GRAPHENE AS ADDITIVE IN SILICA TREAD APPLICATIONS

Abstract

The introduction of graphene as an additive in rubber compounds is disclosed. The product shows increased barrier protection for tire innerliners, with no tradeoffs in other characteristics.

Claims

1. A rubber composition comprising: styrene butadiene rubber; silicon dioxide; bis[3-(triethoxysilyl)propyl]polysulfide; graphene, wherein the graphene has a thickness of less than about 3.2 nm, a particle size of between about 50 nm and about 10 μm, and contains greater than about 95% carbon; aliphatic hydrocarbon resin; treated distillate aromatic extract; N-(1.3-dimethylbutyl)-N′-phenyl-1,4-benzenediamine; 2,2,4-trimethyl-1.2-dihydroquinoline; paraffinic wax; microcrystalline wax; zinc oxide; stearic acid; N-cyclohexyl-2-benzothiazole sulfonamide; 1,3 diphenylguanidine; sulfur; and pre vulcanization inhibitor.

2. A rubber composition comprising: styrene butadiene; silicon dioxide; organosilane; and graphene, wherein the graphene has a thickness of less than about 3.2 nm, a particle size of between about 50 nm and about 10 μm, and contains greater than about 95% carbon.

3. The rubber composition of claim 2, wherein the graphene is a graphene plate, wherein the graphene plate is between about 0.5 PHR and about 10.0 PHR.

4. The rubber composition of claim 3, wherein the graphene plate has a surface area from about 100 m.sup.2/gram to about 250 m.sup.2/gram.

5. The rubber composition of claim 4, wherein the graphene plate has an oxygen content of less than about 1%.

6. The rubber composition of claim 2, wherein the thickness is less than about 1 nm and the aspect ratio is about 1000.

7. The rubber composition of claim 3, wherein the graphene plate is between about 0.5 PHR and about 8.0 PHR.

8. The rubber composition of claim 7, wherein the rubber composition further comprises: aliphatic hydrocarbon resin; treated distillate aromatic extract; an antiozonant; and, an antioxidant.

9. The rubber composition of claim 8, wherein the rubber composition further comprises: paraffinic wax; microcrystalline wax; zinc oxide; stearic acid; an accelerator, a secondary accelerator; sulfur; and a pre vulcanization inhibitor.

10. The rubber composition of claim 9, wherein the antiozonant is N-(1,3-dimethylbutyl)-N′-phenyl-1,4-benzenediamine and the antioxidant is 2,2,4-trimethyl-1,2-dihydroquinoline.

11. The rubber composition of claim 10, wherein the accelerator is N-cyclohexyl-2-benzothiazole sulfonamide and the secondary accelerator is 1.3-diphenylguanidine.

12. The rubber composition of claim 6, wherein the graphene plate is between about 1.0 PHR and about 2.0 PHR, wherein the composition has no clay fillers.

13. The rubber composition of claim 6, wherein the graphene plate is between about 3.0 PHR and about 5.0 PHR.

14. The rubber composition of claim 2, wherein the graphene is graphene plates, wherein substantially all of the graphene plates are parallel and in contact with each other.

15. The rubber composition of claim 14, wherein the graphene plate is between about 15.0 PHR and about 20.0 PHR.

16. The rubber composition of claim 1, wherein the rubber composition is a silica tread composition.

17. The rubber composition of claim 2, wherein the rubber composition is chosen from the group consisting of a silica tread composition, seals, gaskets, medical gloves, beverage bottles, and chemical and solvent resistant gloves.

Description

III. Brief Description Of The Drawings

[0025] The present teachings are described hereinafter with reference to the accompanying drawings.

[0026] FIG. 1 depicts a graph showing rapid reduction in permeability;

[0027] FIG. 2 depicts the structures of graphene, graphene oxide, and reduced graphene oxide;

[0028] FIG. 3 depicts a tire;

[0029] FIG. 4 is a graphical representation of the graphene plates acting as a barrier to gas flow;

[0030] FIG. 5 shows a chart of Mooney viscosity;

[0031] FIG. 6 shows a chart of rheometer results;

[0032] FIG. 7 shows a chart of cure rate index;

[0033] FIG. 8 shows a chart of tear strength;

[0034] FIG. 9 shows a chart of peel adhesion;

[0035] FIG. 10 shows a chart of electrical resistivity;

[0036] FIG. 10A shows a diagram of quadruplex and pentaplex units;

[0037] FIG. 11 shows a chart of storage modulus G′; and

[0038] FIG. 12 shows a chart of loss compliance J″.

IV. DETAILED DESCRIPTION

[0039] With reference to FIGS. 1-4. in one aspect of the present teaching. a tire innerliner is a calendered halobutyl rubber sheet compounded with additives that result in low air permeability. The innerliner assures that the tire will hold high-pressure air inside, without an inner tube, minimizing diffusion through the rubber structure. Compounding is the operation of bringing together all the ingredients required to mix a batch of rubber compound. Each component has a different mix of ingredients according to the properties required for that component. Mixing is the process of applying mechanical work to the ingredients in order to blend them into a homogeneous substance. Internal mixers are often equipped with two counter-rotating rotors in a large housing that shear the rubber charge along with the additives. The mixing is done in two or three stages to incorporate the ingredients in the desired order. The shearing action generates considerable heat, so both rotors and housing are water-cooled to maintain a temperature low enough to assure that vulcanization does not begin.

[0040] With continuing reference to FIGS. 1-4, the graphene is added to the rubber and mixed as noted above. Graphene will be added to a rubber formulation, such as one based on bromobutyl, at levels from about 0.1 PHR to about 50.0 PHR, including about 0.5 PHR to about 45.0 PHR, about 0.5 PHR to about 40.0 PHR, about 0.5 PHR to about 35.0 PHR, about 0.5 PHR to about 30.0 PHR, about 0.5 PHR to about 25.0 PHR, about 0.5 PHR to about 20.0 PHR, about 0.5 PHR to about 15.0 PHR, and from 0.5 PHR to 10.0 PHR. In another aspect of the present teachings. the graphene is added at less than about 50.0 PHR, less than about 45.0 PHR. less than about 30.0 PHR, less than about 25.0 PHR, less than about 20.0 PHR, less than about 15.0 PHR, and less than about 10.0 PHR. In another aspect of the present teachings, the graphene is added at greater than about 0.5 PHR. greater than about 1.0 PHR, greater than about 5.0 PHR, greater than about 10.0 PHR, greater than about 15.0 PHR, greater than about 20.0 PHR, greater than about 25.0 PHR. greater than about 30.0 PHR, greater than about 35.0 PHR. greater than about 40.0 PHR, and greater than about 45.0 PHR. With continuing reference to FIGS. 1-4. the graphene is added to the rubber and mixed as noted above. Graphene in this aspect is described as in Table 1.

TABLE-US-00001 TABLE 1 Typical Properties of Graphene Form Powder, dark grey, odorless Carbon >95% Particle size 50 nm to 10 μm Moisture, Oxygen, Ash <0.75 wt. %, <2.0 wt. %, <4.5 wt. %, respectively Resistivity <150 ohm cm Particle (sheet) thickness) <3.2 nm Particle layers <16 Specific gravity 2. gm/cubic centimeter Surface area (specific) 180 square m.sup.2/gm

[0041] The particle size range of graphene used in the present teachings can range from about 50 nm to about 10 Mm. In one aspect, the particle size range is from about 100 nm to about 5 μm. In one aspect. the particle size range is greater than about 50 nm, greater than about 100 nm, greater than about 150 nm, greater than about 200 nm. greater than about 250 nm, greater than about 300 nm, greater than about 350 nm. greater than about 400 nm, greater than about 450 nm, greater than about 500 nm, greater than about 550 nm, greater than about 600 nm, greater than about 650 nm, greater than about 700 nm, greater than about 750 nm, greater than about 800 nm, greater than about 850 nm, greater than about 900 nm, greater than about 950 nm, greater than about 1 μm, greater than about 2 μm, greater than about 3 μm, greater than about 4 μm. greater than about 5 μm, greater than about 6 μm, greater than about 7 μm, greater than about 8 μm. or greater than about 9 μm. In one aspect, the particle size range is less than about 10 μm, less than about 9 μm. less than about 8 μm. less than about 7 μm. less than about 6 μm. less than about 5 μm, less than about 4 μm, less than about 3 μm, less than about 2 μm, less than about 1 μm, less than about 950 nm, less than about 900 nm. less than about 850 nm, less than about 800 nm, less than about 750 nm, less than about 700 nm, less than about 650 nm, less than about 6(X) nm, less than about 550 nm. less than about 500 nm, less than about 450 nm, less than about 400 nm, less than about 350 nm, less than about 300 nm, less than about 250 nm, less than about 200 nm. less than about 150 nm, or less than about 100 nm. The form is plate-like rather that cylindrical or fibrous. To further define the material, carbon content is greater than 95%, and in one aspect greater than 99%. The carbon content can be greater than 96%, greater than 97%, or greater than 98% as well. Ash and oxygen content is less than 1% in one aspect of the present teachings. In one aspect, the average particle thickness is about 2.5 nm and the number of layers in a particle would is less than 15. thus allowing attainment of a near exfoliated condition when compounded. Specific surface area of the graphene plate will range from 100 m.sup.2/gram to 250 m.sup.2/gram and in one aspect is about 180 m.sup.2/gram. In one aspect, the surface area of the graphene plate is greater than 150 m.sup.2/gram. greater than 100 m.sup.2/gram, less than 250 m.sup.2/gram, less than 200 m.sup.2/gram, or less than 150 m.sup.2/gram.

[0042] Graphene is added to the rubber compound formulations at between about 0.0 PHR and about 50.00 PHR, including in the range of about 0.5 PHR to about 8.00 PHR. Reductions in compound permeability initially show a large decrease (as shown in FIG. 1). tapering as graphene levels increase. Gas-permeability decreases with increasing graphene loading of about 0.4 vol % in rubber composites. The percolation threshold is about 40 times lower than that for clay-based composites. According to the Nielsen model on gas permeability, the thickness of an individual graphene based sheet dispersed in the graphene styrene-butadiene rubber (SBR) composite with 2.0 vol. % of GO was predicted to be 1.47 nm.

[0043] Graphene, when added to a bromobutyl rubber compound formulation, can be in various forms and which can be part of the present teaching, such as a powder, in pastilles or pellets using wax as a carrier, aiding dust suppression, in pre-weight sealed, low-melt temperature polyethylene bags, and melt or solution blended with a compatible polymer, such as butyl rubber or halobutyl rubber and then compounded as part of the total rubber hydrocarbon content.

[0044] Graphene has an aspect ratio of near 1000, assuming the graphene plate thickness is about 1 nm. The plate length/diameter can be up to about 1 micron. The graphene can thus function as a barrier. The graphene exfoliates into sheets when added to the rubber compound. which improves the barrier properties when perpendicular alignment to the sheet direction is achieved. The graphene plates provide a barrier to oxygen and nitrogen migration, and moisture or water vapor molecules migrating through the liner compound of the tire or other product requiring such properties. Such gas molecule transport phenomenon is described as a “tortuous path” as shown in FIG. 4. With continuing reference to FIGS. 1-4. with the addition of graphene as a filler, there is no trade-off or loss in conventional processing and mechanical properties. Graphene has a very high aspect ratio. Small amounts have a large impact on reducing permeability. The nominal aspect ratio of graphene of up to 1000 compares with the typical aspect ratio of 20 for kaolin clay fillers. The clay fillers have to be added at about 40 PHR and also need a surfactant for compatibility. Due to the relatively large size of the graphene plates versus inorganic fillers, graphene can be added at about 1 PHR to about 2 PHR.

[0045] Measurement of Properties of Rubber Compositions

[0046] Mooney viscosity (ML1+4) at 100° C. measured in accordance with ASTM D1646. Vulcanization kinetics and associated properties was measured by following the procedure in ASTM D5289. Tensile strength and associated data generated through measurement of tensile strength was determined following ASTM D412. Shore-A Hardness was measured following the method in ASTM D2240. Tear strength and adhesion were measured following ASTM D624. Oxygen permeability was measured using an Ametek Mocon OX-TRAN 2/22 permeability tester and following ASTM D3985. Air permeability determined according to the method in ASTM D1434.

Example 1

[0047] In this example tire model innerliner compounds were prepared containing graphene levels, ranging from about 0.00 PHR to about 20.00 PHR. The graphene was first blended with bromobutyl rubber and then added as a master-batch to the compounds. The amount of free bromobutyl polymer added to the formulation was adjusted with the graphene master-batch to ensure the total polymer content is 100.00 PHR as described earlier. Graphene was added at 0.5 PHR, 2.0 PHR, 5.00 PHR, 8.00 PHR. and 20.0 PHR. Compounds were prepared using a laboratory internal mixer, using a two-stage mixing procedure. The first stage is referred to as non-productive, followed by the final stage or productive phase, where the vulcanization chemicals are added. The formulations are shown in Table 2. Though not necessary, in Table 1 a re-mill is illustrated which can be included in the mixing procedure should it be desired. A re-mill is a procedure where the compound is passed through a mixer for a short period of time so as to optimized final compound viscosity.

[0048] The mechanical properties illustrated in Table 3 are equivalent to innerliners with no graphene. This is the case for compounds containing graphene at levels up to about 10 PHR. It is noted that industrial levels of graphene usage will be in the range of about 0.5 PHR to about 10.0 PHR. There is no shift in tensile strength, Mooney viscosity, modulus, tack, green strength. or tear strength. However, there is direction improvement in adhesion, consistent with results from other compound classes.

Example 2

[0049] This example shows the excellent reduction in permeability achieved with small amounts of graphene in the bromobutyl innerliner compound. Permeability was measured and two sets of results are reported, (i) permeation of oxygen through the innerliner compounds and (ii) permeation of air. In both instances there is a sharp reduction in permeability with very small amounts of graphene added to the bromobutyl compounds. followed by a less steep drop than would be predicted by computational models proposed by Neilson.

[0050] Addition of graphene to the bromobutyl compound shows a very rapid drop in permeability which is required for tire innerliner applications. This drop is considered significantly greater than that possible using other plate-like additives, such as kaolin clays, other clays, or talc nanocomposites. It is noted that this reduced tire liner permeability is useful for electric vehicle tires, truck tires, bus tires, off road tires, farm equipment tires, and aircraft tires. Graphene has an aspect ratio of near 1000, assuming the graphene plate thickness is about 1 nm. The plate length/diameter can be up to about 1 micron. The graphene thus functions as a barrier or creation of the tortuous path noted above (FIG. 4). The graphene exfoliates into sheets when added to the rubber compound, which improves the barrier properties. The graphene plates provide a barrier to oxygen and nitrogen migration through the liner compound of the tire.

TABLE-US-00002 TABLE 2 Compound 3 (control ) 1 2 4 5 6 Number ERTNB10- ERTNB10- ERTNB10- ERTNB10- ERTNB10- ERTNB10- 54-03 54-01 54-02 54-04 54-05 54-06 BIIR 2222 100.00 98.67 94.67 86.67 78.67 46.70 Carbon Black N660 60.00 60.00 60.00 60.00 60.00 60.00 ERTNB10-53-MB 0.00 1.83 7.33 18.33 29.33 73.30 Naphthenic oil 8.00 8.00 8.00 8.00 8.00 8.00 Struktol 40MS 7.00 7.00 7.00 7.00 7.00 7.00 Koresin 2.00 2.00 2.00 2.00 2.00 2.00 Escorez 1102 2.00 2.00 2.00 2.00 2.00 2.00 Stearic Acid 1.00 1.00 1.00 1.00 1.00 1.00 Zinc Oxide 1.00 1.00 1.00 1.00 1.00 1.00 MBTS 1.25 1.25 1.25 1.25 1.25 1.25 Sulfur 0.50 0.50 0.50 0.50 0.50 0.50 Total 182.75 183.25 184.75 187.75 190.75 202.75 Graphene 0.00 0.50 2.00 5.00 8.00 20.00 1st Pass or Non-Productive Set-up Start Temp. 65° C., 65 RPM, & 50 Ram pressure 0′ add elastomers and ertnb10-53-MB   0.25′ add carbon black 2′ add others 3′ sweep   3.5′ adjust (increase) rotor speed, ramp temperature to 150° C. at 5′ 5′ (try to reach 150° C. at 5′) Re-mill if required Set-up Start Temp. = RT, 65 RPM, & 50 Ram pressure 0′ ADD 1st Pass MB 3′ DUMP MILL 1′ on mill with mill rolls at R.T. 5′ (try to reach 150° C. at 5′) Final Pass Productive Set-Up SANDWICH IN CURES 0′ ADD ⅔ of 2nd pass MB 15″ ADD Sulfur, Accelerator pocket, & ⅓ of 2nd pass MB 1′ SWEEP 5′ (try to reach 150° C. at 5′)

TABLE-US-00003 TABLE 3 Compound 3 1 2 4 5 6 Number ERTNB10- ERTNB10- ERTNB10- ERTNB10- ERTNB10- ERTNB10- 54-03 54-01 54-02 54-04 54-05 54-06 BIIR 2222 PHR 100.00 100.00 100.00 100.00 100.00 100.00 Graphene PHR 0.00 0.50 2.00 5.00 8.00 20.00 Mooney Viscosity ML 1 + 4 57.80 57.50 57.60 58.70 58.60 60.40 100° C. MDR Rheometer 160 C. ° Delta Torque in-lb 2.59 2.67 2.75 2.58 2.74 3.18 Ts1 min 5.08 5.15 5.04 5.10 4.78 5.52 T50 min 6.15 6.32 6.24 6.12 5.90 5.52 T90 min 12.63 12.86 12.86 12.14 11.80 12.49 Tack [Tel Tack] 3.86 2.88 3.31 3.10 3.67 5.12 Tensile Strength MPa 9.47 9.76 9.63 9.49 9.04 8.54 Elongation % 833 836 854 804 785 708  50% Modulus MPa 0.72 0.73 0.75 0.93 0.91 1.28 100% Modulus MPa 1.04 1.05 1.15 1.40 1.46 2.26 200% Modulus MPa 2.05 2.11 2.32 2.66 2.80 4.02 300% Modulus MPa 3.39 3.51 3.66 4.04 4.09 5.21 Shore A 54.00 54.00 53.00 56.00 57.00 60.00 Tear Strength KN/m 53.34 51.33 52.37 52.12 51.96 51.12 Trouser Tear Str. lbf/in 147.00 153.00 142.00 149.00 157.00 169.00 Peel Adhesion 79.00 71.00 73.00 73.00 86.00 46.00

TABLE-US-00004 TABLE 4 Compound 3 1 2 4 5 6 Number ERTNB10- ERTNB10- ERTNB10- ERTNB10- ERTNB10- ERTNB10- 54-03 54-01 54-02 54-04 54-05 54-06 BIIR 2222 PHR 100.00 100.00 100.00 100.00 100.00 100.00 Graphene PHR 0.00 0.50 2.00 5.00 8.00 20.00 Oxygen Permeability using Ametek Mocon (ASTM D3985) (40° C., 100% O.sub.2) Permeation cc*mm/(m.sup.2*day) 220 201 168 146 152 101 Permeability cc*min/(m.sup.2*day*mmHg) 0.289 0.264 0.221 0.192 0.200 0.133 Rating (Lower is better) 100 91 76 73 69 46 Air Permeability to ASTM D1434 60 C. ° Permeability cc STP − cm/ cm2 − s − atm 2.455 1.249 1.495 1.668 1.745 1.610 Rating (Lower is better) 100 51 61 68 71 66 Note: Permeation and Permeability coefficients taken from the industry reference formulation (#3) in the text Tire Engineering, CRC Press 2021

[0051] With reference to FIGS. 4-12, automobile passenger tire performance parameters include tread wear, traction, and low rolling resistance. Optimization of one property achieved by adjusting polymer content often causes loss on another property. The following Table 5 shows a graphene grade slate.

TABLE-US-00005 TABLE 5 Grade EG016 MG016 NCG015 Target Application Electronics Materials Nanocomposites Number 1 2 3 Form Light powder Light powder Light powder Color Dark grey/ Dark grey/ Dark grey/ Black Black Black Odor None None None Carbon wt % 99.50 99.00 95.00 H.sub.2O wt % 0.35 0.50 0.75 O.sub.2 wt % <1.0 <1.0 <2.0 Ash wt % <0.1 <0.5 <4.5 Resistivity ohm <50 <100 <150 (Powder) cm Resistivity <10 <20 <30 (Sheet) Particle size nm 50 nm-5 μm 100 nm-5 μm 150 nm-10 μm Mono, bi- >83% >70% >65% tri-layers Particle max 1.7 nm 2.5 nm 2.8 nm thickness Layer count <10 <15 <16 Density g/cm.sup.3 2.200 2.200 2.200 Specific m.sup.2/g 250.0 180.0 100.0 surface area

[0052] Table 6 below shows a silica tread formulation, with units being in PHR. Graphene is added in increments of 0.5, 1.0, 2.0, 4.0, and 10.0 PHR. The graphene plate aspect ratio is up to 15 times that of clay in rubber nanocomposites. Exfoliation can also be easier than clay nanocomposites, thereby achieving effective properties at lower levels of graphene.

TABLE-US-00006 TABLE 6 SSBR 25% B.S., OE 27% 96.00 Polybutadiene Nd 30.00 Ultrasil 7000 HDS 80.00 Si69 X50S 12.80 Escorez 1102 4.00 TDAE (aromatic oil) 6.00 6PPD 1.50 TMQ 1.00 Paraffinic wax 0.50 Microcrystalline wax 0.50 Zinc Oxide 3.00 Stearic acid 2.00 CBS 1.50 DPG 2.00 Sulfur 1.50 PVI 0.20

[0053] With reference to FIGS. 5-7. the addition of graphene does not shift viscosity or change compound processability. As graphene levels increase toward 10.0 PHR, rheometer torque increases slightly. Tensile strength ranges from 16.0 MPa to 16.7 MPa, 300% modulus is in the range of 11.7 MPa to 15.7 MPa, the modulus ratio is greater than four, the Shore A hardness is between 59 and 60, and the DIN abrasion resistance is within a narrow range. A modulus ratio of at least greater than 3.5 shows quality of mixing.

[0054] With reference to FIGS. 8 and 9. the addition of graphene to silica tire tread compounds shows significant improvement in tear strength and peel adhesion, with increases being observed when graphene amounts are at about 0.5 PHR. The graphene's large aspect ratio plate-like structures arrest tear propagation, increases mixing shear, and improves dispersion and homogeneity.

[0055] With reference to FIGS. 10 and 10A, the addition of graphene can lower electrical resistivity, which increases conductivity. The increased conductivity in silica tire tread compounds can facilitate electrostatic discharge. When quadruplex and pentaplex units are not available, graphene added to the treads produced by duplex or triplex extensions can help meet electrostatic discharge needs. When all, or substantially all, of the graphene plates are parallel and in contact with each other, the electrical resistivity will be optimal. The addition of about between 15.0 PHR and 20.0 PHR of graphene would create full contact of parallel graphene plates. Additionally, graphene can be added to the chimney of the tire tread. 10055) With reference to FIGS. 11 and 12. the increase in storage modulus benefits global wear, irregular wear resistance, and improved cornering coefficient. The lower loss compliance and the tan delta results at 30° C. indicate lower rolling resistance. The addition of graphene also does not lead to any loss in D′, J′ elastic compliance modulus.

TABLE-US-00007 TABLE 7 Compound 1 2 3 4 5 6 Lab Number ERTB10- ERTB10- ERTB10- ERTB10- ERTB10- ERTB10- Grade 78-21 78-22 78-23 78-24 78-25 78-26 SSBR 25% B.S., 96.00 96.00 96.00 96.00 96.00 96.00 OE 27% Polybutadiene Nd 30.00 30.00 30.00 30.00 30.00 30.00 Ultrasil 7000 HDS 80.00 80.00 80.00 80.00 80.00 80.00 Si69 X50S 12.80 12.80 12.80 12.80 12.80 12.80 Graphene 0.00 0.50 1.00 2.00 4.00 10.00 Escorez 1102 4.00 4.00 4.00 4.00 4.00 4.00 TDAE (aromatic oil) 6.00 6.00 6.00 6.00 6.00 6.00 6PPD 1.50 1.50 1.50 1.50 1.50 1.50 TMQ 1.00 1.00 1.00 1.00 1.00 1.00 Paraffinic wax 0.50 0.50 0.50 0.50 0.50 0.50 Microcrystalline 0.50 0.50 0.50 0.50 0.50 0.50 wax Zinc Oxide 3.00 3.00 3.00 3.00 3.00 3.00 Stearic acid 2.00 2.00 2.00 2.00 2.00 2.00 CBS 1.50 1.50 1.50 1.50 1.50 1.50 DPG 2.00 2.00 2.00 2.00 2.00 2.00 Sulfur 1.50 1.50 1.50 1.50 1.50 1.50 PVI 0.20 0.20 0.20 0.20 0.20 0.20 Total PHR 242.50 243.00 243.50 244.50 246.50 252.50

TABLE-US-00008 TABLE 8 Mooney Viscosity ML 1 + 4 100° C. 100° C. 100° C. 100° C. 100° C. 100° C. Mooney Peak 121.6 118.2 123.4 121.3 121.5 134.2 ML 1 + 4 100° C. 80.2 79.5 81.1 80.8 79.5 86.9 Aged Mooney 7 days Mooney Peak 170 163 167 167 162 178 ML 1 + 4 100° C. 93.8 92.8 94.1 93.5 91.8 99.5 MDR Rheometer Temperature 160° C. 160° C. 160° C. 160° C. 160° C. 160° C. Arc 0.5 0.5 0.5 0.5 0.5 0.5 MH 8.01 8.13 8.07 8.29 8.20 8.30 ML 1.74 1.70 1.83 1.84 1.78 1.78 Delta Torque 6.27 6.43 6.24 6.45 6.42 5.98 ts1 1.82 1.77 1.83 1.82 1.82 1.79 t10 1.65 1.60 1.65 1.65 1.62 0.81 t50 3.75 3.69 3.71 3.70 3.75 3.62 t90 23.10 25.38 21.49 21.11 24.25 23.40 CRI 4.66 4.21 5.04 5.14 4.42 4.43

TABLE-US-00009 TABLE 9 Compound 1 2 3 4 5 6 Lab Number ERTB10- ERTB10- ERTB10- ERTB10- ERTB10- ERTB10- Grade 78-21 78-22 78-23 78-24 78-25 78-26 SSBR 2.5% B.S., 96.00 96.00 96.00 96.00 96.00 96.00 OE 27% Polybutadiene Ni or Nd 30.00 30.00 30.00 30.00 30.00 30.00 Ultrasil 7000 HDS 80.00 80.00 80.00 80.00 80.00 80.00 Si69 X50S 12.80 12.80 12.80 12.80 12.80 12.80 Graphene 0.00 0.50 1.00 2.00 4.00 10.00 Tensile Strength MPa 16.64 15.99 16.32 16.88 16.87 16.66 Elongation % 354 353 358 366 380 309  50% Modulus MPa 1.18 1.18 1.16 1.25 1.23 1.70 100% Modulus MPa 2.25 2.30 2.28 2.44 2.38 3.67 200% Modulus MPa 6.17 6.26 6.29 6.50 6.17 8.80 300% Modulus MPa 12.27 12.34 12.51 12.56 11.76 15.61 Modulus Ratio MPa 5.46 5.37 5.49 5.15 4.94 4.25 Shore A 59 60 60 60 60 64 Tear Strength Peak Tear KNm 85.11 92.07 86.45 91.27 94.30 85.82 Tear Die B KNm 40.06 43.65 40.52 43.80 43.60 40.50 Strebler Adhesion lb .Math. in 26.30 40.50 46.70 46.20 31.30 17.30 Din Abrasion Weight Loss 136.3 122.8 134.4 144.5 146.5 201.5 Weight Loss 119.7 129.1 136.7 143.6 158.3 209.5 Weight Loss 124.3 131.6 147.3 154.9 144.1 187.6 Mean 127 128 139 148 150 200 Volume loss 103 93 102 110 111 150 (mm3) Volume loss 91 98 104 109 120 156 (mm3) Volume loss 94 99 112 118 109 140 (mm3) Median 94 98 104 110 111 150 Mean 96 97 106 112 113 149 Electrical ohm*cm Resistivity Sample 1 2.39E+15 2.75E+15 2.89E+15 2.72E+15 2.25E+15 2.62E+15 ASTM D991 2 2.55E+15 2.08E+15 1.81E+15 2.54E+15 1.90E+15 3.02E+15 3 2.14E+15 2.27E+15 1.95E+15 2.59E+15 1.94E+15 2.80E+15 Mean average 2.36E+15 2.37E+15 2.22E+15 2.62E+15 2.03E+15 2.81E+15

TABLE-US-00010 TABLE 10 Compound 1 2 3 4 5 6 Lab Number ERTB10- ERTB10- ERTB10- ERTB10- ERTB10- ERTB10- Grade 78-21 78-22 78-23 78-24 78-25 78-26 SSBR 25% B.S., 96.00 96.00 96.00 96.00 96.00 96.00 OE 27% Polybutadiene Ni or Nd 30.00 30.00 30.00 30.00 30.00 30.00 Ultrasil 7000 HDS 80.00 80.00 80.00 80.00 80.00 80.00 Si69 X50S 12.80 12.80 12.80 12.80 12.80 12.80 Graphene 0.00 0.50 1.00 2.00 4.00 10.00 DMTA Strain Sweep 30 C., 0.2% strain, Sample 1 10 Hz G′ MPa 1.250 1.330 1.320 1.350 1.180 1.420 G″ MPa 0.214 0.229 0.132 0.223 0.219 0.249 tan delta 0.172 0.172 0.163 0.164 0.186 0.175 d* 9.732 9.756 9.279 9.332 10.538 9.954 J′ ×10−7 7.780 7.290 7.370 7.190 8.220 6.840 J″ ×10−7 1.330 1.250 1.200 1.180 1.520 1.200 Sample 2 G′ MPa 1.250 1.330 1.320 1.350 1.180 1.410 G″ MPa 0.212 0.227 0.214 0.221 0.218 0.247 tan delta 0.171 0.171 0.163 0.164 0.185 0.175 d* 9.669 9.700 9.244 9.289 8.360 9.910 J′ ×10−7 7.800 7.130 7.390 7.210 8.220 6.870 J″ ×10−7 1.330 1.250 1.200 1.180 1.520 1.200 Mean G′ MPa 1.250 1.330 1.320 1.350 1.180 1.415 G″ MPa 0.213 0.228 0.173 0.222 0.219 0.248 tan delta 0.171 0.171 0.163 0.164 0.186 0.175 D* 9.701 9.728 9.262 9.310 9.449 9.932 J′ ×10−7 7.790 7.210 7.380 7.200 8.220 6.855 J″ ×10−7 1.330 1.250 1.200 1.180 1.520 1.200 DMTA Temperature Sweep (tension at 0.2% strain) Complex Modulus (E*) 47.600 54.900 44.000 41.600 42.700 57.900 MPa, −20° C. tan delta −10° C. 0.407 0.433 0.401 0.416 0.424 0.441 tan delta 0.244 0.237 0.253 0.234 0.232 0.243 Tg (Max E′) ° C. −46.400 −45.600 −46.200 −46.400 −47.100 −45.600 Tg (Max tan delta) ° C. −25.300 −24.500 −25.000 −25.200 −24.700 −24.600

[0056] Clause 1-A rubber composition including styrene butadiene rubber, silicon dioxide, bis[3-(triethoxysilyl)propyl]polysulfide, graphene, wherein the graphene has a thickness of less than about 3.2 nm, a particle size of between about 50 nm and about 10 μm, and contains greater than about 95% carbon, aliphatic hydrocarbon resin, treated distillate aromatic extract. N-(1,3-dimethylbutyl)-N′-phenyl-1,4-benzenediamine, 2,2,4-trimethyl-1.2-dihydroquinoline, paraffinic wax, microcrystalline wax, zinc oxide. stearic acid, N-cyclohexyl-2-benzothiazole sulfonamide, 1.3 diphenylguanidine, sulfur, and pre vulcanization inhibitor.

[0057] Clause 2-A rubber composition including styrene butadiene. silicon dioxide.

organosilane. and graphene, wherein the graphene has a thickness of less than about 3.2 nm. a particle size of between about 50 nm and about 10 μm. and contains greater than about 95% carbon.

[0058] Clause 3—The rubber composition of clauses 1 or 2. wherein the graphene is a graphene plate, wherein the graphene plate is between about 0.5 PHR and about 10.0 PHR.

[0059] Clause 4—The rubber composition of clauses 1-3. wherein the graphene plate has a surface area from about 100 m.sup.2/gram to about 250 m.sup.2/gram.

[0060] Clause 5—The rubber composition of clauses 1-4, wherein the graphene plate has an oxygen content of less than about 1%.

[0061] Clause 6—The rubber composition of clauses 1-5. wherein the thickness is less than about 1 nm and the aspect ratio is about 1000.

[0062] Clause 7—The rubber composition of clauses 1-6. wherein the graphene plate is between about 0.5 PHR and about 8.0 PHR.

[0063] Clause 8—The rubber composition of clauses 2-7, wherein the rubber composition further includes aliphatic hydrocarbon resin, treated distillate aromatic extract, an antiozonant, and an antioxidant.

[0064] Clause 9—The rubber composition of clauses 2-8, wherein the rubber composition further includes paraffinic wax, microcrystalline wax, zinc oxide, stearic acid. an accelerator, a secondary accelerator, sulfur, and a pre vulcanization inhibitor.

[0065] Clause 10—The rubber composition of clauses 8-10. wherein the antiozonant is N-(1.3-dimethylbutyl)-N′-phenyl-1,4-benzenediamine and the antioxidant is 2,2,4-trimethyl-1.2-dihydroquinoline.

[0066] Clause 11—The rubber composition of clauses 9 or 10, wherein the accelerator is N-cyclohexyl-2-benzothiazole sulfonamide and the secondary accelerator is 1,3-diphenylguanidine.

[0067] Clause 12—The rubber composition of clauses 3-11, wherein the graphene plate is between about 1.0 PHR and about 2.0 PHR, wherein the composition has no clay fillers.

[0068] Clause 13—The rubber composition of clauses 3-11, wherein the graphene plate is between about 3.0 PHR and about 5.0 PHR.

[0069] Clause 14—The rubber composition of clauses 1-13, wherein the graphene is graphene plates. wherein substantially all of the graphene plates are parallel and in contact with each other.

[0070] Clause 15—The rubber composition of clause 14. wherein the graphene plate is between about 15.0 PHR and about 20.0 PHR.

[0071] Clause 16—The rubber composition of clauses 1-15. wherein the rubber composition is a silica tread composition.

[0072] Clause 17—The rubber composition of clauses 2-7, wherein the rubber composition is chosen from the group consisting of a silica tread composition. seals, gaskets. medical gloves, beverage bottles, and chemical and solvent resistant gloves.

[0073] Non-limiting aspects have been described, hereinabove. It will be apparent to those skilled in the art that the above methods and apparatuses may incorporate changes and modifications without departing from the general scope of the present subject matter. It is intended to include all such modifications and alterations in so far as they come within the scope of the appended claims or the equivalents thereof.

[0074] Having thus described the present teachings. it is now claimed: