GRAPHENE AS ADDITIVE IN SIDEWALL APPLICATIONS

I. Background

[0001] This application claims priority to U.S. Serial No. 63/222,101, filed July 15, 2021, U.S. Serial No. 63/222,112, filed July 15, 2021, U.S. Serial No. 63/222,103, filed July 15, 2021, and U.S. Serial No. 63/228,389, filed August 2, 2021, the contents of which are hereby incorporated by reference. The present teaching is directed to the use of graphene as an additive. More specifically, the present technology is directed to the use of graphene as an additive in tire sidewall applications.

[0002] Graphene is an allotrope of carbon consisting of a single layer of atoms arranged in a two-dimensional honeycomb lattice. The hexagonal lattice structure of isolated, single-layer graphene can be directly seen with transmission electron microscopy (TEM) of sheets of graphene suspended between bars of a metallic grid. Some of these images showed a "rippling" of the flat sheet, with amplitude of about one nanometer. The hexagonal structure is also seen in scanning tunneling microscope (STM) images of graphene supported on silicon dioxide substrates. Ab initio calculations show that a graphene sheet is thermodynamically unstable if its size is less than about 20 nm and becomes the most stable fullerene (as within graphite) only for molecules larger than 24,000 atoms. Each atom in a graphene sheet is connected to its three nearest neighbors by a s-bond, and contributes one electron to a conduction band that extends over the whole sheet. This is the same type of bonding seen in carbon nanotubes and polycyclic aromatic hydrocarbons, and (partially) in fullerenes and glassy carbon. These conduction bands make graphene a semimetal with unusual electronic properties that are best described by theories for massless relativistic particles. Charge carriers in graphene show linear, rather than quadratic, dependence of energy on momentum, and field-effect transistors with graphene can be made that show bipolar conduction. Charge transport is ballistic over long distances; the material exhibits large quantum oscillations and large and nonlinear diamagnetism. Graphene conducts heat and electricity very efficiently along its plane. The material strongly absorbs light of all visible wavelengths, which accounts for the black color of graphite; yet a single graphene sheet is nearly transparent because of its extreme thinness. The material is also about 100 times stronger than would be the strongest steel of the same thickness.

[0003] Single layers of carbon atoms are grown epitaxially on top of other materials. This "epitaxial graphene" consists of a single- atom- thick hexagonal lattice of sp ² -bonded carbon atoms, as in free-standing graphene. However, there is significant charge transfer between the two materials, and, in some cases, hybridization between the d-orbitals of the substrate atoms and p orbitals of graphene; which significantly alter the electronic structure compared to that of free standing graphene.

[0004] Three of the four outer-shell electrons of each atom in a graphene sheet occupy three sp ² hybrid orbitals - a combination of orbitals s, p _x and p _{y —} that are shared with the three nearest atoms, forming s-bonds. The length of these bonds is about 0.142 nanometers. The remaining outer-shell electron occupies a p _z orbital that is oriented perpendicularly to the plane. These orbitals hybridize together to form two half-filled bands of free-moving electrons, p and p*, which are responsible for most of graphene's notable electronic properties. Graphene sheets stack to form graphite with an interplanar spacing of 0.335 nm (3.35 A). Graphene sheets in solid form usually show evidence in diffraction for graphite's layering.

[0005] Graphene is a zero-gap semiconductor, because its conduction and valence bands meet at the Dirac points. The Dirac points are six locations in momentum space, on the edge of the Brillouin zone, divided into two non-equivalent sets of three points. The two sets are labeled K and K'. The sets give graphene a valley degeneracy of gv = 2. By contrast, for traditional semiconductors the primary point of interest is generally G, where momentum is zero. Four electronic properties separate it from other condensed matter systems. However, if the in-plane direction is no longer infinite, but confined, its electronic structure would change. They are referred to as graphene nanoribbons. If it is "zig-zag," the bandgap would still be zero. If it is "armchair," the bandgap would be non-zero. Graphene's hexagonal lattice can be regarded as two interleaving triangular lattices. This perspective was successfully used to calculate the band structure for a single graphite layer using a tight-binding approximation. Electrons propagating through graphene's honeycomb lattice effectively lose their mass, producing quasi-particles that are described by a 2D analogue of the Dirac equation rather than the Schrodinger equation for spin-½ particles.

[0006] Graphene displays remarkable electron mobility at room temperature, with reported values in excess of 15000 cm ² -V ¹ -s ¹ . Hole and electron mobilities are nearly the same. The mobility is independent of temperature between 10 K and 100 K, and shows little change even at room temperature (300 K), which implies that the dominant scattering mechanism is defect scattering. Scattering by graphene's acoustic phonons intrinsically limits room temperature mobility in freestanding graphene to 200000 cm ² -V ^_1 -s ^_1 at a carrier density of 10 ¹² cm ^-2 . The corresponding resistivity of graphene sheets would be 10 ^-6 W-cm. This is less than the resistivity of silver, the lowest otherwise known at room temperature. However, on S1O2 substrates, scattering of electrons by optical phonons of the substrate is a larger effect than scattering by graphene's own phonons. This limits mobility to 40000 cm ² -V ^_1 -s ^_1 . Charge transport has major concerns due to adsorption of contaminants such as water and oxygen molecules. This leads to non-repetitive and large hysteresis I-V characteristics. Electrical resistance in 40-nanometer wide nanoribbons of epitaxial graphene changes in discrete steps. The ribbons' conductance exceeds predictions by a factor of 10. The ribbons can act more like waveguides or quantum dots, allowing electrons to flow smoothly along the ribbon edges. In copper, resistance increases in proportion to length as electrons encounter impurities. Transport is dominated by two modes. One is ballistic and temperature independent, while the other is thermally activated. Ballistic electrons resemble those in cylindrical carbon nanotubes. At room temperature, resistance increases abruptly at a particular length — the ballistic mode at 16 micrometers and the other at 160 nanometers (1% of the former length).

[0007] Graphene's permittivity varies with frequency. Over a range from microwave to millimeter wave frequencies it is roughly 3.3. This permittivity, combined with the ability to form both conductors and insulators, means that theoretically, compact capacitors made of graphene could store large amounts of electrical energy. Graphene's unique optical properties produce an unexpectedly high opacity for an atomic monolayer in vacuum, absorbing pa ~ 2.3% of light, from visible to infrared. Here, a is the fine-structure constant. [0008] When single-layer graphene is supported on an amorphous material, the thermal conductivity is reduced to about 500 - 600 W-m ^_1 -K ^_1 at room temperature as a result of scattering of graphene lattice waves by the substrate, and can be even lower for few layer graphene encased in amorphous oxide. Likewise, polymeric residue can contribute to a similar decrease in the thermal conductivity of suspended graphene to approximately 500 to 600 W-m ^_1 -K ^_1 for bilayer graphene. It has been suggested that the isotopic composition, the ratio of ¹² C to ¹³ C, has a significant impact on the thermal conductivity. For example, isotopically pure ¹² C graphene has higher thermal conductivity than either a 50:50 isotope ratio or the naturally occurring 99:1 ratio. It can be shown by using the Wiedemann-Franz law, that the thermal conduction is phonon-dominated. Potential for this high conductivity can be seen by considering graphite, a 3D version of graphene that has basal plane thermal conductivity of over a 1000 W-m ^_1 -K ^_1 (comparable to diamond). In graphite, the c-axis (out of plane) thermal conductivity is over a factor of -100 smaller due to the weak binding forces between basal planes as well as the larger lattice spacing. Despite its 2-D nature, graphene has three acoustic phonon modes. The two in-plane modes (LA, TA) have a linear dispersion relation, whereas the out of plane mode (ZA) has a quadratic dispersion relation. Due to this, the f ¹ dependent thermal conductivity contribution of the linear modes is dominated at low temperatures by the T ¹⁵ contribution of the out of plane mode.

[0009] The (two-dimensional) density of graphene is 0.763 mg per square meter. Graphene has an intrinsic tensile strength of 130 GPa (19,000,000 psi) (with representative engineering tensile strength -50-60 GPa for stretching large-area freestanding graphene) and a Young's modulus (stiffness) close to 1 TPa (150,000,000 psi). The spring constant of suspended graphene sheets has been measured using an atomic force microscope (AFM). Graphene sheets were suspended over S1O2 cavities where an AFM tip was used to apply a stress to the sheet to test its mechanical properties. Its spring constant was in the range 1-5 N/m and the stiffness was 0.5 TPa, which differs from that of bulk graphite.

[0010] Graphene has a theoretical specific surface area (SSA) of 2630 m ² /g. This is much larger than for carbon black (typically smaller than 900 m ² /g) or for carbon nanotubes (CNTs), from ~100 to 1000 m ² /g and is similar to activated carbon. Graphene is the only form of carbon (or solid material) in which every atom is available for chemical reaction from two sides (due to the 2D structure). Atoms at the edges of a graphene sheet have special chemical reactivity. Graphene has the highest ratio of edge atoms of any allotrope. Defects within a sheet increase its chemical reactivity. The onset temperature of reaction between the basal plane of single-layer graphene and oxygen gas is below 260 °C (530 K). Graphene burns at very low temperature (e.g., 350 °C (620 K)). Examples of types of graphene are monolayer sheets, bilayer graphene, graphene superlattices, graphene nanoribbons, graphene quantum dots, graphene oxide, reduced graphene oxide, pristine graphene, graphene ligand/complex, graphene fiber, 3D graphene, pillared graphene, reinforced graphene, molded graphene, graphene aerogel, graphene nanocoil, and crumpled graphene. The present teaching uses graphene forms which exfoliate into monolayer sheets, as in a polymer nanocomposite, and are of an inert condition, i.e., limited to no chemical functionality such as carboxylic acid, ketone, aldehyde, or hydroxyl groups on the graphene plate surface or plate edges.

II. Summary

[0011] Graphene in polymer nanocomposites has been reported to contain many attributes such as antioxidant properties, thermal conductivity, electrical conductivity, and reduction in permeability. Abrasion resistance of rubber nanocomposites is also noted, suggesting better tire wear. In addition, improvement in hysteresis (measured by the loss modulus in shear or in tension (G” or E”) divided by the storage modulus, either in shear or in tension (G’ or E’) to calculate the tangent delta) has been noted. In this instance such improvements can facilitate reductions in whole tire rolling resistance, with no loss in traction qualities.

[0012] In addition to the thermal properties of graphene, it is reported to show the following properties: electrical conductivity, odorless and no known toxicity, inert, and in polymer composites, demonstrates impermeability. It is therefore desirable to provide graphene as an additive to rubber compounds. Applications where impermeability is desirable are, for example, automotive air conditioning hoses, bladders, rubber sheeting, and the innerliner of a tire. In this specific case, it teaches the reduction of permeability of a tire innerliner beyond that achieved by use of compounded bromobutyl polymers and chlorobutyl polymers, which sometimes is used in automobile air conditioning hose and other comparable applications, such as sheeting. [0013] The present teaching further focuses on innerliners for automobile tires, light truck tires, and tires for commercial vehicles, which all typically use innerliners based on compounded bromobutyl polymers, but is equally applicable to innerliners using chlorobutyl polymers. Bromobutyl used in the present teaching has a nominal bromine content of 2.0 weight percent (wt.%) and Mooney viscosity between 26 and 52 Mooney Units, and typically 32 +/- 2 Mooney Units. Mooney viscosity of the polymer is measured according to the procedure described in ASTM D1624 at 125°C using a large rotor and testing for 8 minutes, after a 1.0 minute preheat to generate a number described as ML 1+8.

[0014] Innerliner compound formulation will also contain carbon black, including the grades N660, N762, or N774. Rubber compound process oils can be paraffin, naphthenic, or the derivative described as mild extraction solvate (MES), aromatic or its derivative, treated distillate aromatic extract (TDAE), or residual aromatic extract (RAE). Tackifying resins, such as those produced from C5 monomers or aromatic monomers, are added to the bromobutyl innerliner compound formulation to further improve compound factory processing. In present teachings, an exemplary C5 resin is purchased from ExxonMobil, identified as Escorez 1102™. In the present teaching, Escorez 1102™ was blended with a phenolic tackifying resin (Koresin ^® from BASF), to further optimize tack and compound processing. The process aids required for a halobutyl formulation also include a homogenization agent to aid uniform dispersion of the compounding additives. There are a number available, but in the present teaching, Stmktol 40MS™ was selected. The final part of the compound formulation is the vulcanization system, which in the case of halobutyl compounds typically contains four chemicals - zinc oxide, stearic acid, sulfur, and an accelerator to promote the vulcanization reaction. For halobutyl compounds the accelerator 2,2-dithiobis(benzothiazole), sometimes referred to as MBTS, is used near universally in tire innerliners for this purpose. The amount of each material used in the innerliner compound or in any other application is expressed relative to the total amount of polymer which is expressed as 100.00 parts per hundred rubber or PHR. The amount of each compounding additive in the formulation is expressed in PHR relative to the amount of weight of polymer at 100.00 as can be seen in Example 1 Table 1. [0015] Such formulations may also contain inorganic fillers, in addition to carbon black, to optimize cost. Such fillers are kaolin clays, talc, and calcium carbonate. However, such fillers can create factory processing challenges such as excessive tack.

[0016] In the case of tires, the gauge of an innerliner containing 100.00 PHR of bromobutyl polymer, compounded as described, will be 1.00 millimeter (mm) for passenger and light truck tires, and 2.00 mm for commercial heavy duty truck and bus tires, and extend uniformly and fully from the lower bead, or toe, of the tire on one side to the same position on the opposite side of the tire, thus allowing full interior innerliner material coverage. Such attainment is useful for satisfactory tire - vehicle performance.

[0017] Further reference to the art of compounding tire innerliners may be obtained in the text, Rubber Compounding Chemistry and Applications by B. Rodgers and published by CRC Press. Such innerliner compositions allow for adequate performance of a typical tire referring specifically to tire air retention quality, tire rolling resistance attributable to air retention qualities, tire - vehicle handling and stability performance, wear, traction, and durability. Further reference to the impact of tire innerliner quality and tire performance can be found in the text, Tire Engineering by B. Rodgers and published by CRC Press.

[0018] New generation vehicles such as electric powered automobiles are driving significant need in tires where major improvement in tire inflation pressure retention is needed. Whole tire rolling resistance is increasingly important due to vehicle energy consumption. Reductions in green-house gas emissions and safety are further factors of importance. Reductions in whole tire rolling resistance must not be achieved through loss in safety and durability. Improvements in tire air pressure retention have an immediate impact on tire warranty claims, improved vehicle fuel efficiency, reductions in emissions, and improved tire and traction wear performance.

[0019] Additionally, improvement in innerliner quality, through addition of an additive, must not negatively impact manufacturing efficiency, either in compound mixing and handling, extrusion and calendaring, handling at tire building machines, or be a source of blemishes and defects on final product inspection.

[0020] It is thus desirable to provide graphene as an additive in rubber compounds, in particular to the innerliner of a tire. The present teaching enables improvement in air retention in tires. The teachings are equally applicable to other automotive products such as hoses, which use a halobutyl liner to minimize gas or other medium permeation through the part, thereby ensuring pressure retention and no loss to the environment of cooling mediums. It is also contemplated to include graphene in caulks, sealants, seals, gaskets, medical gloves, beverage bottles, and chemical and solvent resistant gloves.

[0021] The present teaching demonstrates reducing the liner permeability beyond that achieved by bromobutyl and chlorobutyl polymers.

[0022] Still other benefits and advantages of the present subject matter will become apparent to those skilled in the art to which it pertains upon a reading and understanding of the following detailed specification.

III. Brief Description Of The Drawings

[0023] The present teachings are described hereinafter with reference to the accompanying drawings.

[0024] FIG. 1 depicts a graph showing rapid reduction in permeability;

[0025] FIG. 2 depicts the structures of graphene, graphene oxide, and reduced graphene oxide; [0026] FIG. 3 depicts a tire;

[0027] FIG. 3A depicts a partial cross-section of a tire;

[0028] FIG. 4 is a graphical representation of the graphene plates acting as a barrier to gas flow; [0029] FIG. 5A depicts the structure of paraffin wax;

[0030] FIG. 5B depicts the structure of microcrystalline wax;

[0031] FIG. 5C depicts the structure of an antiozonant;

[0032] FIG. 5D depicts the structure of an antioxidant;

[0033] FIG. 6 is a chart showing sidewall components; and [0034] FIG. 7 is a chart showing antiozonant percentage over time.

IV. Detailed Description

[0035] 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.

[0036] 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 1

Typical Properties of Graphene

[0037] The particle size range of graphene used in the present teachings can range from about 50 nm to about 10 pm. In one aspect, the particle size range is from about 100 nm to about 5 pm. 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 pm, greater than about 2 pm, greater than about 3 pm, greater than about 4 pm, greater than about 5 pm, greater than about 6 pm, greater than about 7 pm, greater than about 8 pm, or greater than about 9 pm. In one aspect, the particle size range is less than about 10 pm, less than about 9 pm, less than about 8 pm, less than about 7 pm, less than about 6 pm, less than about 5 pm, less than about 4 pm, less than about 3 pm, less than about 2 pm, less than about 1 pm, 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 ² /gram to 250 m ² /gram and in one aspect is about 180 m ² /gram. In one aspect, the surface area of the graphene plate is greater than 150 m ² /gram, greater than 100 m ² /gram, less than 250 m ² /gram, less than 200 m ² /gram, or less than 150 m ² /gram.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] Measurement of Properties of Rubber Compositions

[0042] 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.

[0043] Example 1

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.

[0044] 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.

[0045] Example 2

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.

[0046] 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 2

Compound 3 (control) 1 2 4 5 6 ERTNB 10- ERTNB 10- ERTNB 10- ERTNB 10- ERTNB 10- ERTNB 10-

Number 54-03 54-01 54-02 54-04 54-05 54-06 BUR 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

ERTNB 10-53- 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

O' add elastomers and ertnblO-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

O' ADD 1st Pass MB

3' DUMP

MILL G on mill with mill rolls at R.T.

5' (try to reach 150° C at 5')

Final Pass Productive

Set-Up SANDWICH IN CURES

O' ADD 2/3 of 2nd pass MB

ADD Sulfur, Accelerator pocket, &

15" 1/3 of 2nd pass MB

1 SWEEP

5' (try to reach 150° C at 5')

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

BUR 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

ML 1+4

Mooney Viscosity 100°C 57.80 57.50 57.60 58.70 58.60 60.40

MDR Rheometer 160C° Delta Torque in-lb 2.59 2.67 2.75 2.58 2.74 3.18

Tsl 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 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

BUR 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 )

Permeation cc*mm/(m ² *day) 220 201 168 146 152 101

Permeability cc*mm/(m 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

Note: Permeation and Permeability coefficients taken from the industry reference formulation (#3) in the text Tire Engineering, CRC Press 2021

Air Permeability to ASTM D1434 60C cc STP - cm/ cm2 - s -

Permeability atm 2.455 1.249 1.495 1.668 1.745 1.610

Rating (Lower is better) 100 51 61 68 71 66

[0047] Tire sidewall performance requirements include resistance to oxidation, ozone attack, UV light degradation, light, heat, fatigue, discoloration, and low hysteresis. Protection systems include waxes, antioxidants, and antiozonants. Polymer blends of natural rubber, butyl rubber, and styrene-butadiene rubber facilitate fatigue resistance. Table 5 below shows a tire sidewall formulation (units are PHR).

Table 5

Natural Rubber (TSR10) 50.00

Polybutadiene 50.00

Carbon black (N330) 45.00

Peptizer (Renacit 11) 0.25

Process oil (TDAE) 5.00

Paraffinic wax 1.50

Microcry stahine wax 1.50

Antioxidant TMQ 1.50

Antiozonant 6PPD 3.50

Stearic acid 1.50

Zinc oxide 4.00

Sulfur 1.00

Accelerator (TB B S ) 1.00

Retarder (PVI) 0.25

[0048] With reference to FIGS. 5A-5D, waxes, antiozonants, and antioxidants are used to protect the sidewall compounds. Paraffin wax provides short term protection after manufacturing and in storage. Microcry stahine wax provides three to twelve months protection in storage before installation. /V-(l,3-dimethylbutyl)- V’-phenyl-l,4-benzenediamine (6PPD) provides medium protection against ozone and fatigue. 6PPD is an effective antiozonant, but blooms, which causes sidewall discoloration. 2, 2, 4-trimethyl- 1,2-dihydroquinoline (TMQ) provides short to long term protection against heat and light, and acts as an antioxidant. TMQ and 6PPD block rubber polymer degradation via free radical termination, chain termination, and free radical removal.

[0049] With reference now to FIGS. 6 and 7, 6PPD is the primary antiozonant used in tire sidewalls. It is insoluble, which results in blooming to the surface causing discoloration. Up to 30% of 6PPD can be exhausted in 32 days. 6PPD is also consumed in protecting the sidewall from ozonolysis and oxidation. Given that 6PPD will ultimately either be consumed or bloom to the sidewall surface, additional protective components are desired. An effective material would be highly aromatic (such as 6-member cyclic carbons), high molecular weight, soluble in rubber, a free molecular scavenger, and non-migratory. In one aspect of the present teaching, graphene can be used to replace 6PPD.

[0050] The addition of graphene to tire sidewall compounds can extend the life and performance of the sidewall. Graphene is non-staining and is persistent (i.e., the graphene stays in the compound and in the tire). Graphene can function as an antioxidant and antiozonant, all while having no trade off or loss in basic mechanical properties, processing, or vulcanization kinetics. [0051] A rubber tire sidewall compound formulation will consist of many types of materials and chemicals. Typically the sidewall compound formulation used on a passenger tire light truck tire, heavy duty truck tire mounted on a commercial truck and trailer, earthmover or OTR tire, aircraft, and farm tires will consist of natural rubber and synthetic rubber blend. 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 sidewall compound containing 30 PHR to 100 PHR of natural rubber can be utilized but a level of 30 PHR to 50 PHR is typical. A synthetic rubber is added from about 0 PHR to abouty 70 PHR and the natural rubber correspondingly adjusted between about 30 PHR about 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, and ethylene propylene diene rubber ((EPDM). Blends of such synthetic rubbers may also be used as part of the total rubber hydrocarbon content. The ideal tire tread sidewall compound will have between 30 PHR and 50 PHR of natural rubber and 70 PHR to 50 PHR of polybutadiene and a preferred ratio of the two polymers of 50 PHR and 50 PHR. Carbon black may be of different grades as described in the text “Rubber Compounding Chemistry and Applications, 2 ^nd edition, by CRC Press (2015)”. Though grades including N330, N326, N347, and N358 are often used, other examples of grades could be selected from the SAF, ISAF, or HAF, FEF groups might also be selected depending on the manufacturer, and is noted they will have no material impact on the present teaching. Carbon black can be N330 at amounts of about 40 PHR to about 55 PHR and can be about 45 PHR. In addition, a peptizer designed to improve compound mixing efficiency may be added at between about 0.0 and about 0.5 and can be about 0.25 PHR. An antioxidant is added at between about 0.0 and about 2.0 PHR. An antiozonant is added at between about 0.0 and about 5.0 PHR and between about 2.5 to about 4.5 PHR. Waxes such as paraffinic was and microcrystalline wax are added at between about 0.0 and about 3.0 PHR in total and can be about 1.5 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 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 about 4.0 PHR to about 5.0 PHR.

[0052] Tire sidewalls may also have a white appearance, applied as stripes in addition to letters molded onto the sidewall, and to which this invention equally applies. White sidewall compounds will contain blends of all four polymers, natural rubber, chlorobutyl rubber, polybutadiene and EPDM or blends chosen form this selection. Rather than carbon black the filler system will consist of titanium dioxide, calcium carbonate, clays and silica. In such instances, no antiozonant such as 6PPD would be used.

[0053] 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 is 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. 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.

[0054] Clause 1 - A rubber composition including natural rubber, polybutadiene, carbon black, peptizer, process oil, paraffinic wax, microcrystalline wax, stearic acid, zinc oxide, sulfur, accelerator, pre vulcanization inhibitor, and graphene, wherein the sidewall has no additional antioxidant or antiozonant.

[0055] Clause 2 - A rubber composition including natural rubber, polybutadiene, carbon black, and graphene, wherein the sidewall has no additional antiozonants.

[0056] Clause 3 - The rubber composition of clause 2, wherein the sidewall has no additional antioxidants.

[0057] Clause 4 - The rubber composition of clauses 2 or 3, wherein the graphene is between about 0.5 PHR and about 10.0 PHR.

[0058] Clause 5 - The rubber composition of clauses 2-4, wherein the composition has no N- ( 1 ,3-dimethylbutyl)- V’ -phenyl- 1 ,4-benzenediamine.

[0059] Clause 6 - The rubber composition of clauses 2-5, wherein the composition has no 2,2,4- trimethyl- 1 ,2-dihydroquinoline.

[0060] Clause 7 - The rubber composition of clauses 2-6, wherein the graphene is a graphene plate, wherein the graphene plate is between about 0.5 PHR and about 10.0 PHR.

[0061] Clause 8 - The rubber composition of clauses 2-7, wherein the graphene plate has a surface area from about 100 m ² /gram to about 250 m ² /gram.

[0062] Clause 9 - The rubber composition of clauses 2-8, wherein the graphene plate has an oxygen content of less than about 1%.

[0063] Clause 10 - The rubber composition of clauses 2-9, wherein the graphene has a thickness less than about 1 nm and an aspect ratio of about 1000. [0064] Clause 11 - The rubber composition of clauses 2-9, wherein the graphene has a thickness of less than about 3.2 nm, a particle size of between about 50 nm and about 10 pm, and contains greater than about 95% carbon.

[0065] Clause 12 - The rubber composition of clauses 2-11, wherein the graphene plate is between about 0.5 PHR and about 8.0 PHR.

[0066] Clause 13 - The rubber composition of clauses 2-12, wherein the composition further includes peptizer, process oil, paraffinic wax, microcrystalline wax, stearic acid, zinc oxide, sulfur, accelerator, and pre vulcanization inhibitor.

[0067] Clause 14 - The rubber composition of clauses 2-4 or 7-13, wherein the composition contains no /V-(l,3-dimethylbutyl)- V’-phenyl-l,4-benzenediamine or 2,2,4-trimethyl- 1,2- dihy droquinoline .

[0068] Clause 15 - The rubber composition of clause 1, wherein the composition contains no N- ( 1 ,3-dimethylbutyl)-A/’ -phenyl- 1 ,4-benzenediamine or 2,2,4-trimethyl- 1 ,2-dihydroquinoline. [0069] Clause 16 - The rubber composition of clauses 1-15, wherein the rubber composition is a tire sidewall.

[0070] 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.

[0071] Having thus described the present teachings, it is now claimed: