DESC:TECHNICAL FIELD OF THE INVENTION
The present invention relates to the field of Polymer Technology. The present invention in particular relates to bio filler-based tyre tread rubber composition and its method of preparation.
BACKGROUND OF THE INVENTION
Conventionally, spiked tires in which small pieces of hard alloy called studs or spike pins are implanted in the tread surface have been used as tires that are often run on icy and snowy roads.
However, studless tires have come to be used due to problems such as damage to paved road surfaces caused by studs sticking into the road surface and pollution caused by dust from asphalt and the like. Typical conventional techniques for realizing studless tires are as follows:
One known technique is to improve the adhesion of the tread rubber to the road surface by reducing the storage elastic modulus of the tread rubber in a low-temperature region corresponding to the temperature of the icy and snowy road surface. Also known is a technique of adding a filler having hardness higher than that of ice into the tread rubber to improve the frictional force due to the effect of the filler on ice scratching (Japanese Patent Publication No. 6-102737).
However, with such a method, when a thin water film is formed between the road surface and the tread of the tire, the water film may not achieve the necessary friction, which is a problem.
Moreover, the method of decreasing the storage elastic modulus has a problem of decreasing the wear resistance of the tire.
In order to remove the water film formed between the tire tread and the road surface when driving on ice and snow, it has been proposed to blend a general water-absorbing resin such as an acrylate polymer into the tire tread.
However, the water film generally contains alkali and alkaline earth metal ions (Na+, K+, Ca+, Mg+), sulfate ions (SO42-), chloride ions (Cl-), hydrogen carbonate ions (HCO3- ) and other electrolytes, the water-absorbing resin sometimes fails to exhibit sufficient water-absorbing performance due to the interfering action of these ions.
Therefore, in Japanese Patent Application Laid-Open No. 2000-44732, silica is blended as a filler that exerts a scratching effect, and highly hydrophilic A-type zeolite or silica gel is used as a water absorbing agent for removing the water film. is proposed. Japanese Patent Application Laid-Open No. 5-269884 discloses a method of adding leather granules such as pulverized cowhide and gelatin granules, or vegetable granules containing walnut shell powder as a filler, can be used in the same way.
Publication no. JP2003041058 provides a rubber composition for tire tread improving the skid resistance (antiskid performance) on the ice/now-covered road and keeping the high abrasion resistance of the tread rubber. This rubber composition is obtained by compounding 100 pts.wt. of a rubber polymer component comprising a diene rubber with 0.5-20 pt.(s). wt. of Y-type zeolite or mordenite and 3-30 pts.wt. of walnut shell powder.
Publication no. JP5389487 provides a tread rubber composition for a studless tire in which cut chip resistance is enhanced without impairing low-temperature performance and wear resistance. This tread rubber composition for the studless tire comprises: 100 pts.wt. of a rubber component containing 20 to 60 pts.wt. of a butadiene rubber and 40 to 80 pts.wt. of a natural rubber and/or an isoprene rubber; 0.1 to 10 wt. pts. of an alkyl group-modified sugar derivative (for example, alkyl-D-glucopyranoside represented by general formula (1) (where n=0 to 24)); and a granule substance having an average particle diameter of 0.1 to 500 µm.
Publication no. US9868851 provides a rubber composition for a tire tread comprising 100 parts by mass of a diene rubber, 10 to 150 parts by mass of a reinforcing filler, and 0.1 to 30 parts by mass of an acid-treated silk powder having a 90% volume particle diameter (D90) of 500 µm or less. A pneumatic tire having a tread comprising the rubber composition.
Publication no. JP2011012111 provides a rubber composition having excellent on-ice performance and a pneumatic tire using the rubber composition. The rubber composition is obtained by mixing 100 pts.wt. of diene-based rubber with 0.3-20 pts.wt. of bowl-like fine particles composed of, for example, a methacrylic resin and having an average particle diameter of =100 µm. The pneumatic tire comprises tread composed of the rubber composition. Ground porous carbonized material of plant, e.g., plant-based granule such as ground walnut husk or ground bamboo charcoal and the porous cellulose particles may be used at the same time.
Publication no. JP2011012110 provides a rubber composition having excellent on-ice performance and a pneumatic tire using the same. The rubber composition is obtained by mixing 100 pts.wt. of diene-based rubber with 0.3-20 pts.wt. of porous cellulose particles, for example, composed of a methacrylic resin and having a porosity of 75-95% and an average particle diameter of =1,000 µm. The pneumatic tire has tread composed of the rubber composition. Ground porous carbonized material of plant, e.g., plant-based granule such as ground walnut husk or ground bamboo charcoal and the porous cellulose particles may be used at the same time.
Publication no. JP2010285536 provides a rubber composition having the excellent on-ice performance; and a pneumatic tire formed using this rubber composition. This rubber composition comprises 100 pts.wt. of a diene-based rubber and 0.3-20 pts.wt. of a porous hydroxyapatite powder. This pneumatic tire is provided with a tread formed with the rubber composition. The powder uses a natural hydroxyapatite powder obtained from domestic-animal bones or the like and may combine a plant granular material such as a pulverized product of walnut shell or a plant granular material whose surface is surface-treated with a resin liquid of a rubber adhesion improver.
Publication no. JP2010280748 provides a rubber composition having excellent performance on ice, and a pneumatic tire produced using the rubber composition. This rubber composition includes 0.5-10 pts.wt. of walnut husk powders of improved powder flowability, that is, ground walnut husks in which angles are rounded off to increase roundness and 100 pts.wt. of a diene rubber. The pneumatic tire equipped with a tread produced using the rubber composition is also disclosed. The ground walnut husks of improved powder flowability has an angle of repose of =23 degrees.
Publication no. JP2010184991 provides a rubber composition having excellent on-ice performance and to provide a pneumatic tire obtained by using the rubber composition. The rubber composition is obtained by mixing 100 parts wt. of a diene-based rubber component with 0.3 to 20 parts wt. of granules that are composed of a fossil of a shellfish. The pneumatic tire includes a tread composed of the rubber composition. A vegetative granular body such as granules of a walnut shell and granules of vegetative porous carbonized product such as granules of bamboo charcoal may be used together with the granules of the fossil of the shellfish.
Publication no. JP2003041058 provides a rubber composition for tire tread improving the skid resistance (antiskid performance) on the ice/snow-covered road and keeping the high abrasion resistance of the tread rubber. This rubber composition is obtained by compounding 100 pts.wt. of a rubber polymer component comprising a diene rubber with 0.5-20 pt.(s). wt. of Y-type zeolite or mordenite and 3-30 pts.wt. of walnut shell powder.
Publication no. JPH03210342 provides the title rubber excellent in the braking and driving performance on a frozen road by using a sponge rubber made from a rubber composition. obtained. by compounding a raw material rubber with leather particles and specific vegetable particles in a specified ratio to make at least the surface layer. At least the surface layer is made up of a sponge rubber made from a rubber composition prepared by compounding 100 pts.wt. raw material rubber comprising a natural and/or diene rubber, 3-30 pts.wt. leather particles (e.g., particles of hide), and 3-30 pts.wt. vegetable particles obtained by grinding seed shells or fruit pits (e.g., particles of walnut shell).
Publication no. IN1401/DEL/2015 provides a novel activated carbon exhibiting a feature of carbon and calcium oxide. It finds application as filler material for rubber sole and tyre tread manufacturing, to obtain good, vulcanized rubber, when compared with conventional rubber prepared using carbon black as filler. It may also be chemically activated and used as adsorbent for removal of toxic metals from waste water. The invention also provides a process for the preparation of the activated carbon from limed animal fleshing.
The article entitled “Walnut tire treads” by Joey Haar; 10/28/2016; trend hunter talks about the winter tires offer impressive traction during the slippery winter months without resorting to tire studs that are banned on many roads. The treads on Toyo Observe tires are coated with purified walnut shells. While hard enough to crack through sheets of ice, the walnut shells are still softer than pavement, making Toyo Observe tires completely safe for driving city roads.
The article entitled “Toyo's walnut-infused tires are cracking good on ice” by David Booth; 1/31/2017; driving talks about the walnut shells to act as studs in your snow tires. It turns out that walnut shells are around 3 to 4 on the Mohs hardness scale (invented by Friedrich Mohs in 1812, which compares the hardness of materials to diamonds and talc) and are frequently used instead of sand to blast paint and rust off delicate car parts.
The article entitled “Tread wright tire” by tread wright; 2023 talks about the kedge grip is a fine combination of walnut shells and glass particles that are mixed into the entire tread compound during the manufacturing process.
The article entitled “Toyo proves its tires have the nuts to tackle winter driving” by auto file; 2/17/2020 talks about the four-groove, directional tread pattern that stands out is the unique 360-degree spiral edge sipes that are designed to improve traction while cornering, accelerating, or braking. The tread also has tapered evacuation grooves that get wider toward the edges, helping to move water and slush away from the center of the tire. This reduces the risk of hydroplaning or getting caught in slushy ruts. Much attention has also been given to the design of the tread’s inner and shoulder blocks, as well as the various siping throughout the tread – all intended to enhance grip in typical winter conditions. The structure of the tire has also been improved to ensure the tire’s contact patch is evenly distributed across the tread. These improvements in the tire’s design have resulted in better performance on wet surfaces and greater stability, while still maintaining excellent capabilities on ice and snow. Toyo says the upgrades do not compromise the tire’s wear life. Toyo has expanded its GSi-6 lineup to suit the growing range of vehicles manufacturers are offering consumers. The base GSi-6 is intended for use on the various categories of passenger cars and smaller CUVs. Slight variations in the construction and design of the GSi-6 HP are said to result in increased handling prowess, making this tire better suited for higher-performance vehicles.
The article entitled “Winter tire innovations” by Rich Ashley; tire review; 5/2/2016 talks about the tires that helped keep trucks and cars under control had a real impact on keeping drivers, pedestrians, and horses safe. They turn to special technologies that strike a balance among the conflicting demands. These include softer and more flexible tread compounds, the shape of the contact patch, specially designed grooves, advanced sipe technology including complex 3-D sipes, and distinctive tread designs. Tread compounds all harden as temperatures drop – the compound determines the rate of that hardening.
In order to overcome above listed prior art, the present invention aims to provide a tyre tread rubber composition using bio filler and its method of preparation thereof.

OBJECT OF INVENTION
It is the primary object of the present disclosure to provide a tyre tread rubber composition with improved winter/snow, ice traction, wet taction along with lower rolling resistance property.
It is the principal object of the present disclosure to provide high performance motor cycle tyre tread rubber composition using a walnut shell powder having the strong broad band at 3362.84 cm-1 indicates O-H stretching vibration of hydroxyl groups. The band nearly at 2887.60 cm-1 is due to C-H stretching bond of alkane. The bands at 1733.30 cm-1 (presence of C=O ester fatty acid group) and 1593.07 cm-1 indicates the C?=?C stretching vibration of aromatic carboxyl groups. In particular, the band at 1504.76 Cm-1 indicates the skeletal lignin band. The band region from 1231.51 cm-1 to 1029.67 cm-1 corresponds to C–O functional group in Alcohol, Ether, Ester, Carboxylic Acid, Anhydride and it is measured from FTIR ATR.
It is another object of the present disclosure to provide a tyre tread rubber composition constituting a walnut shell powder offering better winter/snow traction, ice traction, wet traction along with lower rolling resistance.
It is another object of the present disclosure is to reduce the carbon foot print.
It is yet another object of the present disclosure to provide better processing characteristics.
SUMMARY OF THE INVENTION
In one aspect of the present disclosure, a high-performance tire tread rubber composition is provided.
The tyre tread rubber composition includes non-oil extended solution-polymerized styrene-butadiene rubber (S-SBR) in an amount ranging from 50 to 70 phr. The composition further includes natural rubber (NR) in an amount ranging from 5 to 15 phr. The composition further includes ultra-high cis polybutadiene rubber (Nd-BR) in an amount ranging from 10 to 30 phr. The composition further includes carbon black in an amount ranging from 5 to 90 phr. The composition further includes precipitated silica in an amount ranging from 0 to 50 phr. The composition further includes walnut shell powder as a bio-filler in an amount ranging from 0.1 to 20 phr. The composition further includes coupling agent in an amount ranging from 0 to 5 phr. The composition further includes activators in an amount ranging from 1 to 8 phr. The composition further includes anti-degradants comprising 6PPD in an amount ranging from 1 to 5 phr and MC wax in an amount ranging from 0.5 to 3 phr. The composition further includes a vulcanizing agent comprising sulfur in an amount ranging from 1 to 3 phr. The composition further includes primary accelerators in an amount ranging from 1 to 3 phr. The composition further includes hydrocarbon resin ranging from 2 to 4 phr.
In some aspects of the present disclosure, the non-oil extended solution-polymerized styrene-butadiene rubber (S-SBR) comprises a vinyl content of 55%, a bound styrene content of 20%, and a polymer glass transition temperature (Tg) of -36°C.
In some aspects of the present disclosure, the ultra-high cis polybutadiene rubber (Nd-BR) is produced by 1,3-butadiene polymerization using a neodymium catalyst with a 1,4-cis content greater than 97%.
In some aspects of the present disclosure, the carbon black is selected from grades in the N100 series, N200 series, or N300 series.
In some aspects of the present disclosure, the walnut shell powder has a mesh size between 80 and 100.
In some aspects of the present disclosure, the coupling agent is selected from bis(3-triethoxysilylpropyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, or mixtures thereof.
In some aspects of the present disclosure, the activators include zinc oxide and stearic acid.
In some aspects of the present disclosure, the anti-degradants comprising 6PPD in an amount ranging from 1 to 5 phr and MC wax in an amount ranging from 0.5 to 3 phr.
In some aspects of the present disclosure, the primary accelerators comprise N-cyclohexyl-2-benzothiazolesulfenamide (CBS) and Diphenylguanidine (DPG).
In second aspect of the present disclosure, a method for preparing a rubber composition is provided.
The method includes preparation of Master Batch that includes charging a mixing chamber with elastomers and mixing at a rotation speed of 45 to 70 rpm and a head temperature of 75°C to 95°C for 0 to 30 seconds. The preparation of Master Batch further includes adding a bio filler and mixing for 60 to 180 seconds. The preparation of Master Batch further includes adding 100% of a reinforcing filler comprising carbon black, 100% of an inorganic reinforcing filler comprising silica, and a coupling agent, and mixing for 100 to 120 seconds. The preparation of Master Batch further includes adding MC wax, stearic acid, hydrocarbon resin to a mixture obtained and mixed for 30-40 seconds. The preparation of Master Batch further includes conducting silanisation by reducing the rotor speed to 15 to 25 rpm, at a temperature of 120°C to 145°C for 20 to 30 seconds, followed by sweeping down in an orifice and mixing for 40 to 80 seconds. The preparation of Master Batch further includes dumping the rubber compound at a temperature of 150°C to 165°C. The preparation of Master Batch further includes sheeting out the rubber compound using a laboratory two-roll mill. The method further includes preparation of Step II Master Batch that includes charging the mixing chamber with the master batch prepared in step (1), zinc oxide, and 6PPD, and mixing for 120 to 140 seconds. The preparation of step II master batch further includes dumping the rubber compound at a temperature of 125°C to 140°C. The preparation of step II master batch further includes sheeting out the rubber compound using a laboratory two-roll mill. The method further includes preparation of Step III master batch that includes charging the mixing chamber with the step II master batch and mixing for 120 to 140 seconds. The preparation of Step III master batch includes dumping the rubber compound at a temperature of 125°C to 140°C. The preparation of final batch includes charging the mixing chamber with the step III master batch and curatives comprising sulfur, CBS (N-cyclohexyl-2-benzothiazolesulfenamide), and DPG (Diphenylguanidine), and mixing for 40 to 110 seconds. The preparation of final batch includes dumping the rubber compound at a temperature of 90°C to 110°C. The preparation of final batch includes performing final sheeting out using a laboratory two-roll mill.

BRIEF DESCRIPTION OF DRAWINGS
The accompanying drawings, which are incorporated in and constitute a part of this specification, show certain aspects of the subject matter disclosed herein and together with the description, help explain some of the principles associated with the disclosed implementations. In the drawing,
Figure 1 illustrates a graph representing FTIR analysis, in accordance with an aspect of the present disclosure.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Various embodiments of the disclosure are discussed in detail below. While specific implementations are discussed, it should be understood that this is done for illustration purposes only. A person skilled in the relevant art will recognize that other components and configurations may be used without parting from the spirit and scope of the disclosure. Thus, the following description and drawings are illustrative and are not to be construed as limiting. Numerous specific details are described to provide a thorough understanding of the disclosure. However, in certain instances, known details are not described in order to avoid obscuring the description.
References to one or an embodiment in the present disclosure can be references to the same embodiment or any embodiment; and such references mean at least one of the embodiments.
Reference to "one embodiment", "an embodiment", “one aspect”, “some aspects”, “an aspect” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the disclosure. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Moreover, various features are described which may be exhibited by some embodiments and not by others.
The terms used in this specification generally have their ordinary meanings in the art, within the context of the disclosure, and in the specific context where each term is used. Alternative language and synonyms may be used for any one or more of the terms discussed herein, and no special significance should be placed upon whether or not a term is elaborated or discussed herein. In some cases, synonyms for certain terms are provided.
A recital of one or more synonyms does not exclude the use of other synonyms.
The use of examples anywhere in this specification including examples of any terms discussed herein is illustrative only and is not intended to further limit the scope and meaning of the disclosure or of any example term. Likewise, the disclosure is not limited to various embodiments given in this specification. Without intent to limit the scope of the disclosure, examples of instruments, apparatus, methods and their related results according to the embodiments of the present disclosure are given below. Note that titles or subtitles may be used in the examples for convenience of a reader, which in no way should limit the scope of the disclosure. Unless otherwise defined, technical and scientific terms used herein have the meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. In the case of conflict, the present document, including definitions will control.
Additional features and advantages of the disclosure will be set forth in the description which follows, and in part will be obvious from the description, or can be learned by practice of the herein disclosed principles. The features and advantages of the disclosure can be realized and obtained by means of the instruments and combinations particularly pointed out in the appended claims. These and other features of the disclosure will become more fully apparent from the following description and appended claims or can be learned by the practice of the principles set forth herein.
As mentioned before, there is a need for technology that overcomes these drawbacks associated with the prior arts. The present disclosure, therefore, also provides a high-performance tyre tread rubber composition. The present disclosure also provides a method of preparing high performance tyre tread rubber composition.
In some aspects of the present disclosure, a high-performance tyre tread rubber composition is provided. The present invention relates to a high performance motorcycle tyre tread composition, capable of providing a motorcycle tyre with improved wet, ice traction and snow traction along with lower rolling resistance property.
The high-performance tyre tread rubber composition may include a rubber composition derived from natural rubber non-oil extended solution polymerized styrene butadiene rubber and neodymium catalyzed polybutadiene rubber based polymers and a dual-filler system consisting of reinforcing fillers carbon black and silica. The high-performance tyre tread rubber composition further include walnut shell powder as a bio filler, a coupling agent, activators, anti-degradants, a vulcanization agent, secondary, and primary accelerators.
In some aspects of the present disclosure, the rubber component is selected from the group consisting of natural rubber, solution styrene butadiene rubber, butadiene rubber, and mixtures thereof.
In some aspects of the present disclosure, the styrene butadiene rubber ranges from 50-70 phr. In some aspects of the present disclosure, the non-oil extended solution polymerized styrene butadiene rubber with a vinyl content of 55% and bound styrene content of 20% and a polymer Tg of -36 Deg C.
In some aspects of the present disclosure, the Indian standard natural rubber (ISNR 20 or NR) from 5-15 phr. In some aspects of the present disclosure, the NR has a Mooney Viscosity, ML (1+4) at 100°C is 65 to 80 MU. In some aspects of the present disclosure, the NR is obtained from Mamparambil Rubber India Pvt Ltd, India.
In some aspects of the present disclosure, the ultra-high cis polybutadiene rubber ranges (Nd BR) from 10-30 phr.
In some aspects of the present disclosure, the ultra-high cis polybutadiene rubber is produced by way 1, 3-butadiene polymerization with a novel neodymium catalyst having more than 97% of 1, 4 cis contents. In some aspect of the present disclosure, the Nd Br is procured from Kumho Petro chemical, India.
In certain aspects of the present disclosure, the carbon black content ranges from 5 to 90 phr. In some aspects of the present disclosure, the carbon black used is selected from carbon black grade N100 series, carbon black grade N200 series, carbon black grade N300 series, combination thereof. Additionally, in certain aspects, the carbon black conforms to ASTM Grade N110 and includes the reinforcing filler SAF (Superior Abrasion Furnace). It has an iodine adsorption number ranging from 140 to 150 mg/g, a tinting strength value between 118% and 128% ITRB, a nitrogen surface area ranging from 122 to 132 m²/g, and a COAN value ranging from 92 to 102 cc/100 g.
In some aspects of the present disclosure, the PPT silica ranges from 0-50phr. In some aspects of the present disclosure, the reinforcing filler silica is selected from precipitated silica or any of the high dispersible silica grades.
In some aspects of the present disclosure, the walnut shell powder ranges from 0.1-20phr. Walnut shell powder characterized in FTIR ATR having the strong broad band at 3362.84 cm-1 indicates O-H stretching vibration of hydroxyl groups. The band nearly at 2887.60 cm is due to C-H stretching bond of alkane. The bands at 1733.30 cm-1 (presence of C=O ester fatty acid group) and 1593.07 cm-1 indicates the C?=?C stretching vibration of aromatic carboxyl groups. In particular, the band at 1504.76 Cm-1 indicates the skeletal lignin band. The band region from 1231.51 cm-1 to 1029.67 cm-1 corresponds to C–O functional group in Alcohol, Ether, Ester, Carboxylic Acid, Anhydride and it is measured from FTIR ATR. In some aspects of the present disclosure, the walnut shell powder is selected from 80-100 mesh size as shown in figure 1.
In some aspects of the present disclosure, the coupling agent ranges from 0-5phr. In some aspects of the present disclosure, the coupling agent is selected from the group consisting of bis(3-triethoxysilylpropyl)tetrasulfide, 3- mercaptopropyltrimethoxysilane, and mixtures thereof.
In some aspects of the present disclosure, the activators such as zinc oxide and stearic acid ranges from 1-8phr.
In some aspects of the present disclosure, the antidegradants are selected from a group includes 6PPD and MC wax. In some aspects of the present disclosure, the 6PPD ranges from 1-5phr. In some aspects of the present disclosure, the MC wax ranges from 0.5-3phr.
In some aspects of the present disclosure the primary accelerator is selected from a group comprising N-cyclohexyl-2-benzothiazolesulfenamide (CBS) and diphenylguanidine (DPG). In some aspects of the present disclosure, the CBS ranges from 1-3phr. In some aspects of the present disclosure, the DPG ranges from 1-3phr.
In some aspects of the present disclosure, the hydrocarbon resin ranges from 2-4phr.
In some aspects of the present disclosure, the vulcanizing agent is sulphur that ranges from 1-3phr.
In some aspects of the present disclosure, the primary accelerators are selected from the group consisting of N-cyclohexyl-2-benzothiazolesulfenamide (CBS) and diphenylguanidine (DPG).
Table 1: Rubber compositions in Phr.
Ingredients Control C1, Phr Formulation related to invention
Ingredients Con F1, Phr F2, Phr
SLR 563 1 70.00 70.00 70.00
ISNR 20 2 10.00 10.00 10.00
Nd BR 3 20.00 20.00 20.00
Carbon Black N110 4 45.00 40.00 25.00
PPT Silica 5 12.00 12.00 12.00
Walnut Shell powder 6 5.00 20.00
Coupling agent SI75 7 1.20 1.20 1.20
Zinc oxide 8 2.50 2.50 2.50
Stearic acid 9 1.30 1.30 1.30
6 PPD 10 3.00 3.00 3.00
MC WAX 11 1.10 1.10 1.10
Hydrocarbon Resin 12 3.00 3.00 3.00
CBS 13 1.00 1.00 1.00
DPG 14 1.00 1.00 1.00
Sulfur 15 1.20 1.20 1.20

1- SLR 563 - It is a non-oil extended solution polymerized styrene butadiene rubber with a vinyl content of 55% and bound styrene content of 20% and a polymer Tg of -36 Deg C.
2- ISNR 20 - Indian Standard Natural Rubber ISNR 20 with the Mooney Viscosity, ML (1+4) at 100°C is 65 to 80 MU and it is obtained from Mamparambil Rubber India Pvt Ltd, India.
3- Nd BR – It is ultra high cis polybutadiene rubber, produced by 1, 3-butadiene polymerization with a novel neodymium catalyst having more than 97% of 1, 4 cis content and it is from Kumho Petro chemical, India.
4- Carbon Black –ASTM Grade N110 is the reinforcing filler SAF, Superior Abrasion Furnace having the Iodine adsorption No. 140 to 150 mg/gm, tinting strength value between 118 to 128 % ITRB, nitrogen surface area value between 122 to 132 m2/gm and COAN value ranges between 92 to 102 cc/100 gm.
5- Precipitated Silica – It is from Madhu Silica Private Ltd, India. It is the reinforcing filler having nitrogen surface area value 170 to 190 m2/gm and it is used for the present invention is to provide a high performance motor cycle tyre treads.
6- Coupling Agent - Si75 is a bifunctional, sulfur- containing organosilane from Nanjing Shuguang Silane Chemical Co Ltd, China. It is used to provide a satisfactory bonding of, chemical/or physical nature between the inorganic filler and diene elastomer(s).
7- Walnut shell powder – it is obtained from HNCO Organics Pvt. Ltd, office : 56/A, Block-J, Sumel Business Park-5 NR. Chamanpura Circle, Asarwa, Ahmedabad-380016 – It is
8 - Zinc Oxide- It is used as an activator for the sulphur vulcanization of rubbers enhances the vulcanization efficiency and reduces the vulcanization time from Ambica Dhatu Private Limited, India.
9- Stearic acid- It is from 3F Industries Ltd., India. It is used as a Process aid. Also, Zinc oxide and Stearic acid are added to form zinc soap, improves the solubility of zinc oxide in the compound, and with the accelerator to form a complex, this complex reacts with sulphur to produce a strong cure activating system.
10- 6PPD- It is (N-(1,3-dimethylbutyl)-N’-phenyl-p-phenylenediamine) from Finorchem Limited, India. It is added to the rubber composition to provide resistance to thermo-oxidative ageing of elastomers.
11- MC Wax- (Microcrystalline wax) from GPL, India. It is used to protect against degradation by ozone.
12- Hydrocarbon resin- It is a hydrocarbon resin, Impera resin 1507 having the softening point of 85 Deg C and a Tg of 40 Deg C from Eastman chemical Switzerland LLC, USA.
13- CBS- (N-cyclohexyl-2-benzothiazolesulfenamide) It is a delayed action accelerator suitable for diene rubbers from Nocil Limited, India.
14- DPG- Diphenylguanidine It is secondary accelerator, used to activate the primary accelerator) from PMC Rubber Chemicals India Pvt ltd, India.
15- Sulphur- Sulphur is the vulcanizing agent from The Standard Chemical Co. Pvt Ltd, India.
In other aspects of the present disclosure, a method of preparing the composition is provided.
The method includes mixing the rubbers, walnut shell powder, and reinforcing fillers coupling agent in a Banbury mixer. The method further include adding activators, anti-degradants, and vulcanization agent to the Banbury mixer and mixing until homogeneous. The method further include adding primary accelerators to the Banbury mixer and mixing until homogeneous. The method further includes dumping the compound from the Banbury mixer and sheeting it out.
The present invention depicts a method for preparing a rubber composition, in accordance with an aspect of the present disclosure. The method includes the following steps:
(a) Preparation of Master Batch:
At step 1, charging a mixing chamber with elastomers and mixing at a rotation speed of 45 to 70 rpm and a head temperature of 75°C to 95°C for 0 to 30 seconds.
Further, adding a bio filler and mixing for 60 to 180 seconds.
Further, adding 100% of a reinforcing filler comprising carbon black, 100% of an inorganic reinforcing filler comprising silica, and a coupling agent, and mixing for 100 to 120 seconds.
Further, adding MC wax, stearic acid, hydrocarbon resin to a mixture and further mixed for 30-40 seconds.
Further, conducting silanisation by reducing the rotor speed to 15 to 25 rpm, at a temperature of 120°C to 145°C for 20 to 30 seconds, followed by sweeping down in an orifice and mixing for 40 to 80 seconds.
And dumping the rubber compound at a temperature of 150°C to 165°C; Further, sheeting out the rubber compound using a laboratory two-roll mill;
(b) Preparation of Step II Master Batch
Charging the mixing chamber with the step 1 master batch prepared, zinc oxide, and 6PPD, and mixing for 120 to 140 seconds.
And dumping the rubber compound at a temperature of 125°C to 140°C; sheeting out the rubber compound using a laboratory two-roll mill.
(c) Preparation of Step III Master Batch
Charging the mixing chamber with the step II master batch and mixing for 120 to 140 seconds.
dumping the rubber compound at a temperature of 125°C to 140°C.
(d) Preparation of Final batch
charging the mixing chamber with the step III master batch and curatives comprising sulfur, CBS (N-cyclohexyl-2-benzothiazolesulfenamide), and DPG (Diphenylguanidine), and mixing for 40 to 110 seconds.
Further, dumping the rubber compound at a temperature of 90°C to 110°C.
At last, performing final sheeting out using a laboratory two-roll mill.
In some aspects of the present disclosure, the rubber composition did not contain the ingredient zeolite as they are hydrated aluminosilicate minerals that contain alkali and alkali earth metals. Alkali earth metals are difficult to disperse into Rubber Matrix.
Example 1: Characterization of Cured Rubber Vulcanizate and Uncured Rubber Compound:
Measurements and Tests:
Two test compositions, F1 and F2, were compared against a control composition (C1). The control composition consisted of an SSBR: NR: Nd BR (70 phr: 10 phr: 20 phr) blend reinforced with 45 phr of carbon black and 12 phr of silica. In contrast, the test compositions partially replaced carbon black with walnut shell powder at 5 phr and 20 phr, respectively.
F1 and F2 exhibited a significant reduction in Mooney Viscosity, ranging from 16.69% to 31.30% compared to C1. This indicates that the walnut shell powder improved the processability of the rubber compound, as lower viscosity reflects better flow and ease of mixing during manufacturing. Improved processability not only enhances production efficiency but also reduces energy consumption, making these compositions more cost-effective for industrial applications.
The hardness values of F1 and F2, measured at 62 Shore A to 65 Shore A, were comparable to those of the control composition. This demonstrates that the partial replacement of carbon black with walnut shell powder does not compromise the durability or mechanical integrity of the tyre tread rubber. The balanced hardness ensures that these compositions meet the rigorous requirements for tyre tread applications.
The test compositions showed remarkable improvements in traction properties. Winter/snow traction improved significantly, ranging from 6.23% to 68.46% compared to the control. Additionally, ice traction increased by 24.78% to 32.87%, and wet traction improved by 20.19% to 23.02%. These enhancements indicate superior grip and handling in diverse conditions, particularly in snowy, icy, and wet environments. Moreover, low rolling resistance (LRR) improved marginally by 1.77% to 3.00%, contributing to better fuel efficiency and reduced energy consumption during vehicle operation.
The partial replacement of carbon black with walnut shell powder introduces a sustainable and eco-friendly alternative in rubber compounding. Walnut shell powder, being a natural and renewable material, reduces reliance on traditional carbon-based fillers while maintaining or even improving the performance characteristics of the rubber composition. This makes F1 and F2 environmentally beneficial without compromising functionality.
The compound properties are listed in Table 2 below-
Table 2: Characterization of Uncured Rubber Compound and Cured Rubber Vulcanizate
Properties Control, C1 F1 F2 Index Index
M1. Processability Characteristics of Rubber Compound
Mooney Viscosity @ 125 Deg C, MU (Lower the Index value is better) 62.3 51.9 42.8 83.31 68.70
M2. Hardness of a Rubber Vulcanizate
Hardness, Shore A 67 65 62 - -
M3. Dynamic Mechanical Properties of the Rubber Vulcanizate
Winter traction, E’ -20 Deg C, Lower the index value is better 48.29 45.28 15.23 93.77 31.54
Ice Traction, tan delta at -10 Deg C (Higher the index value is better) 0.356 0.444 0.473 124.78 132.87
Wet traction, tan delta at 0°C
(Higher the index value is better) 0.250 0.301 0.308 120.19 123.02
Rolling resistance, tan delta 60 Deg C
(Lower the index value is better) 0.171 0.166 0.168 97.00 98.23

Example 2: Mooney Scorch Characteristics (M1):
The Mooney Scorch test, conducted using a Mooney Viscometer (MV 2000), assessed the pre-vulcanization characteristics of the rubber compounds. The minimum viscosity values indicated that F1 and F2 compositions had better processability compared to the control composition (C1). The lower Mooney Scorch values reflected easier mixing and handling during manufacturing, which contributed to improved process safety and efficiency.
Example 2: Shore A Hardness (M2):
The Shore A Hardness of the rubber vulcanizate was measured according to ASTM D2240. The results showed that F1 and F2 compositions achieved hardness values between 62 and 65 Shore A. This range ensured that the compositions maintained adequate durability and wear resistance. The findings confirmed that partially replacing carbon black with walnut shell powder did not compromise the mechanical integrity of the rubber.
Example 3: Dynamic Properties of Rubber Vulcanizate (M3)
The dynamic properties were evaluated using a dynamic mechanical analyzer (DMA), which provided predictive insights into the tyre's performance in specific conditions:
- The F1 and F2 compositions exhibited significantly lower E’ values at -20°C compared to C1, indicating improved traction in snowy conditions.
- The tan delta values at -10°C were higher for F1 and F2 than for C1, demonstrating superior ice traction and enhanced safety on icy surfaces.
- The results showed higher tan delta values at 0°C for F1 and F2, which indicated better wet traction, contributing to improved handling and braking performance in wet conditions.
- The tan delta values at 60°C were lower for F1 and F2 than for C1, reflecting reduced rolling resistance. This improvement translated into better fuel efficiency and energy savings during tyre usage.
Advantages:
The present disclosure provides a composition and preparing a rubber composition that reduces carbon footprint.
The present disclosure provides a composition and preparing a rubber composition that improves winter traction/snow traction along with ice traction, wet traction along with lower rolling resistance (LRR) property.
The present disclosure provides a composition and preparing a rubber composition that provide better processing properties.
The present disclosure provides a composition and preparing a rubber composition that provides a bio filler obtained from renewable resources.
The present disclosure provides a composition and preparing a rubber composition that provides high performance motorcycle tyre tread rubber composition.
The implementation set forth in the foregoing description do not represent all implementations consistent with the subject matter described herein. Instead, they are merely some examples consistent with aspects related to the described subject matter. Although a few variations have been described in detail above, other modifications or additions are possible. In particular, further features and/or variations can be provided in addition to those set forth herein. For example, the implementation described can be directed to various combinations and sub combinations of the disclosed features and/or combinations and sub combinations of the several further features disclosed above. In addition, the logic flows depicted in the accompanying figures and/or described herein do not necessarily require the particular order shown, or sequential order, to achieve desirable results. Other implementations may be within the scope of the following claims.
,CLAIMS:1. A high-performance tire tread rubber composition, comprising:
non-oil extended solution-polymerized styrene-butadiene rubber (S-SBR) in an amount ranging from 50 to 70 phr;
natural rubber (NR) in an amount ranging from 5 to 15 phr;
ultra-high cis polybutadiene rubber (Nd-BR) in an amount ranging from 10 to 30 phr;
carbon black in an amount ranging from 5 to 90 phr;
precipitated silica in an amount ranging from 0 to 50 phr;
walnut shell powder as a bio-filler in an amount ranging from 0.1 to 20 phr;
coupling agent in an amount ranging from 0 to 5 phr;
activators in an amount ranging from 1 to 8 phr;
anti-degradants comprising 6PPD in an amount ranging from 1 to 5 phr and MC wax in an amount ranging from 0.5 to 3 phr;
a vulcanizing agent comprising sulfur in an amount ranging from 1 to 3 phr;
primary accelerators in an amount ranging from 1 to 3 phr; and
hydrocarbon resin ranging from 2 to 4 phr.

2. The high-performance tire tread rubber composition as claimed in claim 1, wherein the non-oil extended solution-polymerized styrene-butadiene rubber (S-SBR) comprises a vinyl content of 55%, a bound styrene content of 20%, and a polymer glass transition temperature (Tg) of -36°C.
3. The high-performance tire tread rubber composition as claimed in claim 1, wherein the ultra-high cis polybutadiene rubber (Nd-BR) is produced by 1,3-butadiene polymerization using a neodymium catalyst with a 1,4-cis content greater than 97%.

4. The high-performance tire tread rubber composition as claimed in claim 1, wherein the carbon black is selected from grades in the N100 series, N200 series, or N300 series.

5. The high-performance tire tread rubber composition as claimed in claim 1, wherein the walnut shell powder has a mesh size between 80 and 100.

6. The high-performance tire tread rubber composition as claimed in claim 1, wherein the coupling agent is selected from bis(3-triethoxysilylpropyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, or mixtures thereof.

7. The high-performance tire tread rubber composition as claimed in claim 1, wherein the activators include zinc oxide and stearic acid.

8. The high-performance tire tread rubber composition as claimed in claim 1, wherein the anti-degradants comprising 6PPD in an amount ranging from 1 to 5 phr and MC wax in an amount ranging from 0.5 to 3 phr.

9. The high-performance tire tread rubber composition as claimed in claim 1, wherein the primary accelerators comprise N-cyclohexyl-2-benzothiazolesulfenamide (CBS) and Diphenylguanidine (DPG).

10. A method for preparing a rubber composition comprising the steps of:
(a) Preparation of Master Batch:
charging a mixing chamber with elastomers and mixing at a rotation speed of 45 to 70 rpm and a head temperature of 75°C to 95°C for 0 to 30 seconds;
adding a bio filler and mixing for 60 to 180 seconds;
adding 100% of a reinforcing filler comprising carbon black, 100% of an inorganic reinforcing filler comprising silica, and a coupling agent, and mixing for 100 to 120 seconds;
adding MC wax, stearic acid, hydrocarbon resin to a mixture obtained and mixed for 30-40 seconds;
conducting silanisation by reducing the rotor speed to 15 to 25 rpm, at a temperature of 120°C to 145°C for 20 to 30 seconds, followed by sweeping down in an orifice and mixing for 40 to 80 seconds;
dumping the rubber compound at a temperature of 150°C to 165°C; sheeting out the rubber compound using a laboratory two-roll mill;
(b) Preparation of Step II Master Batch:
charging the mixing chamber with the master batch prepared in step (a), zinc oxide, and 6PPD, and mixing for 120 to 140 seconds;
dumping the rubber compound at a temperature of 125°C to 140°C; sheeting out the rubber compound using a laboratory two-roll mill;
(c) Preparation of Step II Master Batch:
charging the mixing chamber with the step II master batch and mixing for 120 to 140 seconds;
dumping the rubber compound at a temperature of 125°C to 140°C;
(d) Preparation of Final Batch:
charging the mixing chamber with the step III master batch and curatives comprising sulfur, CBS (N-cyclohexyl-2-benzothiazolesulfenamide), and DPG (Diphenylguanidine), and mixing for 40 to 110 seconds;
dumping the rubber compound at a temperature of 90°C to 110°C; and
performing final sheeting out using a laboratory two-roll mill.