GRAPHENE AS ADDITIVE IN TRUCK TIRE TREAD APPLICATIONS

Abstract

The introduction of graphene as an additive in truck tire treads is disclosed. The product shows increased electrical resistance in tire treads, with no tradeoffs in other characteristics.

Claims

1. A truck tire tread comprising: natural rubber; a peptizer; carbon black; 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-tert-butyl-benzothiazole sulfonamide; sulfur; and pre vulcanization inhibitor.

2. A truck tire tread comprising: natural rubber; carbon black; 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 truck tire tread of claim 2, wherein the tread contains no silica.

4. The truck tire tread 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.

5. The truck tire tread of claim 4, wherein the graphene plate has a surface area from about 100 m.sup.2/gram to about 250 m.sup.2/gram.

6. The truck tire tread of claim 5, wherein the graphene plate has an oxygen content of less than about 1%.

7. The truck tire tread of claim 2, wherein the thickness is less than about 1 nm and the aspect ratio is about 1000.

8. The truck tire tread of claim 4, wherein the graphene plate is between about 0.5 PHR and about 8.0 PHR.

9. The truck tire tread of claim 2, wherein the truck tire tread further comprises carbon black.

10. The truck tire tread of claim 9, wherein the truck tire tread further comprises: a peptizer; aliphatic hydrocarbon resin; treated distillate aromatic extract; an antiozonant; and, an antioxidant.

11. The truck tire tread of claim 10, wherein the truck tire tread further comprises: paraffinic wax; microcrystalline wax; zinc oxide; stearic acid; an accelerator; sulfur; and a pre vulcanization inhibitor.

12. The truck tire tread of claim 11, wherein the antiozonant is N-(1,3-dimethylbutyl)-N′-phenyl-1,4-benzenediamine and the antioxidant is 2,2,4-trimethyl-1,2-dihydroquinoline.

13. The truck tire tread of claim 12, wherein the accelerator is N-tert-butyl-benzothiazole sulfonamide and the peptizer is 2,2′-dibenzamido-diphenyldisulphide.

14. The truck tire tread of claim 8, wherein the graphene plate is between about 1.0 PHR and about 2.0 PHR, wherein the composition has no clay fillers.

15. The truck tire tread of claim 8, wherein the graphene plate is between about 3.0 PHR and about 5.0 PHR.

Description

III. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The present teachings are described hereinafter with reference to the accompanying drawings.

[0025] FIG. 1 depicts a graph showing rapid reduction in permeability;

[0026] FIG. 2 depicts the structures of graphene, graphene oxide, and reduced graphene oxide;

[0027] FIG. 3 depicts a tire;

[0028] FIG. 4 is a graphical representation of the graphene plates acting as a barrier to gas flow;

[0029] FIG. 5 is a chart showing the vulcanization rate;

[0030] FIG. 6 is a chart showing the Mooney viscosity;

[0031] FIG. 7 is a chart showing the vulcanization kinetics;

[0032] FIG. 8 is a chart showing the 300% modulus;

[0033] FIG. 9 is a chart showing modulus at 50% strain;

[0034] FIG. 10 is a chart showing the strain crystallization;

[0035] FIG. 11 is a chart showing the tear strength;

[0036] FIG. 12 is a chart showing the peel adhesion in N/mm;

[0037] FIG. 13 is a chart showing the peel adhesion in lbs.in.;

[0038] FIG. 14 is a chart showing the trouser tear strength;

[0039] FIG. 15 is a chart showing the Demattia flex fatigue;

[0040] FIG. 16 is a chart showing the Din abrasion;

[0041] FIG. 17 is a topographical scan;

[0042] FIG. 18 is a chart showing the tan delta at 0° C.;

[0043] FIG. 19 is a chart showing the storage modulus G′;

[0044] FIG. 20 is a chart showing the electrical resistivity; and

[0045] FIG. 21 is a chart showing the electrical resistivity of the tread.

IV. DETAILED DESCRIPTION

[0046] With reference to FIGS. 1-4, in one aspect of the present teaching, a tire is shown with a tread 10, a sidewall 12, belt plies 14, a tire innerliner 16, bead filler 18, beads 20, and body plies 22, wherein the tire innerliner 16 is a calendered halobutyl rubber sheet compounded with additives that result in low air permeability. The innerliner 16 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.

[0047] 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

[0048] The particle size range of graphene used in the present teachings can range from about 50 nm to about 10 μm. 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 600 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] Measurement of Properties of Rubber Compositions

[0053] 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

[0054] 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.

[0055] 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

[0056] 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.

[0057] 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 ADD Sulfur, Accelerator pocket, & 15″ 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 ML1 + 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*mm/(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

[0058] With reference to FIGS. 4-21, a truck tire tread 10, a model natural rubber tread compound is utilized. As shown in Table 5 below, graphene is added at 0.5, 1.0, 2.0, 4.0, and 10.0 PHR. The compounds are mixed via laboratory two-stage mix process using BR scale Banbury.

TABLE-US-00005 TABLE 5 Compound Grade 1 2 3 4 5 6 Natural Rubber TSR20, RSS2 100.00 100.00 100.00 100.00 100.00 100.00 Peptizer (Renecit 11) 0.10 0.10 0.10 0.10 0.10 0.10 Carbon Black (N121) N121, Alter: 50.00 50.00 50.00 50.00 50.00 50.00 N234 Graphene 0.00 0.50 1.00 2.00 4.00 10.00 Escorez 1102 2.00 2.00 2.00 2.00 2.00 2.00 TDAE (aromatic oil) 3.00 3.00 3.00 3.00 3.00 3.00 6PPD 2.50 2.50 2.50 2.50 2.50 2.50 TMQ 1.50 1.50 1.50 1.50 1.50 1.50 Paraffinic wax 1.00 1.00 1.00 1.00 1.00 1.00 Microcrystallinc 1.00 1.00 1.00 1.00 1.00 1.00 wax Zinc Oxide 4.00 4.00 4.00 4.00 4.00 4.00 Stearic acid 2.00 2.00 2.00 2.00 2.00 2.00 TBBS 1.00 1.00 1.00 1.00 1.00 1.00 Sulfur 1.00 1.00 1.00 1.00 1.00 1.00 PVI 0.20 0.20 0.20 0.20 0.20 0.20

[0059] The addition of graphene to the truck tire tread does not shift the viscosity, as well as no change in compound processing or vulcanization kinetics. As can be seen in FIG. 7, as the level of graphene increases toward 10.0 PHR, rheometer torque increases slightly.

[0060] With reference now to FIGS. 8-10, the addition of graphene has no impact on compound viscosity (processability) and vulcanization characteristics. Tensile strength ranges from 25.0 MPa to 27.0 MPa and 300% modulus is in the range of 11.3 MPa to 13.0 MPa. The Shore A hardness is between 59 and 60, and the low strain modulus from tensile strength from one inch strips increased with increasing graphene amounts. This suggests lower Payne effect, which shows better abrasion resistance.

[0061] With reference now to FIGS. 11 and 12, graphene is added in increments, starting at 0.5 PHR up to 10.0 PHR. Significant improvement in tear strength is shown with levels of graphene as low as 0.5 PHR. Graphene has a very large ratio plate-like structures. When the plate-like structures are oriented, the graphene arrests tear propagation, increases mixing shear, which improves dispersion and homogeneity, and acts as a nucleating agent for strain crystallization. The high tear strength and Strebler indicates improved truck tire tread chip/chuck/cut resistance.

[0062] With reference now to FIGS. 13-15, a model wire coat compound was prepared containing natural rubber (100 PHR), carbon black N326 (60 PHR), naphthenic oil (2.5 PHR), TMQ (2,2,4-trimethyl-1,2-dihydroquinoline) as anti-oxidant, N-(1,3-dimethylbutyl)-N′-phenyl-1,4-benzenediamine (6PPD) as an antiozonant, and a vulcanization system. Addition of up to 5.0 PHR of graphene had no effect on viscosity, vulcanization kinetics, or basic mechanical properties. Along with the previously mentioned improvements, the use of graphene can improve fatigue life as well.

[0063] With reference now to FIGS. 16 and 17, truck tire tread compound abrasion is a complex phenomenon, which encompasses tensile tearing mechanism (fast wear) and thermo-oxidative degradation (slow wear). Additions of low amounts of graphene improved Din abrasion performance (tearing mechanism). FIG. 17 shows a control vs. a compound with 3.0 to 5.0 PHR graphene.

[0064] With reference now to FIGS. 18 and 19, the truck tire tread compound dynamic properties are equivalent, with no tradeoffs or other losses. The compound with graphene showed a slight increase in tan delta at 0° C., suggesting better traction.

[0065] With reference now to FIGS. 20 and 21, electrostatic build-up on fuel delivery trucks is a concern in the oil and petroleum transportation industries. The use of graphene in truck tire treads can mitigate potential concerns and ensure safe tire operations. Improved conductivity was found in all compound classes. The combination of carbon black and graphene creates the advantageous electrical conductivity of the graphene plates.

TABLE-US-00006 TABLE 6 Compound 1 2 3 4 5 6 ERTNB10- ERTNB10- ERTNB10- ERTNB10- ERTNB10- ERTNB10- Grade 76-1 76-2 76-3 76-4 76-5 76-6 Natural Rubber TSR20, RSS2 100.00 100.00 100.00 100.00 100.00 100.00 Peptizer (Renecit 11) 0.10 0.10 0.10 0.10 0.10 0.10 Carbon Black (N121) N121, Alter: 50.00 50.00 50.00 50.00 50.00 50.00 N234 Graphene 0.00 0.50 1.00 2.00 4.00 10.00 Escorez 1102 2.00 2.00 2.00 2.00 2.00 2.00 TDAE (aromatic oil) 3.00 3.00 3.00 3.00 3.00 3.00 6PPD 2.50 2.50 2.50 2.50 2.50 2.50 TMQ 1.50 1.50 1.50 1.50 1.50 1.50 Paraffinic wax 1.00 1.00 1.00 1.00 1.00 1.00 Microcrystalline 1.00 1.00 1.00 1.00 1.00 1.00 wax Zinc Oxide 4.00 4.00 4.00 4.00 4.00 4.00 Stearic acid 2.00 2.00 2.00 2.00 2.00 2.00 TBBS 1.00 1.00 1.00 1.00 1.00 1.00 Sulfur 1.00 1.00 1.00 1.00 1.00 1.00 PVI 0.20 0.20 0.20 0.20 0.20 0.20 Total PHR 169.30 169.80 170.30 171.30 173.30 179.30

TABLE-US-00007 TABLE 7 Grade 1 2 3 4 5 6 Mooney Viscosity ML1 + 4 Mooney Peak 95.14 87.93 94.32 96.08 86.60 89.26 ML1 + 4 100° C. 61.63 61.66 62.20 62.20 61.06 61.69 Aged Mooney Viscosity 7 days Mooney Peak 111.60 95.40 99.90 98.80 100.40 94.80 ML1 + 4 100° C. 61.70 61.50 62.00 62.10 61.30 62.00 MDR Rheometer Temperature 160° C. 160° C. 160° C. 160° C. 160° C. 160° C. Arc degrees 0.5 0.5 0.5 0.5 0.5 0.5 MH 9.67 9.56 9.89 9.77 9.67 10.05 ML 1.85 1.75 1.9 1.81 1.78 1.86 Delta Torque 7.82 7.81 7.99 7.96 7.89 8.19 ts1 3.04 3.03 3.04 3.04 3.08 2.97 Torque at t10 2.63 2.53 2.70 2.61 2.57 2.68 Torque at t50 5.76 5.66 5.90 5.79 5.73 5.96 Torque at t90 8.89 8.78 9.09 8.97 8.88 9.23 t10 2.55 2.45 2.65 2.52 2.45 2.66 t50 4.47 4.53 4.51 4.50 4.48 4.51 t90 6.73 6.76 6.81 6.67 6.88 6.91 CRI 23.92 23.20 24.04 24.10 22.57 23.53

TABLE-US-00008 TABLE 8 Compound 1 2 3 4 5 6 ERTNB10- ERTNB10- ERTNB10- ERTNB10- ERTNB10- ERTNB10- Grade 76-1 76-2 76-3 76-4 76-5 76-6 Natural Rubber TSR20, RSS2 100.00 100.00 100.00 100.00 100.00 100.00 Peptizer (Renecit 11) 0.10 0.10 0.10 0.10 0.10 0.10 Carbon Black (N121) N121, Alter: 50.00 50.00 50.00 50.00 50.00 50.00 N234 Graphene 0.00 0.50 1.00 2.00 4.00 10.00 Tensile Strength: ASTM D412 Die C Tensile Strength MPa 26.00 27.00 26.00 26.60 26.70 25.00 Elongation % 568 565 577 593 583 519  50% modulus MPa 1.18 1.15 1.20 1.23 1.35 1.60 100% modulus MPa 2.10 2.00 2.10 2.20 2.50 3.10 200% modulus MPa 5.90 5.90 5.90 5.80 6.50 7.40 300% modulus MPa 11.30 11.40 11.50 11.00 11.90 13.00 1″ strip Tensile Strength Tensile Strength MPa 10.94 12.44 11.35 12.29 13.59 15.40 Elongation % 296 329 312 322 346 343  50% modulus MPa 1.09 1.12 1.15 1.19 1.23 1.60 100% modulus MPa 1.92 2.01 2.02 2.18 2.25 3.20 200% modulus MPa 5.70 5.76 5.58 5.98 5.90 7.60 300% modulus MPa 10.95 10.85 11.19 11.12 13.00 Hardness Shore A 59 58 60 59 60 63 Tear Strength KN/m 112.85 153.4 129.67 109.91 94.07 84.37 Strebler (hot) lbf/in 516.4 439.6 314.4 142.0 80.3 37.7 DMTA Strain Sweep Sample 1 60 C., 0.2% strain, 10 Hz G′ MPa 0.936 0.904 0.986 0.960 0.921 1.020 G″ MPa 0.155 0.149 0.164 0.172 0.188 0.184 tan delta 0.165 0.165 0.167 0.179 0.204 0.180 d* 9.371 9.389 9.458 10.300 11.522 10.212 J′ ×10−7 10.400 10.800 9.860 10.100 10.400 9.480 J″ ×10−7 1.720 1.780 1.640 1.810 2.120 1.710 Sample 2 G′ MPa 0.937 0.917 0.989 0.959 0.930 1.030 G″ MPa 0.152 0.148 0.163 0.170 0.184 0.182 tan delta 0.163 0.163 0.164 0.177 0.198 0.178 d* 9.235 9.270 9.336 10.037 11.212 10.069 J′ ×10−7 10.400 10.800 9.840 10.100 10.300 9.460 J″ ×10−7 1.690 1.760 1.620 1.790 2.050 1.680 Mean G′ MPa 0.937 0.911 0.988 0.959 0.925 1.025 G″ MPa 0.153 0.149 0.163 0.171 0.186 0.183 tan delta 0.164 0.164 0.165 0.178 0.201 0.179 D* 9.303 9.329 9.397 10.168 11.367 10.140 J′ ×10−7 10.400 10.800 9.850 10.100 10.350 9.470 J″ ×10−7 1.705 1.770 1.630 1.800 2.085 1.695

TABLE-US-00009 TABLE 9 Compound 1 2 3 4 5 6 ERTNB10- ERTNB10- ERTNB10- ERTNB10- ERTNB10- ERTNB10- Grade 76-1 76-2 76-3 76-4 76-5 76-6 Natural Rubber TSR20, RSS2 100.00 100.00 100.00 100.00 100.00 100.00 Peptizer (Renecit 11) 0.10 0.10 0.10 0.10 0.10 0.10 Carbon Black (N121) N121, Alter: 50.00 50.00 50.00 50.00 50.00 50.00 N234 Graphene 0.00 0.50 1.00 2.00 4.00 10.00 Payne Effect MPa 1.820 1.810 1.960 2.070 1.970 2.530 Mullens Effect 1.000 15.000 12.000 21.000 9.000 27.000 Graphene 0.00 0.50 1.00 2.00 4.00 10.00 Electrical resistivity ohm .Math. cm × 10.sup..3 1.680 2.490 0.596 0.663 0.493 0.382 ASTM D991 ×10.sup.4 DMTA Temperature Sweep. Shear, 5% strain G* Pa −20° C. 3.8400 3.7500 4.3000 3.8000 4.0100 4.5900 tan delta −10° C. 0.3900 0.3919 0.3973 0.3985 0.4034 0.4060 tan delta    0° C. 0.3078 0.3087 0.3165 0.3132 0.3198 0.3260 tan delta   30° C. 0.2218 0.2205 0.2280 0.2369 0.2364 0.2415 tan delta   60° C. 0.1898 0.1883 0.1932 0.2007 0.2035 0.2110 G′ (MPa)   30° C. 1.5900 1.5400 1.7500 1.5800 1.6000 1.8600 J′ (1/Pa) × 10.sup.−7   30° C. 1.3300 1.3700 1.2400 1.4200 1.4000 1.2300 G′ (MPa)   60° C. 1.2700 1.2300 1.3700 1.3400 1.2800 1.4500 DMTA Temperature Sweep (tension at 0.2% strain) Complex Modulus −20° C. 40.40 40.00 42.30 39.30 38.30 56.20 (E*). MPa, tan delta −10 C. ° 0.173 0.175 0.169 0.169 0.205 0.189 tan delta    0° C. 0.159 0.159 0.157 0.154 0.176 0.175 Tg (Max E′) ° C. −55.60 −55.60 −55.40 −56.00 −55.50 −54.30 Tg (Max tan delta) ° C. −48.00 −48.50 −48.90 −48.40 −49.00 −49.10 Mullins effect Strain softening beyond yield point Payne Effect filler-filler interaction: Lower Payne effect - better dispersion Loss Compliance J″. Decrease: the lower the better - internal component Rolling Resistance Complex Modulus G*. Increase - improve durability

[0066] A rubber tread compound formulation will consist of many types of materials and chemicals. Typically the tread compound formulation used on a heavy duty truck tire mounted on a commercial truck and trailer will consist of natural rubber. The amount of natural rubber will be expressed in parts per hundred rubber (PHR) and which is familiar to those skilled in the art of rubber compounding. A tread compound containing 100 PHR of natural rubber is typical. In some instances a synthetic rubber may be added from 0 PHR to 50 PHR and the natural rubber correspondingly adjusted between 50 PHR and 100 PHR. Synthetic rubbers may be selected from polybutadiene of which there are many types used in tire compounding, halogenated butyl rubbers, emulsion polymerized styrene butadiene rubber (SBR), or solution polymerized SBR. Blends of such synthetic rubbers may also be used as part of the total rubber hydrocarbon content. Carbon black may be of different grades as described in the text “Rubber Compounding Chemistry and Applications, 2.sup.nd edition, by CRC Press (2015)”. Though grades including N121, N110, N234, or N120 are often used, other examples of grades could be selected from the SAF, ISAF, or HAF. Groups might also be selected depending on the manufacturer, and is noted they will have no material impact on the present teaching. The amount of carbon black can be between about 40 PHR and about 55 PHR and between about 45 to about 50 PHR, and for N121 type of carbon black, between about 47 and about 50 PHR. In addition, a peptizer designed to improve compound mixing efficiency may be added at between about 0.0 and about 0.5 and about 0.25 PHR. An antioxidant is added at between about 0.0 and about 2.0 PHR and can be about 1.5 PHR. An antiozonant is added at between about 0.0 and about 5.0 PHR and can be about 2.5 PHR. Waxes such as paraffinic was and microcrystalline wax are added at between about 0.0 and about 3.0 PHR in total and about 1.0 PHR each. Process oil to facilitate compound mixing and extrusion is added at between about 0.0 and about 12.0 PHR and can be about 5.0 PHR. An example of a process oil is treated distilled aromatic extract (TDAE). Other process oils may also be used such as conventional aromatic oil, residual extract aromatic (RAE), naphthenic oil, or MES. Stearic acid is added at between about 0.0 and about 2.0 PHR and can be about 1.5 PHR. Zinc oxide is added at between about 0.0 and about 6.0 PHR and can be between about 4.0 PHR to about 5.0 PHR.

[0067] The vulcanization system contains sulfur, accelerators, and may also use a retarder to optimize compound induction time. Sulfur is used between about 0.5 and about 2.0 PHR and between about 0.8 and about 1.0 PHR. The accelerator may be sulfonamides including cyclohexyl benzothiazole disulfide (CBS) and tertiary butyl benzothiazole disulfide (TBBS). The amount is added at between about 0.25 and about 2.0 PHR and can be about 1.0 PHR. In some instances, a secondary accelerator can be added such as a thiuram such as, though not limited to, tetramethyl thiuram monosulfide (TMTM), tetramethyl thiuram disulfide (TMTD), tetra t-butyl thiuram disulfide (TBTD or tetrabenzyl thiuram disulfide (TBzTD). The amount is added at between about 0.0 and about 2.0 PHR and between about 0.25 PHR to about 0.5 PHR. Alternatively a guanidine secondary accelerator such as DOPG or DPG could be used at between about 0.0 and about 2.5 PHR and about 0.25 PHR can be used. A retarder or pre-vulcanization inhibitor (PVI) is also added at between about 0.0 and about 2.0 PHR and between about 0.15 to about 0.25 PHR.

[0068] Clause 1—A truck tire tread including natural rubber, a peptizer, carbon black, 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-tert-butyl-benzothiazole sulfonamide, sulfur, and pre vulcanization inhibitor.

[0069] Clause 2—A truck tire tread including natural rubber, carbon black, 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.

[0070] Clause 3—The truck tire tread of clause 2, wherein the tread contains no silica.

[0071] Clause 4—The truck tire tread of clauses 2 or 3, wherein the graphene is a graphene plate, wherein the graphene plate is between about 0.5 PHR and about 10.0 PHR.

[0072] Clause 5—The truck tire tread of clauses 2-4, wherein the graphene plate has a surface area from about 100 m.sup.2/gram to about 250 m.sup.2/gram.

[0073] Clause 6—The truck tire tread of clauses 2-5, wherein the graphene plate has an oxygen content of less than about 1%.

[0074] Clause 7—The truck tire tread of clauses 2-6, wherein the thickness is less than about 1 nm and the aspect ratio is about 1000.

[0075] Clause 8—The truck tire tread of clauses 2-7, wherein the graphene plate is between about 0.5 PHR and about 8.0 PHR.

[0076] Clause 9—The truck tire tread of clauses 2-8, wherein the truck tire tread further includes carbon black.

[0077] Clause 10—The truck tire tread of clauses 2-9, wherein the truck tire tread further includes a peptizer, aliphatic hydrocarbon resin, treated distillate aromatic extract, an antiozonant, and an antioxidant.

[0078] Clause 11—The truck tire tread of clauses 2-10, wherein the truck tire tread further includes paraffinic wax, microcrystalline wax, zinc oxide, stearic acid, an accelerator, sulfur, and a pre vulcanization inhibitor.

[0079] Clause 12—The truck tire tread of clauses 10 or 11, wherein the antiozonant is N-(1,3-dimethylbutyl)-N′-phenyl-1,4-benzenediamine and the antioxidant is 2,2,4-trimethyl-1,2-dihydroquinoline.

[0080] Clause 13—The truck tire tread of clauses 11 or 12, wherein the accelerator is N-tert-butyl-benzothiazole sulfonamide and the peptizer is 2,2′-dibenzamido-diphenyldisulphide.

[0081] Clause 14—The truck tire tread of clauses 2-13, wherein the graphene plate is between about 1.0 PHR and about 2.0 PHR, wherein the composition has no clay fillers.

[0082] Clause 15—The truck tire tread of clauses 2-14, wherein the graphene plate is between about 3.0 PHR and about 5.0 PHR.

[0083] 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.

[0084] Having thus described the present teachings, it is now claimed: