ASD

COAN (ml/100g)
Better Dispersion causes less EB 2
N 121

[ml/100g]
EB 3
energy dissipation during 110

periodically deformation
COAN 100 N 234 N 134

90
100 110 120 130 140 150 160
2
STSA [m/g]

2
M. Heinz, R. Friehmelt, M. Borm, KGK (2011) Spec. Surface Area (m /g)
 Influence of the Filler Type
Viscosity and Viscoelastic Properties (RPA)

High viscosities at far less CNT concentrations

Percolation Threshold: CNT ≈ 2 Vol.% vs. CB ≈ 20 Vol.%