Emulsil Silica Masterbatch Technology:

New Approach for High Performance Tread

Tire Technology Expo 2015
Christopher Hardiman Director of Technology INSA, LLC
 Paracril

Who is ? NBR Paraclean

Paracril
OZO
NBR/PVC
INSA has more than 50 years of experience producing Synthetic Rubber.
INSA is the only producer of Emulsion Styrene Butadiene Rubber (ESBR) and Nitrile
Butadiene Rubber (NBR) in Mexico Emulprene Emulblack
The plant is strategically located in one of the most important industrial corridors in the
Gulf Coast of Mexico with its own Petrochemical Terminal to receive BD
SBR Arlatex
Our wide variety of products are used in Applications such as tires, footwear, industrial
rubber goods, adhesives, sealants, food grade, chewing gum, non-woven materials,
paper coatings and textile to mention some. Insagum Emulsil

Sales Information:
Tomas Acevedo Cesar Perez
Commercial Director Sales Manager Website:
tacevedo@negromex.com cesar.perez@negromex.com www.negromex.com
Family of Products
COLD SBR
Is available in both non oil extended and oil extended
types for tires and general rubber industry usage.
PARACRIL NBR
Wide range of grades produced by cold and hot
polymerization process. These grades offer benefits in
thermoplastic modification for lower compression set
and green strength improvement in thermoset
recipes.
CARBON BLACK MASTER BATCH
Offers excellent physical properties and outstanding
processing characteristics due to the complete
dispersion of the carbon black and processing oil in
the polymer
HIGH STYRENE MASTERBATCH
Is excellent for improving hardness and stiffness in
floor tiles, shoe soles, rolls sporting goods, extrusion
and hard rubber compounds.
EMULSIL
Silica-ESBR Polymer-filler system is produced by INSA using
a state of the art technology
HOT SBR
Are used in the manufacture of a variety of adhesives and
sealants. Product is available in several grades, providing a wide
range of solubility and viscosity, cohesive strength and holding
power can be achieved.
INSAGUM
The products complies with U. S. FDA regulation referenced
to SBR used for Chewing Gum
PARACRIL NBR CRUMB AND POWDER GRADES
Particulate products have primary application in thermoplastic
modification, adhesives, and friction products. Linear and an
expanded list of cross-linked grades are available with a variety of
partitioning agents.
 What is ?
Polymer System of 40-70 PHR of high surface area silica fully dispersed

Silica-ESBR
Silica fully functionalized for maximum performance.

Polymer-filler system is Completely alcohol-free product.

produced by INSA using
a state of the art
Dispersion certified by Lot Certificate of Analysis

technology. Oil extended at 10 to 30 PHR level (HAO/Naphthenic/RAE/TDAE).

Composition certified by Lot Certificate of Analysis

Excellent compositional control is a key product feature.

Bale product form

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Silica Surface Reaction
INSAs Emulsil Hydrophobation Process
Complete de-agglomeration of silica Deagglomerated
particles PRIOR to reaction with silane. Silica + Silane
Elimination of silica particles above 10
microns in size.
Silane reaction with silica in a reactor
with the removal of reaction
byproducts.
Clean silanization of entire silica
surface.
Clean
Process protected by US Patent Hydrophobated
8357733. Silica

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 Silica Particle Size Distribution in Emulsil
% PASS %CHAN
100 10

90 9

80 8

70 7 Typical particle size

60

50
6

5
distribution of silica
40 4 feed for the Emulsil
30

20
3

2
SMB production
10 1
process (silica
0 0

1 10
- Size (microns) -
100
dispersion in water).

Summary Percentiles Dia Vol% Width

mv = 3.772 10% = 1.312 60% = 4.226 3.753 100% 3.915
mn = 1.337 20% = 1.843 70% = 4.694
ma = 2.692 30% = 2.55 80% = 6.193
os = 2.229 40% = 3.196 90% = 7.165
sd = 1.958 50% = 3.753 100% = 9.168

Emulsil Technical Data
Composition (PHR)
APPLICATION INSA Code
Oil Type Rubber Oil Silica A/Ox
TIRES 4773R RAE 100 30 70 Staining
TIRES 4773T TDAE 100 30 70 Staining
TIRES X4793 * TDAE 100 30 70 Staining
RETREADING 10483 HAO 100 12 60 Staining
RETREADING 1671R RAE 100 12 60 Staining
INDUSTRIAL 1671N NAPH 100 12 60 Non-staining

* Developmental Grade

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 Mixing Study: Passenger Tires
Comparison of , Experimental HS area and SSBR
Polymer ML 1+4 Styrene Vinyl TDAE Oil Silica Tg
[MU] [Wt.-%] [Wt.-%] [Wt.-%] [Wt.-%] [C]
4773T 96 36.5 --- 14.6 34.0 -37
X4793T 118 36.5 --- 16.4 33.0 -37
High Vinyl SSBR 47 25.0 50 27.3 --- -29
Funct SSBR (~OH end group) 62 21.0 63 --- --- -25

*Tg value from the base polymer

X4793T 4773T
ESBR 100 phr ESBR 100 phr
TDAE Oil 35 phr TDAE Oil 30 phr
Silica (250 CTAB) 70 phr Silica (160 CTAB) 70 phr

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 Tread Formulation - Passenger Tire
std sSBR, std sSBR, fct sSBR E4773T SMB, X4793T SMB,
Ingredients
160 silica (80) 195 silica (76) 160 silica (80) 160 silica (49) 250 silica (49)
E4773T SMB 143.47
X4793T SMB 149.01
High vinyl sSBR, OE 96.25 96.25
Fct sSBR (~OH) 70.00 3-pass mixes in
High cis Nd-BR 30.00 30.00 30.00 30.00 30.00
HDS, 160 ctab 80.00 80.00 BR1600
HDS, 195 ctab 76.00
N-234 CB
TDAE oil
10.00
6.00
14.00
10.00
10.00
28.00
37.00
15.25
22.50
7.50
3 dry mix (DM)
TMQ 1.00 1.00 1.00 1.00 1.00 controls
6PPD 2.00 2.00 2.00 2.00 2.00
MC wax
Stearic Acid
1.00
2.00
1.00
2.00
1.00
2.00
1.00
2.00
1.00
2.00
2 SMB compounds
Zinc Oxide 3.00 3.00
TESPT, S4 silane 6.40 6.40 6.40 Silica surface area
TOTAL 234.65 238.65 230.40 234.72 218.01
First Mixing Pass Reaction Pass Reaction Pass Reaction Pass Straight mix Straight mix based on CTAB
Hold time (4 min at 155C) (4 min at 155C) (4min at 155C) 0 0
Zinc Oxide
Second Mixing Pass
3.00
Add ZnO
3.00
Add ZnO
3.00
Add ZnO Simple remill Simple remill
Sulfur, cure adjusted
Hold time (4 min at 155C) (4 min at 155C) (4 min at 155C) 0 0
Final Pass Mix Cure to 105C Mix Cure to 105C Mix Cure to 105C Mix Cure to 105 C Mix Cure to 105C
TOTAL MIX TIME 17 min 17 min 17 min 12 min 12 min
Cure Package CBS 2, DPG 2 CBS 2, DPG 2 CBS 2, DPG 2 CBS 2, DPG 0.1 CBS 2, DPG 0.1
TBzTD 0.25 TBzTD 0.25
Sulfur 1.2 Sulfur 1.2 Sulfur 1.2
Sulfur 2.2 Sulfur 1.87

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Viscosity all mixing cycles

195 ctab silica has

very high viscosity in
all passes.
SMB viscosities drop
significantly after each
pass.
Note: no extended
SMB mixing at the of
each cycle.

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Final mixing parameters
Low strain shear thinning & high
strain extrudability effects
E4773T is best, while the X4793T
slightly better than std sSBR

115
Garvey Die extrusions, 90 oC, 45 rpm
std sSBR, 160 silica (80), DM

std sSBR, 195 silica (76), DM

X4793T SMB, 250 silica (49)

116
Viscosity vs Torquemin

117
Scorch Safety

118
Cure profile

Silica flocculation
effect on HSA 195
Marching modulus
on dry-mix controls
HSA SMB has
longest incubation
period, cure profile
can be adjusted
further towards
E4773T

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Physicals

Uniform hardness
with the exception
of 195 HSA
SMB range on M300
dependent on cure
Flexibility in
adjustments to
meet criteria

120
Physicals

M300 effect on TS,

%Elongation.
Similar effect on
design flexibility
via cure
adjustments.

121
Abrasion, Tear Index

X4973T HSA SMB is

significantly better
Major advantage in
abrasion & tear
195 HSA dry mix
does not improve
abrasion compared
to the SMB

122
Physical/Dynamic Interactions

IP = s / h
s = slope of stress/strain
between 100-300%
h = filler-filler network based on
G shear modulus, i.e. Payne
effect

123
Tread Compound Performance

124
Tread Compound Performance

125
Overall Performance

195 HSA omitted

due to bad
performance.
X4793T has major
advantages overall.

126
Payne Effect

X4793T has lowest filler-filler interaction as a response to the modulus strain dependence.
E4773T is better than the std sSBR compound.

127
Conclusions
The use of a 250 m2/gm silica filler has been successfully demonstrated with the Emulsil Silica
Masterbatch product technology in the experimental X4793T product.
The X4793T when compared to sSBR/BR and fct sSBR/BR mixes yields:
o Similar or better processability with good extrudability values
o Excellent scorch safety with fastest T90 state of cure
o Good balance between hardness, M300, TS and % elongation
o Allows for further cure adjustment to provide flexibility in physical properties
o Superior DIN abrasion and Tear values
o Outstanding physical/dynamic Interaction Parameters (IP) and Reinforcement Index (RI)
o Lowest filler-filler interaction by Payne effect
o Comparable RR with best wet and ice traction with no loss in dry traction

The E4773T, a commercial product currently available based on 160 m2/gm silica, offers:
o Best processing, mixing and extrudability performance
o Compares favorably against the std sSBR compound
o Similar RR and wet traction
o Better DIN abrasion, dry traction
o Significantly better ice traction and low filler-filler interaction

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 Process and Performance
Reduction in Processing
utility costs Benefits

Mixing Raw Materials

Savings Savings

Overall
Tire
Mixing capacity Performance
increase
Health
Mixer & Safety
Wear Thank You!!!
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