Millathane E34

Millathane E34

Millathane E34

Millathane E34

Millathane E34

Millathane E34

Millathane E34

Millathane E34

Millathane Millathane E34

Millathane E34

E34
Millathane E34

Millathane E34

Millathane E34

Millathane E34

A MILLABLE POLYETHER POLYURETHANE RUBBER

Millathane E34

Millathane E34

Millathane E34

Millathane E34

Millathane E34

Millathane E34

Millathane E34

Millathane E34

Millathane E34

Millathane E34

Millathane E34

TSE INDUSTRIES, INC. Millathane E34

 TABLE OF CONTENTS
GENERAL DESCRIPTION:
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . .3
Typical polymer properties . . . . . . . . . . . . . . .3
Typical physical properties . . . . . . . . . . . . . . .3
End use applications . . . . . . . . . . . . . . . . . . . .3
VULCANIZATION OF MILLATHANE E34
Sulfur curing system . . . . . . . . . . . . . . . . . . . .4
Effect of sulfur . . . . . . . . . . . . . . . . . . . . . . . . .4
Effect of MBTS and MBT . . . . . . . . . . . . . . . . .5
Effect of Thanecure ZM . . . . . . . . . . . . . . . .6
Effect of zinc stearate . . . . . . . . . . . . . . . . . . .7
Peroxide curing system . . . . . . . . . . . . . . . . . .8
Effect of peroxide concentration . . . . . . . . . .8
Comparison of sulfur vs. peroxide . . . . . . . . . .9
BASIC COMPOUNDING
Carbon black loading studies . . . . . . . . . . . .10
Non-black filler studies . . . . . . . . . . . . . . . . .11
Evaluation of plasticizers . . . . . . . . . . . . . . . .12
PROCESSING OF MILLATHANE E34
Mixing on open mills . . . . . . . . . . . . . . . . . .13
Mixing in internal mixers . . . . . . . . . . . . . . . .14
Compression & transfer molding . . . . . . . . . .14
Injection molding . . . . . . . . . . . . . . . . . . . . .14
Calendering and extrusion . . . . . . . . . . . . . . .14
CHEMICAL RESISTANCE . . . . . . . . . . . . . . . . . .15
ADHESION TO METAL . . . . . . . . . . . . . . . . . . .16
GLOSSARY . . . . . . . . . . . . . . . . . . . . . . . . . . . .17

TSE INDUSTRIES PRODUCT LISTING . . . . . . . .18

Millathane, Thanecure and Crystal are registered trademarks of TSE Industries, Inc.

The recommendations for the use of our products are based on tests believed to be reliable.
However, we do not guarantee the results to be obtained by others under different conditions. Nothing
in this brochure is intended as a recommendation to use our products so as to infringe on any patent.

pg. 1 MILLATHANE E34 8/04 (800) 237-7634 TSE INDUSTRIES, INC.

 TSE INDUSTRIES INC.
CLEARWATER, FLORIDA
For the past forty years, TSE Industries has been an industry leader in new, innovative
solutions for the rubber industry. Our millable polyurethane gums, sold under the trade
name MILLATHANE have grown to be the sales leaders in the world today.

TSE Industries has recently completed its Phase Five Expansion encompassing 300,000
square feet spread over twenty acres in Clearwater, Florida. A large part of this is
dedicated to significantly expanding our Research and Development efforts so that
we will remain the Technology Leaders into the 22nd Century.

TSE INDUSTRIES, INC.

4370 112th Terrace North, Clearwater, Florida 33762, USA
Tel: (727) 573-7676 (800) 237-7634
Fax: (727) 572-0487
www.TSE-INDUSTRIES.com www.MILLATHANE.com MILLATHANE E34 8/04 pg. 2
MILLATHANE E34

A High Performance Polyether Polyurethane Rubber

INTRODUCTION TYPICAL POLYMER PROPERTIES

MILLATHANE E34 is a high performance polyether Chemical type Polyether polyurethane
polyurethane rubber for applications requiring: Physical form Solid bale or milled sheets
Color Pale amber to dark
High abrasion resistance
Specific gravity 1.04
Low temperature flexibility
Mooney viscosity range
Ozone resistance
(ML 1+4 @ 100 C) 35 to 65
Oil and fuel resistance Standard Mooney viscosity
Outstanding hydrolytic stability (ML 1+4 @ 100 C) 50 10
Improved processing Odor Faint, characteristic
Storage stability Excellent
Health hazard None
MILLATHANE E34:
Can be compounded and processed by the

use of conventional rubber manufacturing TYPICAL PHYSICAL PROPERTIES

equipment mixed on two roll mills or an Hardness range 45 to 90 A
internal mixer. Tensile strength Up to 5800 psi, 40 MPa
Compounds can be calendered; extruded; Low temperature -62C (-80F) Brittle Point
injection, transfer, or compression molded Ozone resistance Excellent
Oil & fuel resistance Very Good
to produce finished polyurethane parts.
Hydrolytic stability Very Good
It can be vulcanized by organic peroxides or
Weathering Very Good
sulfur with thiazole accelerators. Resilience 40 to 50%

MILLATHANE E34
END USE APPLICATIONS
Printing rollers Copier rollers
Drive belts Radar dome covers
Conveyor belts Footwear outsoles
Copier stops Cable jackets
Aircraft fasteners Dust covers

CRYSTALLIZATION OF MILLATHANE E34

MILLATHANE E34 undergoes a reversible change called crystallization where the polymer chains align themselves
into a crystal network. This causes MILLATHANE E34 to become very hard and white in color.
Crystallization occurs when MILLATHANE E34 is stored for long periods at temperatures slightly below 23C (72F)
or for a short period at temperatures below freezing 0C (32F).

CAUTION: NEVER ATTEMPT TO MIX CRYSTALLIZED MILLATHANE E34. Serious damage to mills or internal mixers
may result. Warm the raw polymer at elevated temperatures up to 100C (212F) until the natural color of the
urethane returns. Partially crystallized MILLATHANE E34 will result in undispersed lumps of polymer in the mix.

pg. 3 MILLATHANE E34 8/04 (800) 237-7634 TSE INDUSTRIES, INC.

 VULCANIZATION OF MILLATHANE E34

Vulcanization of MILLATHANE E34 can be obtained by EFFECT OF SULFUR

either a sulfur or a peroxide cure system. This versatility
allows MILLATHANE E34 a wide variety of cure times and
temperatures to accommodate production requirements.
In addition, the compounder can formulate for improved
flexing, heat aging, or resistance to compression set by
choosing a sulfur or peroxide cure system.
Like many oil resistant polymers, MILLATHANE E34
requires a treated grade of sulfur to ensure proper
dispersion. Various types containing magnesium
carbonate or sulfur dispersed in a polymeric binder
should be used.
Increasing the concentration of sulfur produces a

SULFUR CURING SYSTEM faster cure rate and a higher state of cure.
Modulus and hardness also increase and heat aging
Although some modifications have been employed, properties decrease as the amount of sulfur is
only the thiazole cure system containing MBTS, MBT, increased.
Thanecure ZM, zinc stearate and sulfur is recommended Abrasion resistance is slightly lower at high sulfur
to cure MILLATHANE E34. It should be noted that zinc levels.
oxide and stearic acid are neither necessary nor desirable The optimum amount of sulfur is 1.5 phr for black and
for curing MILLATHANE E34. 2.0 phr for non-black MILLATHANE E34 compounds.
The thiazole sulfur curing system (listed below)
consistently produces the best physical property SULFUR TEST RECIPE
values and ensures processing safety. Before selecting MILLATHANE E34 100.0
this system over peroxide first investigate: Zinc Stearate 0.5
Possible high temperature effects N330 Black 30.0
Compression set resistance Cumar P10 10.0
End use applications flexibility requirements MBTS 4.0
The following combination gives a desirable balance of MBT 2.0
physical properties at a cure time which is practical in Thanecure ZM 1.0
a molding operation. Sulfur As Shown

RECOMMENDED EFFECT OF SULFUR ON RATE OF CURE

SULFUR CURING SYSTEM Torque
inch lbs.
100
INGREDIENT PHR FUNCTION 2.0 parts

90
Thanecure ZM 1.0 zinc activator 1.5 parts
Sulfur 1.5 vulcanizer 80
MBTS 4.0 primary accelerator
MBT 2.0 secondary accelerator 70
Zinc Stearate 0.5 activator/mill release agent 1.0 parts
60

The effect of varying these ingredients from the 50

combination shown above is discussed in the following
sections. 40

30

20
0.5 parts
10

0
0 5 10 15
Time [minutes]

TSE INDUSTRIES, INC. (800) 237-7634 MILLATHANE E34 8/04 pg. 4

 EFFECT OF SULFUR ON PHYSICAL PROPERTIES EFFECT OF MBTS ON PHYSICAL PROPERTIES

Parts SULFUR 0.5 1.0 1.5 2.0 Parts MBTS 2.0 3.0 4.0 5.0 6.0
Cure Time @155C, min. 15.0 12.5 10.0 7.5 Cure Time @ 155C, min. 7.5 8.5 10.0 12.5 12.5
Hardness, Durometer A 58 64 65 66 Hardness, Durometer A 60 63 65 65 66
100% Modulus, psi 247 377 377 377 100% Modulus, psi 319 363 392 435 464
MPa 1.7 2.6 2.6 2.6 MPa 2.2 2.5 2.7 3.0 3.2
200% Modulus, psi 493 812 827 827 200% Modulus, psi 653 783 841 957 1015
MPa 3.4 5.6 5.7 5.7 MPa 4.5 5.4 5.8 6.6 7.0
300% Modulus, psi 856 1421 1450 1436 300% Modulus, psi 1160 1363 1494 1653 1755
MPa 5.9 9.8 10.0 9.9 MPa 8.0 9.4 10.3 11.4 12.1
Tensile, psi 3509 4234 4249 4423 Tensile, psi 4350 4365 4379 4089 3973
MPa 24.2 29.2 29.3 30.5 MPa 30.0 30.1 30.2 28.2 27.4
Elongation, % 684 562 554 561 Elongation, % 624 568 559 504 485
Tear Die C, pli 196 201 208 224 Tear Die C, pli 186 189 200 213 186
kN/m 34.3 35.2 36.4 39.3 kN/m 32.5 33.1 35.0 37.3 32.6
Compression set, % 39.5 32.0 32.2 30.4 Compression set, % 39.4 35.4 32.2 33.7 36.6
22 hr. @ 70C 22 hr. @ 70C

EFFECT OF MBTS ON RATE OF CURE

EFFECT OF MBTS AND MBT Torque
inch lbs.
An increase in the level of MBTS results in a higher 100
6.0 parts
state of cure and increased processing safety. 5.0 parts
Above 5.0 phr, MBTS has no additional benefit. 90
4.0 parts
Increasing MBT reduces scorch time and increases
80 3.0 parts
the state of cure.
No MBT results in a low state of cure and high 70
2.0 parts
compression set.
An increase in either MBTS or MBT has little effect on 60
the rate of cure (see rheometer curves).
50
Along with the best resistance to compression set,
the combination of 4.0 phr MBTS with 2.0 phr MBT 40
allows the best balance of cure and scorch times.
30
MBTS TEST RECIPE
20
MILLATHANE E34 100.0
Zinc Stearate 0.5
10
N330 Black 30.0
Cumar P10 10.0 0
MBT 2.0 0 5 10 15
Time [minutes]
Thanecure ZM 1.0
Sulfur 1.5
MBTS As shown

pg. 5 MILLATHANE E34 8/04 (800) 237-7634 TSE INDUSTRIES, INC.

 MBT TEST RECIPE EFFECT OF THANECURE ZM
MILLATHANE E34 100.0
N330 Black 30.0 Thanecure ZM is a cure activator for sulfur cured
Cumar P10 10.0 MILLATHANE polyurethane rubber. It consists of a partial
MBTS 4.0 complex of zinc chloride and MBTS. The improvement
Thanecure ZM 1.0 in the rate of cure of MILLATHANE E34 is shown in the
Sulfur 1.5 following graph.
Zinc Stearate 0.5 Increasing the amount of Thanecure ZM increases the
MBT As shown rate and state of cure and improves the compression
set resistance.
For the most practical applications, 1.0 part of
EFFECT OF MBT ON PHYSICAL PROPERTIES
Thanecure ZM provides a good balance between
Parts MBT 0.0 1.0 2.0 3.0 cure rate and processing safety.
Cure Time @ 155C, min. 10.5 10.0 10.0 9.0 As the concentration of Thanecure ZM increases
Hardness, Durometer A 64 64 64 65 above 1.0 part, cure rate improves only slightly with
100% Modulus, psi 348 377 363 392
reduced processing safety.
MPa 2.4 2.6 2.5 2.7
If it becomes necessary to increase scorch time for
200% Modulus, psi 711 798 827 841
MPa 4.9 5.5 5.7 5.8 greater processing safety, MBT level can be reduced
300% Modulus, psi 1233 1363 1450 1479 to 1.0 phr without changing the amount of
MPa 8.5 9.4 10.0 10.2 Thanecure ZM.
Tensile, psi 4075 4263 4365 4394
MPa 28.1 29.4 30.1 30.3
THANECURE ZM TEST RECIPE
Elongation,% 603 581 563 553
Tear Die C, pli 228 201 209 204 MILLATHANE E34 100.0
kN/m 39.9 35.2 36.6 35.7
N330 Black 30.0
Compression set, % 35.2 32.5 31.0 31.0
22 hr. @ 70C
Cumar P10 10.0
MBTS 4.0
MBT 2.0
EFFECT OF MBT ON RATE OF CURE Sulfur 1.5
Torque
Zinc Stearate 0.5
inch lbs. Thanecure ZM As Shown
100

90 3.0 parts
EFFECT OF THANECURE ZM
2.0 parts ON PHYSICAL PROPERTIES
80
Parts Thanecure ZM 0.5 1.0 2.0 3.0
70 Cure Time @ 155C, min. 12.5 10.0 9.5 8.0
1.0 parts
Hardness, Durometer A 62 65 64 66
60 100%,Modulus, psi 319 363 377 493
MPa 2.2 2.5 2.6 3.4
50 200% Modulus, psi 653 827 870 1102
MPa 4.5 5.7 6.0 7.6
40 300% Modulus, psi 1146 1421 1494 1871
MPa 7.9 9.8 10.3 12.9
30 Tensile, psi 4017 4365 4046 4384
0.0 parts
MPa 27.7 30.1 27.9 30.3
20 Elongation,% 621 558 541 500
Tear Die C, pli 227 207 224 233
10 kN/m 39.7 36.2 39.3 40.8
Compression set, % 36.4 32.2 33.2 33.4
0 22 hr. @ 70C
0 5 10 15
Time [minutes]

TSE INDUSTRIES, INC. (800) 237-7634 MILLATHANE E34 8/04 pg. 6

 EFFECT OF THANECURE ZM ON RATE OF CURE EFFECT OF ZINC STEARATE
ON PHYSICAL PROPERTIES
Torque
inch lbs. Parts Zinc Stearate 0.0 0.25 0.50 1.0
100
3.0 parts Cure Time @ 155C, min. 12.0 11.5 10.0 9.5
90 Hardness, Durometer A 60 61 64 65
2.0 parts 100% Modulus, psi 363 377 377 392
80 MPa 2.5 2.6 2.6 2.7
200% Modulus, psi 812 827 827 841
70 1.0 parts MPa 5.6 5.7 5.7 5.8
300% Modulus, psi 1436 1421 1450 1407
60 MPa 9.9 9.8 10.0 9.7
Tensile, psi 4669 4524 4379 4249
50 MPa 32.2 31.2 30.2 29.3
Elongation, % 586 582 567 565
40 0.5 parts Tear Die C, pli 183 190 199 198
kN/m 32.0 33.2 34.8 34.6
30 Compression set, % 39.7 38.0 32.4 31.7
22 hr. @ 70C
20

10 EFFECT OF ZINC STEARATE ON RATE OF CURE

Torque
0 inch lbs.
0 5 10 15 100
Time [minutes]

90
EFFECT OF ZINC STEARATE
80
Zinc stearate has replaced cadmium stearate due to 1.0 parts
toxicity concerns with cadmium compounds. 70 .5 parts
When used as a coactivator with Thanecure ZM,
60
zinc stearate reduces cure times and improves 0.25 parts
processing. 50
Zinc stearate does contribute some lubricity to the
0.0 parts
batch, helping mill and internal mixer release, but its 40
primary use is to help activate the cure and produce
a tighter cure. 30

The recommended amount of zinc stearate is 0.5 phr

20
to obtain the best processing and physical properties.
10
ZINC STEARATE TEST RECIPE
MILLATHANE E34 100.0 0
0 5 10 15
N330 Black 30.0 Time [minutes]
Cumar P10 10.0
MBTS 4.0
MBT 2.0
Sulfur 1.5
Thanecure ZM 1.0
Zinc Stearate As Shown

pg. 7 MILLATHANE E34 8/04 (800) 237-7634 TSE INDUSTRIES, INC.

PEROXIDE CURING EFFECT OF PEROXIDE CONCENTRATION
ON MILLATHANE E34
OF MILLATHANE E34
Compared to sulfur cures, peroxide cured compounds Di-Cup 40C 2.0 3.0 4.0 5.0
have: MILLATHANE E34 100.0 100.0 100.0 100.0
Superior compression set Stearic Acid 0.5 0.5 0.5 0.5
Higher modulus N-220 Black 20.0 20.0 20.0 20.0
Better heat resistance

More resistant to reversion Cure Time @ 155C, min.

NOTE Sulfur cured compounds exhibit higher tensile, Hardness, Durometer A 55 60 60 60
100% Modulus, psi 189 232 305 334
tear and elongation properties.
MPa 1.3 1.6 2.1 2.3
Curing of MILLATHANE E34 can easily be done with 200% Modulus, psi 348 537 841 870
dicumyl peroxide. MPa 2.4 3.7 5.8 6.0
Typically, 3.0 phr of Di-Cup 40C is used. 300% Modulus, psi 696 1030 1653 1668
Curing temperatures at 160C to 170C are required MPa 4.8 7.1 11.4 11.5
as dicumyl peroxide is relatively inactive below Tensile strength, psi 2915 2886 2219 2117
MPa 20.1 19.9 15.3 14.6
these temperatures.
Elongation, % 583 430 332 239
Although coumarone indene resins are efficient
plasticizers in sulfur cured stocks, they should not be
used with peroxide curing agents because of an EFFECTS OF PEROXIDE ON RATE OF CURE
unfavorable interaction resulting in a low state of cure. Torque
inch lbs.
NOTE Plasticizers containing vinyl unsaturation
100
generally should not be used when curing with peroxide.
90
EFFECT OF PEROXIDE CONCENTRATION
80 5.0 parts
ON MILLATHANE E34
Increasing the peroxide concentration has a dramatic 70 4.0 parts

effect on the physical properties of MILLATHANE E34.

60
At levels higher than 4 phr of Di-Cup 40C 3.0 parts
modulus, hardness and compression set resistance 50
increase, but elongation and tear strength decrease.
Curing with 3 phr of dicumyl peroxide will result in 40
2.0 parts
lower modulus, high tear strength, higher elongation
30
and good compression set.
Generally, when using either black or non-black
20
fillers, the closer the compound is to a pure gum,
the less peroxide is required. 10
When evaluating other peroxides, test a few levels to

determine the optimum concentration. 0

0 5 10 15
NOTE Choosing a peroxide which requires curing Time [minutes]
MILLATHANE E34 above 170C is not recommended
because of reversion.

TSE INDUSTRIES, INC. (800) 237-7634 MILLATHANE E34 5/04 pg. 8

COMPARISON OF SULFUR
AND PEROXIDE CURES
SULFUR PEROXIDE

MILLATHANE E34 100.0 100.0
Stearic acid 0.5
N220 Black 20.0 20.0
Cumar P-10 10.0
MBTS 4.0
MBT 2.0
Sulfur 1.5
Thanecure ZM 1.0
Zinc Stearate 0.5
Di-Cup 40C 3.0

ORIGINAL PHYSICAL PROPERTIES

Cure temperature 155C 160C
Cure time, min. 10 15
Hardness, Durometer A 60 60
100% Modulus, psi 334 232
MPa 2.3 1.6
200% Modulus, psi 696 537
MPa 4.8 3.7
300% Modulus, psi 1262 1030
MPa 8.7 7.1
Tensile strength, psi 4495 2886
MPa 31.0 19.9
Elongation % 552 430
DIN Abrasion volume loss mm3 40 42
Tear (Die C), pli 217 179
kN/m 38.0 31.4
Compression set, %
22 hours @70C 32.2 18.5

HEAT AGED PHYSICAL PROPERTIES AGED 70 hours @ 70C

Hardness, points change +4 +4
Change in tensile, % -3.2 +5.0
Change in elongation, % -11.1 -4.9

pg. 9 MILLATHANE E34 8/04 (800) 237-7634 TSE INDUSTRIES, INC.

 BASIC COMPOUNDING
CARBON BLACK LOADING STUDIES CARBON BLACK N-330 (HAF)
Physical Properties Press Cured @ 155 C
Five different carbon blacks were evaluated for use Parts per 100 polymer 20 40 60
as fillers in MILLATHANE E34: N-220, N-330, N-550, Cure Time, min. 10 10 10
N-774 and N-990. Hardness, Durometer A 60 70 80
The carbon blacks range from the highly reinforcing 100% Modulus, psi 305 566 1000
N-220 to the large particle non-reinforcing N-990. MPa 2.1 3.9 6.9
200% Modulus, psi 609 1233 2059
The physical property data indicate that modulus,
MPa 4.2 8.5 14.2
hardness, tear strength and abrasion resistance are 300% Modulus, psi 1102 1958 2813
directly related to the particle size and structure of MPa 7.6 13.5 19.4
the carbon black. Tensile Strength, psi 4698 4031 3683
The finer the particle size the higher the reinforcement. MPa 32.4 27.8 25.4
The advantages of the coarse particle size blacks are
Elongation, % 578 554 431
Tear (Die C), pli 228 224 225
easier overall processing and lower heat build-up.
kN/m 39.9 39.3 39.4
The following formulation was used in the carbon black DIN Abrasion, mm3 loss 40.0 46.7 48.0
evaluation. Process aids and plasticizers are beneficial
in wetting out the filler and aid in dispersion and CARBON BLACK N-550 (FEF)
subsequent molding operations. The type and amount Physical Properties Press Cured @ 155 C
of carbon black are indicated in the tables. Parts per 100 polymer 20 40 60
Cure Time, min. 10 10 10
FORMULATION
Hardness, Durometer A 60 70 80
MILLATHANE E34 100.0 100% Modulus, psi 276 508 885
Zinc Stearate 0.5 MPa 1.9 3.5 6.1
Struktol WB 222 0.5 200% Modulus, psi 595 1146 1885
MPa 4.1 7.9 13.0
Poly AC 617A 0.5
300% Modulus, psi 1044 1798 2480
Cumar P10 10.0
MPa 7.2 12.4 17.1
MBTS 4.0 Tensile Strength, psi 4234 3959 3408
MBT 2.0 MPa 29.2 27.3 23.5
Thanecure ZM 1.0 Elongation, % 594 543 427
Sulfur 1.5 Tear (Die C), pli 227 235 215
Carbon Black As shown kN/m 39.8 41.2 37.7
DIN Abrasion, mm3 loss 51.7 55.3 53.8

CARBON BLACK N-220 (ISAF) CARBON BLACK N-774 (SRF)

Physical Properties Press Cured @ 155 C Physical Properties Press Cured @ 155 C

Parts per 100 polymer 20 40 60 Parts per 100 polymer 20 40 60

Cure Time, min. 10 10 10 Cure Time, min. 10 10 10
Hardness, Durometer A 60 70 80 Hardness, Durometer A 55 65 75
100% Modulus, psi 334 609 1102 100% Modulus, psi 218 377 624
MPa 2.3 4.2 7.6 MPa 1.5 2.6 4.3
200% Modulus, psi 696 1305 2219 200% Modulus, psi 435 856 1407
MPa 4.8 9.0 15.3 MPa 3.0 5.9 9.7
300% Modulus, psi 1262 2045 2973 300% Modulus, psi 812 1421 2016
MPa 8.7 14.1 20.5 MPa 5.6 9.8 13.9
Tensile Strength, psi 4495 4133 3611 Tensile Strength, psi 4075 3930 3205
MPa 31.0 28.5 24.9 MPa 28.1 27.1 22.1
Elongation, % 552 544 442 Elongation, % 623 584 523
Tear (Die C), pli 217 219 206 Tear (Die C), pli 232 224 213
kN/m 38.0 38.3 36.0 kN/m 40.6 39.2 37.3
DIN Abrasion, mm3 loss 40.0 44.1 43.2 DIN Abrasion, mm3 loss 55.4 53.0 58.6

TSE INDUSTRIES, INC. (800) 237-7634 MILLATHANE E34 8/04 pg. 10

 CARBON BLACK N-990 (MT) FORMULATION FOR EVALUATION
Physical Properties Press Cured @ 155 C OF NON-BLACK FILLERS
Parts per 100 polymer 20 40 60
Cure Time, min. 10 10 10 MILLATHANE E34 100.0
Hardness, Durometer A 55 60 65 Zinc Stearate 0.5
100% Modulus, psi 203 247 334 MBTS 4.0
MPa 1.4 1.7 2.3 MBT 2.0
200% Modulus, psi 334 479 725 Thanecure ZM 1.0
MPa 2.3 3.3 5.0 Sulfur 1.5
300% Modulus, psi 624 885 1189 Cumar P10 10.0
MPa 4.3 6.1 8.2 Non-Black Fillers As Shown
Tensile Strength, psi 3669 4147 2784
MPa 25.3 28.6 19.2
Elongation, % 607 601 576
PRECIPITATED SILICA HI-SIL 233
Physical Properties Press Cured @ 155 C
Tear (Die C), pli 173 174 178
kN/m 30.3 30.4 31.2 Parts per 100 polymer 20 40 60
DIN Abrasion, mm3 loss 87.6 90.8 97.5 Cure Time, min. 17 17 16
Hardness, Durometer A 60 68 78
100% Modulus, psi 247 261 290
NON-BLACK FILLER STUDIES MPa 1.7 1.8 2.0
200% Modulus, psi 392 435 464
The best reinforcement by non-black mineral fillers MPa 2.7 3.0 3.2
in MILLATHANE E34 is given by fumed silica 300% Modulus, psi 653 711 696
followed by precipitated silica and hard clay. MPa 4.5 4.9 4.8
Fumed silica is nearly comparable to carbon black in
Tensile Strength, psi 4379 4147 3640
MPa 30.2 28.6 25.1
its effect on tensile strength, tear properties and Elongation, % 653 737 760
abrasion resistance. Tear (Die C), pli 207 199 186
Hard clay and talc filled MILLATHANE E34 compounds kN/m 36.2 34.9 32.5
are highly recommended for roll coverings when DIN Abrasion, mm3 loss 45.0 51.8 65.3
curing in direct steam.
On the following pages, four mineral fillers are evaluated
WATER WASHED CLAY POLYFIL HG90
in MILLATHANE E34 at various loading levels. Physical Properties Press Cured @ 155 C
Very high tensile strength values are obtained with
Parts per 100 polymer 20 40 60
precipitated silica (Hi-Sil 233) and fumed silica Cure Time, min. 14 16 22
(Wacker HK-N20). Hardness, Durometer A 54 58 60
Talc (Mistron Vapor) and hard clay (Polyfil HG 90) 100% Modulus, psi 276 406 537
incorporate readily and makes excellent blends with MPa 1.9 2.8 3.7
other silica and carbon black at very high loadings. 200% Modulus, psi 551 899 1146
MPa 3.8 6.2 7.9
To improve processing, we recommend:
300% Modulus, psi 885 1349 1624
A balance of process aids such as low molecular MPa 6.1 9.3 11.2
weight polyethylene (Poly AC 617 A) and aliphatic Tensile Strength, psi 4089 4147 3886
fatty acid esters (Struktol WB222) or blends of fatty MPa 28.2 28.6 26.8
acid esters with hydrocarbon resins like Struktol 60NS. Elongation, % 579 626 620
Plasticizers to improve incorporation of fillers and
Tear (Die C), pli 222 232 210
kN/m 38.9 40.6 36.8
molding efficiency. DIN Abrasion, mm3 loss 68.2 80.5 80.1
Some non-black fillers may retard the cure slightly.

The addition of 1.0 phr diethylene glycol can reduce

the cure time and improve physical properties.

pg. 11 MILLATHANE E34 8/04 (800) 237-7634 TSE INDUSTRIES, INC.

 TALC MISTRON VAPOR EVALUATION OF PLASTICIZERS
Physical Properties Press Cured @ 155 C
IN MILLATHANE E34
Parts per 100 polymer 20 40 60
Cure Time, min. 10 12 13 Plasticizers are used in MILLATHANE E34 compounds
Hardness, Durometer A 54 60 64 to better incorporate fillers and to improve processing.
100% Modulus, psi 276 479 566 A number of plasticizers were evaluated for their
MPa 1.9 3.3 3.9 effect on hardness and low temperature properties
200% Modulus, psi 421 696 798
in MILLATHANE E34.
MPa 2.9 4.8 5.5
All the plasticizers except Cumar P-10 retard the rate
300% Modulus, psi 566 885 957
MPa 3.9 6.1 6.6 of cure.
Tensile Strength, psi 3393 4568 3045 All reduce the compound viscosity and many

MPa 23.4 31.5 21.0 enhance the low temperature properties.

Elongation, % 597 603 606 Coumarone indene resins, such as Cumar P-10, are
Tear (Die C), pli 210 200 190
highly recommended for MILLATHANE E34 sulfur
kN/m 36.8 35.0 33.3
DIN Abrasion, mm3 loss 73.9 94.3 111.3 cured compounds.
NOTE Some plasticizers, such as some naphthenic
and all paraffinic oils, are not compatible with
FUMED SILICA WACKER HK N20
Physical Properties Press Cured @ 155 C
MILLATHANE E34. Other plasticizers not used in this
study should be evaluated before using.
Parts per 100 polymer 20 30 40
Cure Time, min. 10 11 10
Hardness, Durometer A 60 65 70
The following test recipe was used in this evaluation.
100% Modulus, psi 203 218 261
MPa 1.4 1.5 1.8 FORMULATION FOR EVALUATION
200% Modulus, psi 305 363 450 OF PLASTICIZER
MPa 2.1 2.5 3.1 MILLATHANE E34 100.0
300% Modulus, psi 479 566 754 Zinc Stearate 0.5
MPa 3.3 3.9 5.2 N-330 Black 30.0
Tensile Strength, psi 4640 4988 5060
MBTS 4.0
MPa 32.0 34.4 34.9
MBT 2.0
Elongation, % 623 628 624
Tear (Die C), pli 210 220 221
Thanecure ZM 1.0
kN/m 36.8 38.6 38.7 Sulfur 1.5
DIN Abrasion, mm3 loss 30.8 31.8 32.2 Plasticizer 10.0

EFFECT OF PLASTICIZERS ON HARDNESS

AND LOW TEMPERATURE
Durometer A Brittle Point C TR-10 C
Trade Name
No Plasticizer 71 -80 -45
Benzoflex 9-88SG 66 -85 -51
TP-90B 65 -90 -52
TP-95 65 -90 -54
Cumar P-10 67 -85 -48
Sundex 790 66 -90 -48
DBP 66 -90 -51
Paraplex G25 68 -90 -51
Butyl Oleate 63 -85 -53
Plasthall 7050 65 -90 -53
DOA 66 -90 -53
Plasthall DOZ 64 -90 -53

Brittle Point ASTM D746

TR-10 ASTM D1392-88

TSE INDUSTRIES, INC. (800) 237-7634 MILLATHANE E34 8/04 pg. 12

 PROCESSING OF MILLATHANE E34
MILLATHANE E34 polyurethane rubber compounds MIXING ON OPEN MILLS
have been designed for ease of processing, using MILLATHANE E34 is easily mill mixed using the
the standard mixing, calendering and extrusion following typical mixing schedule.
equipment found in rubber manufacturing plants.
The processing properties desired by many TYPICAL MILL MIXING CYCLE
compounders are unique to MILLATHANE E34 rubber Set mill for 75 mm sheet and turn on cooling water.
it bands easily and requires a very short breakdown
period. ROLL TEMPERATURE ACTION
Once it is broken down, the rubber exhibits a 38C - 50C Breakdown of MILLATHANE E34 rubber.
decrease in viscosity.
The extent of polymer breakdown depends on the 50C - 65C Add internal lubricants, processing aids
time and temperature of mixing as well as on the (Stearic Acid, Zinc Stearate, Waxes).
equipment used.
CAUTION: DO NOT MIX CRYSTALLIZED 65C - 82C Add reinforcing fillers (Carbon Black, silica),
work in. Times vary with amounts.
MILLATHANE E34. Warm the raw polymer at elevated
temperatures up to 100C (212F) until the natural
65C - 82C Add plasticizer slowly. Non-reinforcing fillers
color of the urethane returns. can be added with plasticizer.
A summary of suggested processing procedures for
open mill and internal mixing, as well as calendering, 65C - 82C Add curing agents (Sulfur, Thanecure ZM,
extruding and molding, follows. MBTS, MBT, or Peroxide). Cut 6 times each way.
Roll end-to-end 6 times. Batch-off, dip and
place on stack to cool.

CRYSTALLIZATION OF MILLATHANE E34

MILLATHANE E34 undergoes a reversible change called crystallization where the polymer chains align
themselves into a crystal network. This causes MILLATHANE E34 to become very hard and white in color.
Crystallization occurs when MILLATHANE E34 is stored for long periods at temperatures slightly below 23C or
quickly at temperatures below freezing 0C.

CAUTION: NEVER ATTEMPT TO MILL MIX CRYSTALLIZED MILLATHANE E34.

Serious damage to mills or internal mixers may result.
Warm the raw polymer at elevated temperatures up to 100C until the natural color of the urethane returns.
Partially crystallized MILLATHANE E34 will result in undispersed lumps of polymer in the mix.

pg. 13 MILLATHANE E34 8/04 (800) 237-7634 TSE INDUSTRIES, INC.

MIXING IN INTERNAL MIXERS
MILLATHANE E34 rubber is loaded into the mixer
and broken down for one minute.
All the internal lubricants and processing aids are
then mixed for approximately 1.5 minutes.
Next, add one-half of the fillers and mix for an
additional 1.5 minutes.
Finally, add the balance of the fillers, plasticizers and
other ingredients, and mix batch for one or two
minutes.
When the amp meter and stock temperature have
leveled off, the batch is ready to dump.
Another indicator is the characteristic slurping
sound of a good mix.
At this point, stock temperature should not exceed
135C (275F).
A second pass through the internal mixer is
recommended for the incorporation of curatives:
Thanecure ZM, MBTS, MBT, and sulfur are added to
the MILLATHANE E34 masterbatch and mixed
quickly, keeping mixing temperature and drop
temperature below 105C (220F).
NOTE Single pass mixing of MILLATHANE compounds
containing curatives is not recommended because of
the heat build-up generated in mixing. MILLATHANE
compounds will scorch easily and have poor shelf life
if curatives are incorporated at temperatures greater
than 105C (220F).
TYPICAL INTERNAL MIXING OF MILLATHANE E34
Speed: 20 RPM Ram Pressure: Float
TEMPERATURE MATERIALS ADDED
38C-52C Breakdown of MILLATHANE E34
(100F-125F)
52C-82C Internal lubricants, processing aids
(125F-180F) and one half the fillers
82C-100C Balance of the fillers/plasticizer
(180F-212F) colorants
121C-135C Dump
(250F-275F)
COMPRESSION AND
TRANSFER MOLDING
MILLATHANE E34 polyurethane rubber compounds
can be molded by compression, injection and transfer
molding procedures.
Excellent mold definition is obtained in press-cures.
The shrinkage of cured MILLATHANE E34 parts is 1.5
to 2.1%, depending on the filler loading.
Optimum press-cures are obtained with the sulfur
system at temperatures from 140C to 160C, with
curing times ranging from 25 to 10 minutes.
With the peroxide curing system, temperatures range
from 150C to 180C and cure times will range from
15 to 5 minutes depending on temperature and choice
of peroxide.
INJECTION MOLDING
OF MILLATHANE E34
Injection molding of MILLATHANE E34 compounds
can be accomplished without difficulty.
Proper Mooney viscosity of the base polymer is a
critical first step in developing a compound.
Use MILLATHANE E34 with a Mooney viscosity
below 50 (ML 1+4 @ 100C) for most injection
molding applications.
Cure times can be varied by adjusting the temperature
for the peroxide or sulfur cure systems. The
vulcanization section of this bulletin contains
information on the effect of curatives on cure rate.
As with other synthetic rubber compounds,
Water: Full
complete time, temperature and pressure parameters
TIME, MIN.
must be analyzed and tested completely before
0-1.0 going into production.
1.0-3.0 CALENDERING AND EXTRUSION
OF MILLATHANE E34
3.5-5.5
MILLATHANE E34 can be easily calendered and
extruded. Consult the TSE Industries website
4.0-7.0
www.TSE-Industries.com
or www.MILLATHANE.com
or call us at 800-237-7634 or 727-573-7676
and talk with a technical service representative for
compounding and processing assistance.
TSE INDUSTRIES, INC. (800) 237-7634 MILLATHANE E34 8/04 pg. 14
 CHEMICAL RESISTANCE
MILLATHANE E34 compounds exhibit high resistance Chemical MILLATHANE E34 MILLATHANE 76
Polyether Polyester
to deterioration in hydrocarbon oils and fuels, as well as Kerosene 2 2
a number of other classes of chemicals. In the table Linseed Oil 2 2
below there is a comparison on the effects of various Lubricating Oils 2 2
chemicals on the swell of MILLATHANE E34 and Magnesium Hydroxide 1 1
MILLATHANE 76. The following tests are immersed for Magnesium Sulfate 2 2
seven days at 75F (24C). The rating was based on Methyl Alcohol 4 3
Methyl Ethyl Ketone 4 4
volume change according to the following key:
Mineral Oil 1 1
1 = Excellent (0 - 5% swell)
Motor Oils 1 1
2 = Good (6 - 20% swell) Naphtha 2 2
3 = Fair (21 - 40% swell) Natural Gas 2 2
4 = Poor (greater than 40% swell) Nitric Acid: 10% 4 4
Nitric Acid: 70% 4 4
Chemical MILLATHANE E34 MILLATHANE 76 Nitric Acid: Fuming 4 4
Polyether Polyester
Nitrobenzene 4 4
Acetic Acid, Dilute 3 3
Oil: Crude 1 1
Acetic Acid, 30% 4 4
Oil: Lubricating 1 1
Acetone 4 4
Oil: Vegetable 1 1
Acetylene 2 3
Olive Oil 1 1
Air 1 1
Oxygen 1 1
Ammonia 2 3
Perchlorethylene 4 4
Ammonium Hydroxide 2 2
Petroleum Oils 1 1
Ammonium Sulfate 2 2
Phosphoric Acid: 50% 4 4
Animal Fats 2 2
Potassium Chloride 2 2
Barium Hydroxide 1 2
Potassium Hydroxide 2 2
Boric Acid 1 2
Propane 2 2
Calcium Chloride 1 2
Propyl Alcohol 3 3
Calcium Hydroxide 1 2
Skydrol 4 3
Carbon Dioxide 1 1
Soap Solution 1 2
Carbon Tetrachloride 3 4
Sodium Bicarbonate 2 2
Castor Oil 2 2
Sodium Chloride 2 2
Chlorine 2 2
Sodium Hydroxide 2 2
Chloroform 4 4
Sodium Hypochlorite 4 4
Citric Acid 2 2
Sodium Silicate 1 2
Cottonseed Oil 1 2
Sodium Sulfate 2 2
Cupric Chloride 1 2
Sulfuric Acid: 10% 4 4
Cupric Sulfate 2 2
Sulfuric Acid: 50% 4 4
Cyclohexane 2 2
Sulfuric Acid: 70% 4 4
Diethylene Glycol 2 2
Sulfuric Acid: Fuming 4 4
Ethyl Acetate 4 4
Tetrachloroethane 4 4
Ethyl Alcohol 3 2
Tetrachloroethylene 4 4
Ethyl Chloride 3 3
Trichlorethylene 4 4
Ethylene Glycol 2 2
Turpentine 3 2
Formaldehyde 3 2
Water 2 2
Formic Acid 3 4
Water: 212F 1 4*
Freon 12 1 2
Xylene 3 3
Fuel Oil 2 2
Zinc Chloride 2 2
Gasoline 2 2
ASTM Oil #2 2 1
Grease 1 2
ASTM Oil #3 2 1
Hexane 1 2
ASTM Oil #5 1 1
Hydraulic Oil 1 2
ASTM Fuel A 1 1
Hydrochloric Acid 3 3
ASTM Fuel B 2 2
Hydrogen 1 2
Isopropyl Alcohol 2 3 *MILLATHANE with 3 phr
JP4 2 3 of carbodiimide 2

pg. 15 MILLATHANE E34 8/04 (800) 237-7634 TSE INDUSTRIES, INC.

 ADHESION TO METALS
MILLATHANE E34 polyurethane rubber compounds Below is a list of commercially available adhesives:
can be effectively bonded to metal. LORD CORPORATION
To insure consistent bonding results, metal surfaces
Chemlok Ty Ply BN
must be thoroughly clean prior to application of the Chemlok 219
adhesive. Chemlok 218
Oils, greases, etc., should be removed by solvent
Chemlok 250
degreasing or alkaline cleaning. Chemlok 610 Water-base
Rust, scale or oxide coatings should be removed by
Chemlok 205 Adhesive Primer
suitable mechanical or chemical methods.
As in any bonding operation, testing should be ROHM AND HAAS
done to see which adhesive works best in your Thixon 410
application. Thixon 715-1/720
If the single coat system does not produce the Thixon 7010 Water-base
desired results, try a two coat system. Thixon P-15 Adhesive Primer
Two coat systems are generally employed in hard to

bond situations or when the part is intended for a

dynamic application.
Follow manufacturers directions for dilution.

TSE INDUSTRIES, INC. (800) 237-7634 MILLATHANE E34 8/04 pg. 16

 GLOSSARY
Benzoflex 9-88SG plasticizer Vesicol Chemical Co.
Butyl Oleate butyl oleate C. P. Hall Co.
Chemlok adhesive Lord Corporation
Cumar P-10,R-3 plasticizer Neville Chemical
DBP dibutyl phthalate Ashland Chemical Inc.
Di-Cup 40C peroxide GEO Specialty Chemicals
DOA dioctyl adipate Ashland Chemical Inc.
Hi-Sil 233 precipitated silicate filler PPG Industries
MILLATHANE E34 polyurethane TSE Industries, Inc.
Mistron Vapor magnesium silicate filler Luzenac America, Inc.
Paraplex G-25 plasticizer C.P. Hall Co.
Plasthall 7050 plasticizer C.P. Hall Co.
Plasthall DOZ plasticizer C.P. Hall Co.
Poly AC 617A microcrystalline wax Allied Fibers & Plastics
Polyfil HG-90 water-washed clay J.M. Huber
Struktol WB 222 fatty acid process aid Struktol Co.
Sundex 790 aromatic oil Sun Oil Co.
Thanecure ZM activator TSE Industries, Inc.
Thixon adhesive Rohm and Haas
TP-90B, TP-95 plasticizers Rohm and Haas

pg. 17 MILLATHANE E34 8/04 (800) 237-7634 TSE INDUSTRIES, INC.

 TSE INDUSTRIES, INC.,
MILLATHANE DIVISION PRODUCTS LIST:

MILLATHANE 66 A polyester-based millable polyurethane which is peroxide curable.

MILLATHANE 76 A polyester-based millable polyurethane which is sulfur or peroxide curable.
MILLATHANE 97 A transparent polyether-based millable polyurethane which is peroxide curable.
MILLATHANE 5004 A polyester polyurethane with excellent processing characteristics and can be easily injection
molded and must be vulcanized with peroxide (formerly known as Vibrathane 5004)
MILLATHANE CM A polyether polyurethane rubber exhibiting outstanding low temperature properties and
excellent hydrolytic stability (formerly known as Adiprene CM).
MILLATHANE E34 A polyether-based millable polyurethane which is sulfur or peroxide curable.
MILLATHANE HT A polyester-based millable polyurethane which is sulfur or peroxide curable and able to
withstand elevated temperatures.
CAYTUR 4 MBTS/zinc chloride activator for millable polyurethanes.
THANECURE ZM MBTS/zinc chloride activator for millable polyurethanes.
THANECURE T9 Dimeric 2,4-toluene diisocyanate can be used as vulcanization agent for polyurethane rubber;
adhesion promoter for rubber to textile and PVC to textile bonding; as a cross linking
component in heat activated one compound PUR elastomer systems, one component
adhesive systems and one component coatings which include automotive undercoats.
CRYSTAL 1053 A semi-permanent mold release agent recommended for applications in rubber, composite,
and thermoplastic molding. Excellent mold sealer and inhibits mold build-up.
CRYSTAL 2000 A semi-permanent mold release agent used as a mold lubricant and recommended for slab dip,
lubricating extruded goods and prevents water spotting in open steam cure.
CRYSTAL 4100 A semi-permanent mold release agent used for applications in thermoplastic, epoxy,
and urethane molding. Provides a high level of slip to the mold.
CRYSTAL 7000 A semi-permanent mold release agent which allows a greater number of releases for urethane
integral skin foam.

TSE INDUSTRIES, INC. (800) 237-7634 MILLATHANE 76 8/04 pg. 18

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TSE INDUSTRIES, INC.
AN ISO 9001 CERTIFIED COMPANY

Millathane E34

4370 112th Terrace North, Clearwater, Florida 33762, USA

(727) 573-7676 (800) 237-7634 Fax: (727) 572-0487
Millathane E34

www.TSE-INDUSTRIES.com www. MILLATHANE.com 7/04