Update in Rubber Mixing

and
Rubber Technology
R. H. Schuster
Consultant to LANXESS /German Rubber Institute
12 Jornadas Latino-Americanas de Caucho
Buenos Aires 23/24 Sept. 2013

1.Day
-

Mixing of Rubber
Filler Dispersion
Filler Distribution
Rubber-Filler Interaction
Influence of Mixing on
Dynamic-Mechanical Properties

2.Day
-

Influence of Mixing on Ultimate Properties

Vulcanization: Chemistry and Process
Speciality Rubbers
Oxidative Ageing
Oil Resistant TPV

Elasticity
Energy Dissipation

Abrasion Resistance

Traction

Tensile Strength
Wear
Elastomers
Resistance

Oil Resistance

Ageing Resistance

Low Temperature Flexibility

Tires
928.000 t
5.100 Mrd
+7 %

Elastomers

Technical Rubber Goods

672.000 t
5.400 Mrd
+ 28 %

Source: WdK Report 2010

Mixing of
Rubber Compounds

Role of Mechanical Mixing

Filler
Manufacturing
Aggregates

Aggregates
Incorporation

Agglomerates
Pellets

Size reduction
Pellets

large size
hardness and strength
low density (voids)
stability in pneumatic transport

Mixing
Material properties changing Process

- Rheological Properties
- Further Processing
- Dispersion and Distribution of Fillers
- Phase Morphology
- Physical Properties Set
- Life Time of Rubber Products

Mixing

Compound
Properties

Processing

Part Properties

Purpose of the Mixing Process

Special Chemicals
Polymer(s)

Filler(s)

Raw Material
Quality Control

Process oil(s)

Mixing Process
- Mastication and Blending
- Incorporation of Fillers
- Filler Dispersion/distribution
- Dispersion of ingredients
- Oil incorporation
- Curing reaction is not allowed
to start

Curing Agents
Quality check
of the mixture

FurtherProcessing

Rating Criteria for Mixing Quality

Degree of Filler Dispersion
Tensile Strength
Tear Propagation Resistance
Methods do not allow any in-process control
Retroactive information !

Mixing Equipment
Discontinuous Mixing
Batch Mixing

Two-Roll Mill
Internal Mixer

well established
State of the Art
Can use every form
of the raw materials

Continuous Mixing
promising starts for
some production lines
Relies merely on
free flowing raw materials
i.e. granulates

Twin Screw Extruder

Ring Extruder
Planetary Roller Extruder

Two-Roll Mill
Two rolls which rotate in
opposite sense
(Edwin Chaffe, 1835)

stock
blender

Different speed of the rolls

(Friction)
Steam-heating
Cooling
Formation of a band which
adheres to one of the rolls
Mixing Efficiency is high
Cutting of the blanket
High strains in the Nip region

milling of rubber sheets

Mixing on an open mill

Courtesy: Vredestein

Two-Roll Mill
Advantages
Mixing Process is
followed easily
Mixed Material forms
sheets suitable for
Compression Molding

Disadvantages
Handling of Fillers and
Additives cause housekeeping problems
Prolonged Mixing Times
Less Process Control

Dispersive Mixing action

Exposure of large
is high
surfaces to atmosphere

Internal Mixer Brief History

Internal Mixer
Closed Mixers equipped with
counter-rotating rotors
Rotors with a
screw-like geometry
Axial mixing along the
rotors towards the center
Rotors may or
may not overlap

Ram:
- seals the mixing chamber
- Presses Polymers into
the mixing chamber
- compress large volumes
of fillers

Internal Mixer basic elements

Modular design
- Feeding hopper
- Mixing chamber
- Base Plate
Mixing Chamber
- Mixing chamber halves
- Rotor end plates
- Rotors

Temperature Control
Cooling systems

Internal mixers in tyre industry adopt materials

in any kind of trade form

Courtesy: Harburg Freudenberger Maschinenbau Group

(formerly Krupp / WP)

Internal mixers for technical rubber goods

Types of Internal Mixers

Tangential Rotors

- The rotors do not overlap

- Curved flights which
pump in opposite direction
- Independent speed on each
rotor
- Gap between the rotors favours
improved feeding
- larger batch volume
- Short incorporation time

Intermeshing Rotors

- The rotors overlap

- Intermeshing of the
rotor flights
- small interdistance
- same angular velocity
- high surface/volume ratio
- Better cooling
- Less batch volume
- Good dispersive mixing

Technological Comparison (I)

6

Tangential
5

Intermeshing

4
3
2
1
0
Energy
Efficiency

Thermal
Performance

Co-mastication Plasticizer
Blending

Machine
Utilization

Intake and
Discharge
Behavior

Technological Comparison (II)

Same batch size

Void Volume [m ]

350

tangential
intermeshing

250
150
50
0
1

3
4
5
6
7
Cooling Surface [m ]
tangential

Intermeshing
courtesy: Techint Pomini

Tandem Mixing
Combination of
a master batch mixer (Intermix)
a larger ramless mixer (Tandem)
effectively cooled
intermeshing rotors
Consecutive mixing
Rubber and Filler into the hot
Intermix (upper mixer)
After premixing the compound is
dropped into the tandem mixer.
Mixing time reduced
Cooling and Dispersion
by remilling in the Tandem
J. Peter (1987)

Tandem Mixing
From Tandem Mixer
The final batch is dumped
on a mill or into an
extruder were it will
be sheeted and
conveyed to the batch off
unit.
Advantage:
1) the batch does
not need to be stored between
1st and 2nd stage

Temp.
Add Curatives

2) Better temperature control

i.e. for Silanization

110C

3) Higher troughput
Discharge

Feeding Hopper: Concepts

Pneumatic Feeding Hopper

Hydraulic Feeding Hopper

Advantages of Hydraulic Feeding Hopper

Low noise
level

Constant process
conditions

Hydraulic Feeding Hopper

Fast ram
movement

Little operation
costs
Precise ram force
control

Ram Position Control

Usually ram speed, ram pressure are adjusted during the
installation of the mixer
Problems for hopper functionality:
- Dusty fillers can deposit on the ram
- Sticky compounds on the hopper walls
- Ram jamming
Digital ram position control
- Compound quality can
be improved
- Operation disruptions can
be avoided

Depending on the ram position, ram speed

and ram pressure can be better controlled

Mixing Chamber (I)

Hard Coating

Corosion
Resistance

Equal coating
thickness
Hard Coating
free of Cracks

High tensile
Strength

High Hardness
Intensive Cooling

Mixing Chamber (II)

Temperature Control
Temperature recording is affected by
- Compound flow
- good thermal contact
- extension of the sensor
- placement in sidewall or drop door

- Sensitivity of the sensor

Mixing Chamber (III)

Plasticizer Oil Injection

Feeding liquid components into the mixing chamber

Injection valves are fitted into the mixing chamber
Large mixers are equipped with 4 injection valves
Injection in short time and different types of plasticizer

Rotors
Functions of the Rotors
Impart shear and elongation into the compound
Dispersive Mixing

Distribute ingredients inside the compound

Distributive Mixing

Dissipate heat out of the compound

Cooling
Rotors occupy a high portion
of the mixing chamber
Cooling of rotors improves
mixing efficiency by
increasing the viscosity
of the mix.

Ring cooling

Spray cooling
Strength is achieved by rotor
body walls
Better cooling efficiency with
Ring cooling.
Two body rotor with reduced wall
Thickness. Good heat transfer

Tangential Rotors (I)

Tangential Rotors invented by
F. H. Banbury
Diametrical located
one wing extended in length
Relative low productivity

Most effective mixing

between the rotor flights and the wall
Particular features for tangential Rotors
- Number of wings
- Posisition of wings
- Length of wings
- Angularity of wings
- Outline (active/passive side)
-Tip Width of the wings

Tangential Rotors (II)

2-Wing Rotors

N -Rotors

(Lasch & Frei 1930)

Normal Rotor (Standard)

- Short wings are smaller in height
- used in older mixers
Unwined
Rotor Geometry

Full-4-Wing Rotors (F-4 W)

( Tyson and Comper, 1966)

2 long main wings with

- short pitch angle and large flight depth
- 2 shorter wings at higher pitch angle

Full-4-W-Rotors

High specific energy in a

short period of time
Rapid material intake and
good discharge Properties

Unwined
Rotor Geometry

Tangential Rotors (III)

ST -Rotor Synchronous Technology
(Nortey 1987)

4-wing rotor with special geometry

Each long and each short flight
starts at another end of the rotor.
Improved mixing performance
Best with even speed of the rotors
ZZ 2-Rotor
(Wiedemann & Schmidt 1982)

Flight Angle at 40
Length of fhe flight is shorten
Distributive mixing capacity
Temperature control
Discharge temperature is reduced
30 % throughput than N-rotor
Mixes for Technical Rubber Goods

Tangential Rotors (IV)

High Dispersion Super Cooled (HDSC)
Long Wings are extended to
80% of the rotor length
The wing arrangement supports
The flow over the wing tips
Application in tire industry
Maximum Dispersion Super Cooled (MDSC)
Four Wings uniformly distributed
Spiral cooling
Very agressive rotors
Master Batch Mixing in tire industry
High productivity and good
dispersion

Tangential Rotors (v)

6 Wing-Rotor
Good mixing performance
Faster mixing cycles
Viscosity is reduced faster
Good Compound quality

Intermeshing Rotors
Cooke, 1934

Each rotor equipped with

one helical wing extended
over the full length of the rotor

Interlocking Technology
Johnson (1980)

Long wing of helical formation

Wide wing tip
Two smaller wings are radially
Spaced before and after the long
Wing.

Intermeshing Rotors
PES Technology
Wiedemann & Schmidt (1982)

Partielle Evolventen Schaufel

PES-3 Rotor
Increased width of the wing tips
Material flow between the
Counter-rotating rotors
Good dispersive Mixing

Mixer Base Plate

To absorb forces bearing upon
Individual components
High torsional stability and low weight

Drop Door and Latch

Processing Aspects of
Rubber Mixing

Form of the Main Components

Active Fillers
Pelletized Materials

Rubber Bales

Softener/Plasticizer

Changes in Material Properties

during Mixing
Polymer

Carbon black

Deformation behaviour
Yield point
Wall slippage
Wall adhesion

Surface activity
Agglomerate size
Strength of
agglomerate

Operating param.

Rotational speed
Geometry
Ram pressure
Fill factor
Thermal boundary
conditions
Feed sequences

Material behaviour during mixing

Feed in behaviour
Temperature profile

Change in material properties

viscoelasticity
density

heat capacity
heat transfer

Result of mixing
Degree of dispersion
Fluctuations in viscoelasticity
Thermal loading

Incorporation and
dispersion of carbon black
or other fillers

Break-down of Particle/Domaine Size

Formation of large Interphases

Elongational Flow
Shear Stress

Dispersive Mixing
Breakage
No Breakage

Time

Distributive Mixing
Homogenization of ingredients
Even concentration of ingredient

Laminar Mixing

Increased interface between

two layers
shear

strain

Flow pattern in an internal mixer

A
B

Front Wall (Peripherical Direction)

Influences to Flow
- rotor geometry
- angle of the rotor blades
- number of the main
and side blades
- fill factor

mA
Converging Flow

mB
II
C
Leakage Flow

III

Material can be transported

(i) rotationally with the rotor flight
(ii) through the gap between
the wing tip and the chamber wall
(iii) along the flight and pass
around the rotor end

Axial Direction

Distributive and Dispersive Mixing Zones

around the Rotor Wing

Mixing Cycle
and
Influence of Material Parameters

Masterbatch Mixing Cycle

Mastication

Polymer
charging

Incorporation

Dispersion

5 6

Filler
incorporation

Mastication
Filler
charging

Oil injection

Distribution

8
Discharge

Ram
sweep

After
mixing

Incorporation of the Filler

Rubber

Filler

Incorporation Time
depends on:
- type of Filler
- type of Rubber
- content of oil
- type of Mixer
- Processing Parameters

Incorporated Filler

Filler is incorporated into the Rubber

Reduction of total Volume of the Mix
Dispersion is not satisfactory

Example of a mixing process optimised

for throughput
Mixer:
2

5 6

2000

200

1500

150

1000

100

500

50

0
0

50

100

150

time (s)
G. Nijman, DIK Seminar 2007

200

0
250

Temperature (C)

Power supply (kW)

GK400N
Rotor:
4 Wing
Fixed speed

Power
Ram position
Avg Power
Temperature

Power Demand for Mastication

Power Peak [kWh]

16
14
12
10
8
6

20

40

60

80

Polymer Dosing Temperature (C)

Ram Setting Time

Ram Setting: Rubber Temperature

120

30 C
60 C

100

90 C

80
60
40
30

40

50

60

Rotor Speed

70

80

Ram Setting: Influence of CB

Effect of Filler Structure
(DBP)

End of
Incorporation

Ram Displacement

Ram Displacement

Effect of Filler Loading

N 347
N 330

N 326
Mixing Time t
Addition of
the Filler

Mixing Time t

Incorporation Time increases with

- the Filler Loading
- the DBnumber

Lecture_POA_11.06.2007_54

Ram Setting: Influence of Filler Type

CB vs CNT

CB needs long incorporation time

Caused by the high structure or
OA Number
CNTs do not have structure
Incorporation time is reduced to
1/3 compared to CB

Ram Setting Time [s]

100
80
60

CB

40

NBR
HNBR

20

CNT

12

Filler [Vol.%]

Mixing Temperature

spec. Power Consumption

Power Consumption & Temperature

Mixing time t

Mixing time t

The second power peak is more pronounced when

the filler loading increases
The mixing temperature increases with loading
The viscosity decreases with temperature of the mix

Energy Input: Influence of Filler Type

CB vs CNT
HNBR

Energy input is much higher for

CNT compounds than for
CB compounds
The effect is caused by the increase of
Viscosity in CNT compounds.
A limit for processability is reached for
CNT compounds

Energy Input [MJ]

NBR

CNT

5
4
3

CB
2

12

Filler [Vol.%]

Mixer Energy-Balance
(Typical example)

15% 10%

compound enthalpy
for cooling

30%
45%

mechanical
mixer enthalpy

Influence of oil incorporation

If the Oil and CB are added at the same time
-Oil is incorporated quickly
-Maximum torque is relatively small

If the Oil addition is delayed.

-Better dispersion
-Time should be chosen

If the Oil addition is strongly delayed.

-Lubrication films impair the dispersion
-energy uptake is small
-Long mixing time

Strategies for Oil Dosage

High amount of oil
Mixing time is very long
Mixer requires long time
to recover torque

Automatic intermitent
Oil injection

Energy uptake
Shorter mixing cycle
Lecture_POA_11.06.2007_60

Scaling-Up
Important Step for Production
Requirements
- Geometrical Similarity
same clearance between rotor and
mixing chamber
Frequency of the rotors should be inversely
proportional to the width of their tips

- increase the initial temperature and reduce

cooling of the smaller mixer

- identical shear strain and shear stress power/

unit volume

- same frequency of passage of any small element

through mixing regions

How to increase productivity and quality

Design of the mixing process
Mixing effectivity

Throughput

Target Conflict: Quality-Throughput

Quality

Wiedmann & Schmidt RCT 1984

Fill factor for optimal filler dispersion:

- Increases with ram pressure and temperature
- Decreases with rotor speed and temperature

Design of the mixing Process:

Effect of Mastication & CB Incorporation

Power kW/h

: Bales are cut

: Crumby structure
: Homogeneous Blend
a: Ram down
b: (minimum)
c: Ram at lowest position
d: Maximum density
e: CB incorporation completed
Time (s)
Mixer: GK45E
Rotor: PES-3 fixed speed

G. Nijman, DIK Seminar 2007

Experimental Design
Fill factor
Rotor speed (rpm)
Blending time (s)
Dispersion time (s)

low
0.58
40
30
42

high
0.63
60
60
60

FRbD
crumby
160
180
loose black

FRBD
homogeneous
162C
182 s
completed

Results
Blend appearance
Dump temperature
Cycle time
CB incorporation

G. Nijman, DIK Seminar 2007

Mixer: GK45E
Rotor: PES-3 fixed speed

Fingerprints
FRBD

Power kW/h

Power kW/h

FRbD

Time (s)

Time (s)
Mixer: GK45E
Rotor: PES-3 fixed speed

G. Nijman, DIK Seminar 2007

Influences on Compound Properties

Process

Material
Polymer
Filler
Plasticizer
Additives
Curing system

Quality

Equipment

Dosage
Weighing tolerance
Calibration

Discontinuous
Continuous
Tandem
Feeding Sequence
Duration of
Mixing Phases

Human
Education
Qualification
Motivation

Geometry
Maintenance
Cooling
Control
Sensors

Batch to batch variation in Fingerprints

A variation in mixing quality could lead to

too heavy components
too much material (i. e. 0.5 kg in one PCR tyre)
a huge amount of rework
over dimensioned compound recipes
and therefore a rather inefficient production
3,5
3,4
3,3

Dimension

3,2
3,1
3
2,9
2,8
1

Sample

10

What can be measured on-line

to control the mixing process ?
Ram Displacement
Ram Pressure

Mixing Chamber
Temperature

Rotor Speed

Power

On-line Electrical Measurements

Ram

ring electrode

Chamber wall

Electrode
Rotor wing
Amplifier
Picoamperemeter
El. Source

Benefits and Disadvantages of

Batch Mixers
Benefits
Accepts almost any
trade form
Proven technology
No need for special
dosing equipment
Both automatic and
manual control
Efficient dispersion
effect
Flexibility in run length
easy to maintain and
robust machine
Wide application field

Disadvantages
High power peaks
Batch to batch variation
heat history
material weight variation

Dust forming by air

movement
Labour intensive
Many adjustable
parameters
High installation costs
Complicated
downstream
Lecture_POA_11.06.2007_72