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A Unique Compounding Ingredient for Easier Processing, Higher Hardness Radial Tire Beadfiller Compounds
by
Mark A. Lawrence INDSPEC Chemical Corporation
a subsidiary of Occidental Chemical Corporation 1010 William Pitt Way Pittsburgh, PA 15238
Phone: 412-826-3675
Abstract: There are many different approaches to increasing the hardness of a beadfiller compound, including the use of increased carbon black, high styrene SBR resins and phenolic reinforcing resins. If one wants to improve the processability of a beadfiller compound, liquid rubbers, processing aids, oils or even reduced levels of carbon black can be employed. With the introduction of Ulti-Pro® 100 reactive processing aid, it is now possible to use a single ingredient that will both increase the compound’s hardness while improving its’ processability. This paper compares Ulti-Pro 100 reactive processing aid to the above mentioned materials for their effect on both cured and uncured rubber properties, including rubber processability.
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Background: The market for high performance passenger car tires and self supporting run flat tires has created a demand for high hardness compounds for beadfiller (apex) and sidewall support applications. A number of different approaches have been used to increase the hardness of beadfiller compounds. The conventional approach is to use a high level of carbon black. Unfortunately increased levels of carbon black lead to higher viscosity, poorer processing compounds with increased hysteresis1. Alternate methods to increase compound hardness include using a phenolic resin or high styrene SBR resin. Unfortunately there are problems with each of these methods as well. Lowering the viscosity of a high carbon black, high hardness beadfiller compound frequently entails adding oil or a processing aid, such as a fatty acid derivative, a liquid rubber or even a specialty polymer such as trans-polyoctenamer. Unfortunately all of these materials either have little effect on the compound hardness or actually work to lower the hardness. A new material, Ulti-Pro® 100 reactive processing aid, provides the high hardness desired in a high performance tire beadfiller compound while actually reducing the compound viscosity and improving processability. As a means of demonstrating the benefits of Ulti-Pro 100 on the processability of a beadfiller compound, a number of traditional measures of processability such as the Mooney viscosity, Mooney stress relaxation and capillary rheometer tests are compared to the newer RPA (rubber process analyzer).
Experimental Method: Eight different materials (Table 1) were added to a 75 durometer beadfiller compound (Table 2). Some of the materials are known to increase the hardness of a compound, while others are known to lower the viscosity of a compound. As added controls, compounds with + 10 phr carbon black and – 10 phr carbon black were included as representations of the traditional way of increasing a compound’s hardness and of lowering hardness and viscosity. Both SP6701 phenolic reinforcing resin and Ulti-Pro 100 reactive processing aid require the addition of a methylene donor to fully crosslink. Hexamethylenetetramine (HMTA) was selected as the methylene donor for this experiment because SP6701 can be very slow curing with the other common methylene donor, hexamethoxymethylmelamine (HMMM). The methylene donor HMTA was added at typical levels, a 90/10 resin/HMTA ratio for the phenolic resin SP6701, and a
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75/25 ratio for the monomer, Ulti-Pro 100. Testing was conducted according to the methods listed in Table 3.
Results and Discussion:
Rubber Processability There are any number of properties of a rubber compound that can affect processability, including viscosity, die swell, tackiness, stickiness, green strength, time to scorch and cure rate. The first part of this study concentrates on viscosity and die swell using four measures of rubber processability – the Mooney viscosity test, the Mooney stress relaxation test, the capillary rheometer and the rubber process analyzer (RPA). The cure properties (time to scorch and cure rate) will be considered later in the paper. The Mooney viscosity and Mooney stress relaxation tests are very low shear rate tests with a shear rate of about 1.5 s-1.2 Unfortunately most rubber processing equipment operates at higher shear rates than that tested in the Mooney viscometer.3 In a conventional Mooney viscosity test, as expected, the compound with the increased level of carbon black caused a significant increase in Mooney viscosity ML 1+4, as did the compounds containing Vestenamer 8012 and the phenolic reinforcing resin, SP6701. The addition of Pliolite S6H high styrene resin had no effect on ML1+4, while the remaining materials caused a reduction in ML1+4. (Figure 1)
The Mooney stress relaxation test attempts to use the Mooney viscometer to resolve the viscosity of the compound into viscous and elastic components. This is accomplished by rapidly stopping the rotor at the end of the Mooney viscosity test and measuring the decay in torque, or the stress relaxation of the compound. Assuming a power law model for the compound’s response, a log/log plot of Mooney viscosity vs. time should result in a straight line, the steeper the slope of the line, the faster the stress relaxation, the less the uncured elasticity of the compound relative to the viscous component. This could potentially translate into a compound with less nerve, which may permit faster filler incorporation during mixing or less die swell during extrusion.4 Based on these criteria, all of the materials evaluated should improve the processablity of the compound except the compound containing the phenolic reinforcing resin, SP6701 and the low molecular weight polyisoprene, LIR 30. (Figure 2) However, with the exception of the control compounds with the increased and decreased levels of carbon black, the difference in Mooney stress relaxation among the compounds tested was small.
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The capillary rheometer is capable of much higher shear rates than the Mooney viscometer. In this experiment shear rates as high as 1000 s-1 were examined, in the range of conditions experienced during some extrusion and injection molding operations. Over the range of shear rates from 10-300 s-1 Vestenamer 8012 produced among the highest apparent viscosities of any of the materials examined (Figures 3-8). None of the materials was able to reduce the apparent viscosity below that of the reduced carbon black formulation nor did any increase it above that of the increased carbon black formulation. LIR 30, WB-212 and Ulti-Pro 100 consistently produced the lowest apparent viscosities of the experimental materials. At 1000 s-1 shear rate, all of the compounds exceeded the maximum pressure limitation of the capillary rheometer (1050 bar) except the compounds containing the oil, Ulti-Pro 100 and SP6701. However, at 1000 s-1 shear rate there is some deviation from a power law shear thinning response for these three materials, calling into question the validity of the 1000 s-1 results. Discounting the 1000 s-1 data, the lowest die swell during the capillary rheometer testing was achieved with LIR 30, Vestenamer 8012 and Ulti-Pro 100 containing compounds. (Figure 9) The RPA is one of the newer test instruments for evaluating the processability of a rubber compound. To a large extent it can measure similar properties to the capillary rheometer but goes a step beyond the capillary rheometer in its’ ability to resolve the physical properties of the rubber compound into their viscous and elastic components. At 40°C, the complex dynamic viscosity of all of the experimental materials fell between that of the + 10 carbon black and the – 10 carbon black compounds, as was the case with the capillary rheometer testing. (Figures 3, 10) However, under this set of test conditions (40°C, 6.98% strain), the Ulti-Pro 100, SP6701 and S6H containing compounds all developed slightly greater complex dynamic viscosity than the control. At all strain levels tested, at 40°C, the S6H containing compound generated significantly greater elastic modulus (G’) than the control. (Figure 11) At 40°C, SP6701 and Ulti-Pro 100 generated greater G’ than the control compound, but only at lower strains, 6.98%, 10% and 20%. At higher strains, they equaled the control. The WB-212, oil and LIR containing compounds consistently generated lower G’ at 40°C than the control compound. It has been reported that compounds with high G’ have high “nerve” and are difficult processing5. While 40°C is below normal processing temperatures, it is in the range of temperatures experienced during breakdown on a mill or in a cold feed extruder, implying that the S6H and possibly the SP6701 and Ulti-Pro 100 compounds might be more difficult to break down than the other materials.
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At 100°C (6.98% strain) SP6701 developed greater complex dynamic viscosity than any of the other compounds, even the compound with + 10 carbon black. (Figure 12) The rest of the compounds were similar to the control under this test condition. With higher strains at 100°C, the SP6701 and the Vestenamer 8012 containing compounds generated greater elastic modulus (G’) than the control, but only at 10% and 20% strain. (Figure 13) The rest of the additives provided lower elastic modulus (G’) at 100°C than the control. At both 40°C and 100°C, Ulti-Pro 100 generated significantly greater tangent delta during RPA testing than any of the other compounds evaluated, indicating that there is a large viscous component imparted on the compound by this material. (Figures 14, 15) SP6701 also increased the tangent delta relative to the control compounds, but not as much as Ulti-Pro 100. The high tangent delta values for the Ulti-Pro 100 compound are consistent with the low die swell reported during the capillary rheometer testing. (Figure 9) Depending on which processing parameters are most important, one can classify the eight materials evaluated any number of ways as to their effect on processability. One potential way to group the materials is as follows:
Improves Rubber Processability Sundex 790T – aromatic oil
LIR 30 – liquid polyisoprene Strucktol WB-212 – fatty acid emulsion
May Improve Rubber Processability Epolene N34W – low molecular weight polyethylene
Ulti-Pro 100 – m-hydroxydiphenylamine
May Degrade Rubber Processability Pliolite S6H – high styrene resin SP6701 – phenolic reinforcing resin
Vestenamer 8012 – trans-polyoctenamer
Other Physical Properties The first part of this study involved examining the effect of various rubber additives on the processability of the rubber compound. The second part of the study looks at their effect primarily on the cure and cured properties of the compound. Although not
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included in the processability evaluation, the cure properties of a compound effect its’ processability. Ulti-Pro 100 significantly reduced the scorch safety of the rubber compound, while the high styrene resin Pliolite S6H slightly increased scorch safety. (Figure16) The reduction in scorch safety with Ulti-Pro 100 was largely caused by the selection of HMTA as the methylene donor. There is less of an effect on scorch safety when HMMM is used. HMTA was selected as the methylene donor for this study because the other material that requires a methylene donor, SP6701 phenolic resin, is extremely slow curing when HMMM is used as the methylene donor. Methods for increasing the short scorch time exhibited by Ulti-Pro 100 are addressed later in this paper. Even with HMTA as the methylene donor, SP6701 significantly increased the Rheometer t’90 of the compound, while Ulti-Pro 100 reduced the compound’s t’90. Vestenamer 8012 and Pliolite S6H also slowed the compound cure. (Figure 17) Ulti-Pro 100, Vestenamer 8012, SP6701 and Pliolite S6H all significantly increased the hardness and modulus of the compound. (Figures 18, 19) The other materials had little effect on these properties. Although it increased the modulus of the compound, Pliolite S6H also slightly reduced the compound’s tensile strength as did the liquid polyisoprene, LIR 30 and the low molecular weight polyethylene, Epolene N34W. (Figure 20) The other materials had little effect on tensile strength. Vestenamer 8012 and to a lesser extent Ulti-Pro 100 both caused a slight reduction in elongation at break. (Figure 21) In addition to altering the uncured viscoelastic properties of the rubber compound, as measured by the RPA, the materials evaluated in this study also altered the cured viscoelastic properties, as measured by the Rheometrics RMS-800. At 23°C, SP6701, Pliolite S6H and Ulti-Pro 100 all significantly increased the elastic modulus (G’) of the compound, even beyond that caused by an increase in carbon black. (Figure 22) Vestenamer 8012 only caused a slight increase in elastic modulus, while the other additives had little effect. At 60°C, SP6701, Pliolite S6H and Ulti-Pro 100 still caused a large increase in elastic modulus, however the high styrene resin, Pliolite S6H, softened significantly compared to the other two materials. Vestenamer 8012 still maintained a slight advantage over the control compound. (Figure 23) Of the additives that increased the elastic modulus of the compound (SP6701, Pliolite S6H, Ulti-Pro 100 and Vestenamer 8012), only the high styrene resin, Pliolite S6H significantly increased the tangent delta of the compound as well. This was especially evident at the 60°C test temperature. (Figures 24, 25) The other materials (SP6701, Ulti-Pro 100 and Vestenamer 8012) actually caused a reduction in tangent delta compared to the control compound. At low strains, the Ulti-Pro 100 containing compound reduced the tangent delta of the compound below that of the control with reduced carbon black. Both
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LIR 30 and the aromatic oil, Sundex 790T, which had little effect on elastic modulus, caused a significant increase in tangent delta at both 23°C and 60°C. (Figures 24, 25) During high temperature dynamic testing, up to 130°C, both Ulti-Pro 100 and SP6701 maintained their increased elastic modulus over the higher carbon black control, while Vestenamer 8012 maintained its’ slight advantage over the control compound. Although starting at low temperatures with an elastic modulus greater than the increased carbon black formulation, Pliolite S6H softened with heating so much, that above 76°C, the elastic modulus was actually below that of the control. (Figure 26) As the high styrene resin Pliolite S6H went through a phase change, the tangent delta peaked at about 65°C, until it eventually returned to a par with the control. (Figure 27) Up until about 58°C the SP6701 containing compound maintained a tangent delta lower than the control, while Ulti-Pro 100 maintained a tangent delta below that of the control until about 93°C. At all temperatures, the Ulti-Pro 100 compound maintained a significantly lower tangent delta than the phenolic resin SP6701. Vestenamer 8012 produced a lower tangent delta than the control under all temperatures tested. (Figure 27) Of the eight materials evaluated only two significantly increased the modulus of the compound without negatively affecting the other compound properties (less cure properties which will be addressed later):
Significantly Increases Hardness/Modulus SP6701 – phenolic reinforcing resin Ulti-Pro 100 – m-hydroxydiphenylamine Vestenamer 8012 also caused a significant increase in hardness/modulus (albeit not to the degree of the above two materials), however it also caused a significant reduction in elongation at break which may or may not be an aberration, as that experiment was not repeated to verify the results. While both the phenolic resin SP6701 and Ulti-Pro 100 increase the hardness/modulus of the compound, only Ulti-Pro 100 has no effect on the processability of the compound and may even make the compound more processable, depending on one’s measure of processability.
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Increasing the Scorch Safety of Ulti-Pro 100 Containing Compounds The reduction in scorch safety observed when using Ulti-Pro 100 and HMTA (hexamethylenetetramine) is significant. The easiest way to correct the problem is to substitute HMMM (hexamethoxymethylmelamine) for HMTA, which causes a much smaller reduction in scorch than does HMTA. (Tables 4, 5) The slight reduction in scorch safety caused by HMMM can then be adjusted by the addition of a small amount of CTP (n-cyclohexyl thiophthalimide). (Table 4) The reduction in scorch caused by using HMTA with Ulti-Pro 100 can be improved by the addition of CTP, however CTP is more effective when it is used with an amine scavenger6 such as calcium stearate. (Table 5)
Conclusions:
• Depending on the method used to judge processability, Ulti-Pro 100 reactive processing aid significantly improves the processability of a natural rubber beadfiller compound.
• Ulti-Pro 100 also significantly increases the cured hardness/modulus of the compound without negatively impacting the compound’s hysteresis.
• Ulti-Pro 100 containing compounds are significantly scorchier than compounds without Ulti-Pro 100, however the scorch problem can be corrected through the use of CTP, when using HMMM as the methylene donor, or a combination of CTP with an amine scavenger such as calcium stearate, when using HMTA as the methylene donor.
• Of the eight rubber additives evaluated in this study, only Ulti-Pro 100 improved the processability of the compound and increased the hardness/modulus. The other seven additives could only accomplish one of the two targets.
1 The Vanderbilt Rubber Handbook. Ed. Robert F. Ohm. 13th Edition. Norwalk, CT: R.T. Vanderbilt Company, Inc. 1990: 421-422. 2 White, James L. Rubber Processing, Technology-Materials-Principals. Cincinnati: Hanser/Gardner Publications Inc. 1995: 89. 3 Rubber Technology, Compounding and Testing for Performance. Ed. John S. Dick. Cincinnati: Hanser/Gardner Publications Inc. 2001: 27. 4 Basic Rubber Testing. John S. Dick Ed. West Conshohoken, PA: ASTM International. 2003: 26-28. 5 Rubber Technology, Compounding and Testing for Performance: 30. 6 Dunnom, Donald D. Rubber Compositions. PPG Industries, Inc., assignee. Patent 3,738,948 June 1973.
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Table 1 – Materials Evaluated
Material Tradename Chemical Composition Manufacturer Abbreviation Epolene™ N34W Low MW polyethylene
wax, 2900 MW, 103°C softening point
Eastman Chemical Company
N34W
LIR 30 Liquid polyisoprene, 30,000 MW
Kuraray Co. Ltd. LIR
Pliolite® S6H High styrene SBR resin, 82.5% styrene, 17.5% butadiene, 36.8°C tg
Eliokem, Inc. S6H
SP6701 Tall oil modified phenolic reinforcing resin
Schenectady International Inc.
SP6701
Struktol® WB-212 Emulsion of fatty acid esters on an inorganic carrier
Strucktol Company of America
WB-212
Sundex® 790T Aromatic oil Sunoco Oil
Vestenamer® 8012 Trans-polyoctenamer Degussa Corporation
Vest
Ulti-Pro® 100 reactive processing aid
M-hydroxydiphenylamine INDSPEC Chemical Corporation
Ulti-Pro 100
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Table 2 – Rubber Formulations, Control Compounds
Control Control -10 Black
Control +10 Black
1st Mix Stage, Internal Mixer
SIR-20 Natural Rubber 100 phr 100 100
N-330 Carbon Black 70 60 80
TMQ 2 2 2
Zinc Oxide 5 5 5
Stearic Acid 2 2 2
2nd Mix Stage, 2 Roll Mill Remill Remill Remill
3rd Mix Stage, 2 Roll Mill
Insoluble Sulfur (80%) 3.13 3.13 3.13
MBS 1.5 1.5 1.5
Total Parts 183.63 173.63 193.63
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Table 2 (continued) – Rubber Formulations, Experimental Compounds
Ulti-Pro 100
WB-212
S6H N34W SP6701 Oil Vest LIR
1st Mix Stage, Internal Mixer
SIR-20 Natural Rubber
100 100 100 100 100 100 90 90
N330 Carbon Black 70 70 70 70 70 70 70 70
TMQ 2 2 2 2 2 2 2 2
Zinc Oxide 5 5 5 5 5 5 5 5
Stearic Acid 2 2 2 2 2 2 2 2
Vestenamer® 8012 10
LIR 30 10
2nd Mix Stage, 2 Roll Mill
Ulti-Pro® 100 reactive processing aid
3
Struktol® WB-212 3
Pliolite® S6H 10
Epolene™ N34W 3
SP6701 3
Sundex® 790T 3
3rd Mix Stage, 2 Roll Mill
Insoluble Sulfur (80%) 3.13 3.13 3.13 3.13 3.13 3.13 3.13 3.13
MBS 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
HMTA 1 0.33
Total Parts 187.63 186.63 193.63 186.63 186.93 186.63 183.63 183.63
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Table 3 – Test Methods Test Test Method Mooney Viscosity, 100°C, Large Rotor ASTM D-1646-96
Mooney Stress Relaxation, 100°C, Large Rotor ASTM D-1646-96
MDR Rheometer, 160°C, 0.5° Arc ASTM D-5289-95
Shore A Hardness, 23°C ASTM D-2240-97
Stress Strain Testing, 23°C ASTM D-412-97, Method A
Rheometrics RMS-800 Viscoelastic Properties, Torsion Rectangular Specimen, 23°C, 1 hz. 0-10% strain sweep
INDSPEC Test Procedure
Rheometrics RMS-800, Viscoelastic Properties, Torsion Rectangular Specimen, 60°C, 1 Hz., 0-5% strain sweep
INDSPEC Test Procedure
Rheometrics RMS-800, Viscoelastic Properties, Torsion Rectangular Specimen, 1 Hz, 2% strain, 0-130°C temperature sweep
INDSPEC Test Procedure
Göttfert Capillary Rheometer, 20:1 L/D, Round Geometry 100°C, 10, 30, 100, 300, 1000 s-1 shear rate
Solgenesis Test Procedure, Testing conducted at Solgenesis
Alpha Technologies RPA Rubber Process Analyzer, 1. 40°C, 1 minute, 0.5 Hz, 3% strain 2. 40°C, 1 minute, 0.1, 2.0, 20, 30 Hz, 7% strain 3. 40°C, 1 minute, 1.0 Hz, 10, 20, 50, 100% strain 4. 100°C, 1 minute, 0.5 Hz, 3% strain 5. 100°C, 1 minute, 0.1, 2.0, 20, 30 Hz, 7% strain 6. 100°C, 1 minute, 1.0 Hz, 10, 20, 50, 100% strain
Testing Conducted at Smithers Scientific Services
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Table 4 – Effect of HMMM on the Scorch Safety of Ulti-Pro 100 Containing Compounds Control Ulti-Pro 100,
HMMM Ulti-Pro 100, HMMM, CTP
1st Mix Stage, Internal Mixer
CV60 Natural Rubber 100 100 100
N330 Carbon Black 70 70 70
TMQ 2 2 2
Zinc Oxide 5 5 5
Stearic Acid 2 2 2
2nd Mix Stage, 2 Roll Mill
Ulti-Pro® 100 reactive processing aid
3 3
3rd Mix Stage, 2 Roll Mill
Insoluble Sulfur (80%) 3.13 3.13 3.13
MBS 1 1 1
HMMM (72%) 1.39 1.39
CTP 0.2
Total Parts 183.13 187.52 187.72 Mooney Scorch, 125°C Initial Peak, Mooney units 88 78 76
ML, Mooney units 64 58 59
t5, minutes 19.3 13.1 23.0
t35, minutes 22.6 15.8 26.5
MDR Rheometer, 160°C
MH, dN-m 26.84 32.51 32.77
ML, dN-m 3.29 3.24 3.29
ts2, minutes 1.64 1.51 2.41
t’50, minutes 3.12 3.19 4.25
t’90, minutes 5.67 8.95 9.63
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Table 5 – Effect of HMTA on the Scorch Safety of Ulti-Pro 100 Containing Compounds Control Ulti-Pro 100
HMTA Ulti-Pro 100 HMTA, CTP
Ulti-Pro 100 HMTA, CTP, Calcium Stearate
1st Mix Stage, Internal Mixer
CV60 Natural Rubber 100 100 100 100
N330 Carbon Black 70 70 70 70
TMQ 2 2 2 2
Zinc Oxide 5 5 5 5
Stearic Acid 2 2 2 2
Calcium Stearate 1
2nd Mix Stage,2 Roll Mill
Ulti-Pro® 100 reactive processing aid
3 3 3
3rd Mix Stage, 2 Roll Mill
Insoluble Sulfur (80%) 3.13 3.13 3.13 3.13
MBS 1 1 1 1
HMTA 1 1 1
CTP 0.2 0.2
Total Parts 183.13 187.13 187.33 188.33 Mooney Scorch, 125°C Initial Peak, Mooney units 88 77 74 76
ML, Mooney units 64 61 60 59
t5, minutes 19.3 7.2 9.7 12.4
t35, minutes 22.6 10.0 16.1 17.8
MDR Rheometer, 160°C
MH, dN-m 26.84 40.79 42.02 41.80
ML, dN-m 3.29 3.26 3.14 3.20
ts2, minutes 1.64 0.87 1.36 1.52
t’50, minutes 3.12 2.03 2.56 2.75
t’90, minutes 5.67 4.26 4.80 5.09
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Figure 1 – Mooney Viscosity Results
Mooney Viscosity, ML1+4, 100°C
50
55
60
65
70
75
80
85
90
Moo
ney
Vis
cosi
ty, M
L 1+
4
-10Black
N34W
10 LIR
Oil
WB-212
Ulti-Pro 100
10 S6H
Control
10 Vest.
SP6701
+10Black
Control
-10 Black
+10 Black
Figure 2 – Mooney Stress Relaxation Results
Mooney Stress Relaxation, 100°C
-0.50
-0.45
-0.40
-0.35
-0.30
-0.25
-0.20
Slo
pe (M
oone
y un
its/s
econ
d)
-10Black
Ulti-Pro 100
10 S6H
WB-212
10 Vest.
N34W
Oil
Control
10 LIR
SP6701
+10BlackControl
-10 Black
+10 Black
16
Figure 3 – Capillary Rheometer Results
Capillary Rheometer, Apparent Viscosity, 100°C
1.00E+02
1.00E+03
1.00E+04
1.00E+05
10 100 1000
Shear Rate, 1/s
App
aren
t Vis
cosi
ty, P
a-s
Control
Ulti-Pro 100
WB-212
10 S6H
N34WSP6701
Oil
10 Vest.
10 LIR
-10Black
+10Black
Figure 4 – Capillary Rheometer Results
Capillary Rheometer, 100°C, 10/s Shear Rate
2.00E+04
2.20E+04
2.40E+04
2.60E+04
2.80E+04
3.00E+04
3.20E+04
3.40E+04
App
aren
t Vis
cosi
ty, P
a-s
-10Black
10 LIR
Ulti-Pro 100
Oil
N34W
WB-212
10 S6H
SP6701
Control
10 Vest.
+10Black
Control
-10 Black
+10 Black
17
Figure 5 – Capillary Rheometer Results
Capillary Rheometer, 100°C, 30/s Shear Rate
8.00E+03
9.00E+03
1.00E+04
1.10E+04
1.20E+04
1.30E+04
1.40E+04
App
aren
t Vis
cosi
ty, P
a-s
-10Black
WB-212
10 LIR
Ulti-Pro 100
N34W
Oil
10 S6H
SP6701
Control
10 Vest.
+10Black
Control
-10 Black
+10 Black
Figure 6 – Capillary Rheometer Results
Capillary Rheometer, 100°C, 100/s Shear Rate
3.00E+03
3.50E+03
4.00E+03
4.50E+03
5.00E+03
5.50E+03
6.00E+03
App
aren
t Vis
cosi
ty, P
a-s
-10Black
10 LIR
WB-212
N34W
Ulti-Pro 100
Oil
10 S6H
SP6701
Control
10 Vest.
+10Black
Control
-10 Black
+10 Black
18
Figure 7 – Capillary Rheometer Results
Capillary Rheometer, 100°C, 300/s Shear Rate
1.00E+03
1.20E+03
1.40E+03
1.60E+03
1.80E+03
2.00E+03
2.20E+03
2.40E+03
App
aren
t Vis
cosi
ty, P
a-s
-10Black
WB-212
10 LIR
Ulti-Pro 100
Oil
N34W
Control
10 S6H
SP6701
10 Vest.
+10Black
Control
-10 Black
+10 Black
Figure 8 – Capillary Rheometer Results
Capillary Rheometer, 100°C, 1000/s Shear Rate
6.00E+02
7.00E+02
8.00E+02
9.00E+02
1.00E+03
1.10E+03
1.20E+03
App
aren
t Vis
cosi
ty, P
a-s
Oil
Ulti-Pro 100
SP6701
All 3 controls exceeded maximumpressure of the capillary rheometer
19
Figure 9 – Capillary Rheometer Results
Capillary Rheometer, Running Die Swell, 100°C
0%
5%
10%
15%
20%
25%
0 100 200 300 400 500 600 700 800 900 1000
Shear Rate 1/sec
Die
Sw
ell,
%
Control
Ulti-Pro 100
WB-212
10 S6H
N34W
SP6701
Oil
10 Vest.
10 LIR
-10Black
+10Black
Figure 10 – RPA Results
RPA, Complex Dynamic Viscosity, 40°C, 6.98% Strain
1,000
10,000
100,000
1,000,000
10,000,000
0.1 1.0 10.0 100.0
Frequency, Hz
Com
plex
Dyn
amic
Vis
cosi
ty η
* (P
a-s)
Control
Ulti-Pro 100
WB-212
10 S6H
N34W
SP6701
Oil
10 Vest.
10 LIR
-10Black
+10Black
20
Figure 11 – RPA Results
RPA, Complex Viscosity, 40°C, 1 Hz
0
50,000
100,000
150,000
200,000
250,000
300,000
350,000
400,000
450,000
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Strain
Com
plex
Vis
cosi
ty η
* (P
a-s)
Control
Ulti-Pro 100
WB-212
10 S6H
N34W
SP6701
Oil
10 Vest.
10 LIR
-10Black
+10Black
Figure 12 – RPA Results
RPA, Complex Dynamic Viscosity, 100°C, 6.98% Strain
1,000
10,000
100,000
1,000,000
0.1 1.0 10.0 100.0
Frequency, Hz
Com
plex
Dyn
amic
Vis
cosi
ty η
* (P
a-s)
Control
Ulti-Pro 100
WB-212
10 S6H
N34W
SP6701
Oil
10 Vest.
10 LIR
-10Black
+10Black
21
Figure 13 – RPA Results
RPA, Elastic Modulus, 100°C, 1 Hz
60
110
160
210
260
310
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Strain
Ela
stic
Mod
ulus
, G' (
kPa)
Control
Ulti-Pro 100
WB-212
10 S6H
N34W
SP6701
Oil
10 Vest.
10 LIR
-10Black
+10Black
Figure 14 – RPA Results
RPA, Tangnt Delta, 40°C, 1 Hz
0.200
0.300
0.400
0.500
0.600
0.700
0.800
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Strain
Tan
gent
Del
ta
Control
Ulti-Pro 100
WB-212
10 S6H
N34W
SP6701
Oil
10 Vest.
10 LIR
-10Black
+10Black
22
Figure 15 – RPA Results
RPA, Tangent Delta, 100°C, 1 Hz
0.400
0.500
0.600
0.700
0.800
0.900
1.000
1.100
1.200
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Strain
Tan
gent
Del
ta
Control
Ulti-Pro 100
WB-212
10 S6H
N34W
SP6701
Oil
10 Vest.
10 LIR
-10Black
+10Black
Figure 16 – Mooney Scorch Results
Mooney Scorch, 125°C
0.0
5.0
10.0
15.0
20.0
25.0
Moo
ney
Sco
rch
t5 (m
inut
es)
Ulti-Pro 100
+10Black
SP6701
Control
WB-212
Oil
10 LIR
10 Vest.
-10Black
N34W
10 S6H
Control
-10 Black
+10 Black
23
Figure 17 –MDR Rheometer Results
Rheometer t'90, 160°C
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
t'90
(min
utes
)
Ulti-Pro 100
+10Black
Control
WB-212
Oil
N34W
10 LIR
-10Black
10 Vest.
10 S6H
SP6701
Control -10 Black
+10 Black
Figure 18 – Shore A Hardness Results
Shore A Hardness, 23°C
65
70
75
80
85
90
Sho
re A
Har
dnes
s
-10Black
Oil
WB-212
N34W
Control
10 LIR
10 Vest.
+10Black
SP6701
10 S6H
Ulti-Pro 100
Control
-10 Black
+10 Black
24
Figure 19 – Tensile Modulus Results
100% Tensile Modulus
4.00
4.50
5.00
5.50
6.00
6.50
7.00
7.50
8.00
100%
Mod
ulus
, MP
a
-10Black
Oil
WB-212
N34W
Control
10 LIR
10 S6H
SP6701
10 Vest.
Ulti-Pro 100
+10Black
Control
-10 Black
+10 Black
Figure 20 – Tensile Strength Results
Tensile Strength
19.0
20.0
21.0
22.0
23.0
24.0
25.0
26.0
Ten
sile
Stre
ngth
, MP
a
+10Black
10 LIR
10 S6H
N34W
WB-212
10 Vest.
Oil
Control
SP6701
Ulti-Pro 100
-10Black
Control
-10 Black
+10 Black
25
Figure 21 – Elongation at Break Results
Elongation at Break
200
220
240
260
280
300
320
340
360
380
400
Elo
ngta
ion
at B
reak
, %
+10Black
10 Vest.
Ulti-Pro 100
10 LIR
10 S6H
Control
SP6701
N34W
WB-212
Oil
-10Black
Control
+10 Black
-10 Black
Figure 22 – Viscoelastic Properties, Rheometrics RMS-800 Results
G', 23°C, 1 Hz
0
5
10
15
20
25
30
35
0 1 2 3 4 5 6 7 8 9 10
% Strain
G' (
MP
a)
Control
Ulti-Pro 100
WB-212
10 S6H
N34W
SP6701
Oil
10 Vest.
10 LIR30
-10Black
+10Black
26
Figure 23 – Viscoelastic Properties, Rheometrics RMS-800 Results
G', 60°C, 1 Hz
0
5
10
15
20
25
30
35
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
% Strain
G' (
MP
a)
Control
Ulti-Pro 100
WB-212
10 S6H
N34W
SP6701
Oil
10 Vest.
10 LIR30
-10Black
+10Black
Figure 24 – Viscoelastic Properties, Rheometrics RMS-800 Results
Tan Delta, 23°C, 1 Hz
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0 1 2 3 4 5 6 7 8 9 10
% Strain
Tan
Del
ta
Control
Ulti-Pro 100
WB-212
10 S6H
N34W
SP6701
Oil
10 Vest.
10 LIR30
-10Black
+10Black
27
Figure 25 – Viscoelastic Properties, Rheometrics RMS-800 Results
Tan Delta, 60°C, 1 Hz
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
% Strain
Tan
Del
ta
Control
Ulti-Pro 100
WB-212
10 S6H
N34W
SP6701
Oil
10 Vest.
10 LIR30
-10Black
+10Black
Figure 26 – Viscoelastic Properties, Rheometrics RMS-800 Results
G' (23°C, 1Hz), 2% Strain, Temperature Sweep
0.00
5.00
10.00
15.00
20.00
25.00
30.00
0.0 20.0 40.0 60.0 80.0 100.0 120.0
Temperature, C
G' (
MP
a)
Control
Ulti-Pro 100
WB-212
10 S6H
N34W
SP6701
Oil
10 Vest.
10 LIR30
-10Black
+10Black
28
Figure 27 – Viscoelastic Properties, Rheometrics RMS-800 Results
Tan Delta (23°C, 1Hz), 2% Strain, Temperature Sweep
0.000
0.050
0.100
0.150
0.200
0.250
0.300
0.350
0.400
0.0 20.0 40.0 60.0 80.0 100.0 120.0
Temperature, C
Tan
Del
ta
Control
Ulti-Pro 100
WB-212
10 S6H
N34W
SP6701
Oil
10 Vest.
10 LIR30
-10Black
+10Black
