F1ELD OF THE INVENTION:
The present invention relates to a novel functionally graded polymer(s)/polymeric nanocomposite(s) [FGP(S)/FGPNC(s)] having glass transition temperature variation and a process for preparation thereof. This graded materials having a variation of glass transition temperature including other mechanical properties.
BACKGROUND OF THE INVENTION
An important material property often discussed in polymer/elastomer including semiconductor packaging circles is the glass transition temperature, or simply Tg. The some key points about Tg are given below:
1) The glass transition temperature (Tg) of a non-crystalline material is the critical
temperature at which the material changes its behavior from being 'glassy' to being 'rubbery'.
'Glassy' in this context means hard and brittle (and therefore relatively easy to break), while
'rubbery' means elastic and flexible.
2) Again the concept of Tg only applies to non-crystalline solids, which are mostly either
glasses or polymers/rubbers. A glass is defined as a material that has no long-range atomic or
molecular order and is below the temperature at which a no rearrangement of its atoms or
molecules can occur. On the other hand, a rubber/polymer is a non-crystalline solid whose
atoms or molecules can undergo rearrangement.
3) Non-crystalline solids are also known as 'amorphous materials'. Amorphous materials are
materials that do not have their atoms or molecules arranged on a lattice that repeats
periodically in space.
4) At room temperature, hammering a piece of glass will break it, while hammering a piece
of rubber/polymer won't. The rubber/polymer would simply absorb the energy by
momentarily deforming or stretching. However, if the same piece of rubber/polymer is
submerged in liquid nitrogen (LN2), it will behave like brittle glass - easy to shatter with a
hammer. This is because LN2-cooled rubber/polymer is below its Tg.
5) For all amorphous solids, whether glasses, organic polymers, or even metals, Tg is the
critical temperature that separates their glassy and rubbery behaviors.
6) If a material is at a temperature below its Tg, large-scale molecular motion is not possible
because the material is essentially frozen. If it is at a temperature above its Tg, molecular
motion on the scale of its repeat unit (such as a single mer in a polymer) takes place, allowing
it to be 'soft' or 'rubbery'.
7) Since the definition of Tg involves atomic or molecular motion, time does have an effect
on its value, i.e., the mechanical behavior of an amorphous material depends on how fast a
load is applied to it. The faster a load is applied to a material at its Tg, the more glass-like its
behavior would be because its atoms or molecules are not given enough time to 'move.'
Thus, even if an amorphous material is at its Tg, it can break in a 'glass-like' fashion if the
loading rate applied to it is too high.
8) In the semiconductor/automobile industries, knowledge of the Tg's of the various
materials used in packaging (such as die attach materials, molding compounds, and
encapsulating resins) is important not only in optimizing manufacturing processes, but in
understanding the reliability implications of exposure of the products to thermo-mechanical
stresses as well.
In ceramic and metal based functional graded materials, lots of processing methods that developed earlier with slight modifications, are available like thermal spraying, powder metallurgy, coating process, melt processing, etc with certain advantages and disadvantages of each technique [B. Kieback, A. Neubrand and H. Riedel, "Processing techniques for

functionally graded materials", Materials Science and Engineering, A362, (2003) pp 81-105], In polymers, compositional and microstructural gradients are intended to allow an optimum combination of component properties, like surface hardness, wear resistance, impact resistance and toughness. Graded polymers that have been processed so far include graded porosity in polyurethane [H. Piechota, H. Rohr, Integralschaumstoffe, Hanser, Wien, 1975], graded fiber composites [Q. Wang, Z. Huang and S. Ramakrishna, in K. Trumble, K. Bowman, I. Reimanis, and S. Sampath (Eds), Functionally graded materials 2000, Proceedings of the 6th International Symposium on Functionally Graded Materials 2000, Ceramic Transactions 114, American Ceramic Society, Westerville, OH, 2001, pp 89-96], graded interpenetrating polymer networks [Y.S. Lipatov and L.V. Karabanova, J. Materials Science, 30, (1995) pp 2475-2484], graded biodegradable polyesters [C. Schiller, M. Siedler, F. Peters and M. Epple, Functionally graded materials 2000, Ceramic Transactions 114, American Ceramic Society, Westerville, OH, 2001, pp 97-107], graded index polymer fibers and microlenses [S. Sato, T. Nose, S. Masuda, S. Yanase, in W.A. Kaysser (Ed.), Functionally graded materials 1998, Proceedings of the 5th International Symposium on Functionally Graded Materials 1998, Trans Tech Publications, Switzerland, (1999), pp 567-572], polymer alloys [Y. Kano, K. Ishikura, S. Kawahara and S Akiyama, "Analysis of surface segregation in blends of acrylate copolymer with fluoro eopolymer", Polymer Journal, (1992), 24(2), 135-144.], graded crystalline phase on the properties of semicrystalline polymers [Y. Agari, "Development of functionally graded polymer materials", Kagaku Kogyo (1999), 50(8), 630-639] and graded SiC reinforcement in polymer matrix using centrifuging prior to polymerization [N.J. Lee, J. Jang, M. Park, C.R. Choe, J. Materials Science, 32 (1997) pp 2013-2020].
On the other hand, polymeric materials in the industrial field are composites comprising of three dimensional network structures and fillers. However, studies on graded polymers prepared by solid polymer matrix are not known. Again one of the major drawbacks associated with experimental studies is the preparation of FGMs having large scale gradation and also availability of matrix materials in solid form. The present invention discloses graded FGMs comprising of polymer matrix, curing agent (sulfur), accelerator and filler (nano sized amorphous carbon) and a method to prepare the same.
PROBLEM DEFINITION:
Functionally Graded Materials (FGMs) are nonhomogeneous materials in which the material composition varies spatially to optimize the performance of the material for a specific application. With this concept, research into the various aspects of FGMs such as processing, material behavior under different types of loading, fracture mechanics etc., have gained considerable attention.
Conventional polymeric FGMs are prepared from polymer, which are available in liquid form wherein the gradation is carried out by fiber or particles. In this case it is difficult to produce a large-scale gradation. In addition to this it is not possible to produce FGMs in radial direction.
DISADVANTAGES OF THE EXISTING FGMS:

(1) From the application point of view conventional polymers and its composite is
suitable for a narrow range of temperature.
(2) Uniform gradation, both increasing and decreasing order from inner surface to outer
surface and from outer surface to inner surface, and also in radial direction is not
possible till date.
(3) Large scale gradation is not possible in the existing FGMs.
(4) It is not possible to prepare polymeric FGM where the matrix material is available at
solid form at room temperature, 25°C.
OBJECTS OF THE INVENTION
An object of the present invention is to provide a novel functionally graded polymer(s)/polymeric nanocomposite(s) having glass transition temperature variation and a process for preparation thereof.
Another object of the present invention is to provide a novel functionally graded polymer(s)/polymeric nanocomposite(s) having glass transition temperature variation and a process for preparation thereof wherein the glass transition temperature varies with distance. Further object of the present invention is to provide a novel functionally graded polymer(s)/polymeric nanocomposite(s) having glass transition temperature variation and a process for preparation thereof which allows ~25°C graded glass transition temperature. Yet another object of the present invention is to provide a novel functionally graded polymer(s)/polymeric nanocomposite(s) having glass transition temperature variation and a process for preparation thereof wherein the surface, which has a low Tg is suitable for low temperature application whereas the surface having high Tg is suitable for high temperature application. Therefore, the same material can be used for a wider range of temperature. Yet another further object of the present invention is to provide a novel functionally graded po!ymer(s)/po!ymeric nanocomposite(s) having glass transition temperature variation and a process for preparation thereof which overcomes the disadvantages associated with the prior arts.
SUMMARY OF THE INVENTION:
In the present invention functionally graded polymeric materials (FGPs) and functionally graded polymeric nanocomposites (FGPNCs] have been developed.
Another embodiment of the present invention comprising a method to fabricate functionally graded polymers [FGPs] and functionally graded polymeric nanocomposites [FGPNCs] having various shape (Fig I) and gradation using polymer matrix(s), nanosized filler(s), antioxidant(s), accelerator(s), accelerator activator(s), processing oil(s) and curing agent(s). Another embodiment of the present invention comprises various processing oils i.e., paraffinic oil, naphthenic oil, aromatic oil, vegetable oil, and mixture etc which are used to make a novel functionally graded materials. Here the concentration of oil decreases or increases based on the requirement.
Another embodiment of the present invention comprises various carbon nanopatticles (act as reinforcing materials) i.e., N-l10, N-l 15, N-120, N-121, N-125, N-134, N-135, N-212, N-220, N-231, N-234, N-293, N-299, N-315, N-326, N-330, N-335, N-339, N-343, N-347, N-351, N-356, N-358, N-375, N-539, N-550, N-582, N-630, N-642, N-650, N-660, N-683, N-754, N-762, N-765, N-772, N-774, N-787, N-907, N-908, N-990, N-991, etc which are used to make a novel functionally graded polymer nanocomposites. Here the concentration of nanoparticles decreases or increases based on the requirement, but the particle size remains constant in each FGPNCs.

Another embodiment of the present invention comprises various carbon nanoparticles i.e., N-110, N-115, N-120, N-121, N-125, N-134, N-135, N-212, N-220, N-231, N-234, N-293, N-299, N-315, N-326, N-330, N-335, N-339, N-343, N-347, N-351, N-356, N-358, N-375, N-539, N-550, N-582, N-630, N-642, N-650, N-660, N-683, N-754, N-762, N-765, N-772, N-774, N-787, N-907, N-908, N-990, N-991, etc which are used to make FGPNCs. Here, the total volume fraction of carbon nanoparticles in FGPNCs is constant but the particle size of nanoparticles decreases or increases from one surface to the opposite surface. Another embodiment of the present invention comprises various mixed carbon nanoparticles i.e., combination of any two or more following carbons, i.e., N-110, N-l 15, N-120, N-121, N-125, N-134, N-135, N-212, N-220, N-231, N-234, N-293, N-299, N-315, N-326, N-330, N-335, N-339, N-343, N-347, N-351, N-356, N-358, N-375, N-539, N-550, N-582, N-630, N-642, N-650, N-660, N-683, N-754, N-762, N-765, N-772, N-774, N-787, N-907, N-908, N-990, N-991, etc which are also used to make FGPNCs. Here, both concentration and particle size of nanoparticles decreases or increases at a time. Another embodiment of the present invention comprises various silica nanoparticles i.e., precipitated silica (i.e., HS-200, HS-500, HS-700, etc) and fumed silica, which are used to make a novel FGPNCs.
Another embodiment of the present invention comprises nanoclay, which is used to make a novel FGPNCs.
Another embodiment of the present invention comprises various mixed nanoparticles i.e., combination of any one of the following carbons, i.e., N-l 10, N-115, N-120, N-121, N-125, N-134, N-135, N-212, N-220, N-231, N-234, N-293, N-299, N-315, N-326, N-330, N-335, N-339, N-343, N-347, N-351, N-356, N-358, N-375, N-539, N-550, N-582, N-630, N-642, N:650, N-660, N-683, N-754, N-762, N-765, N-772, N-774, N-787, N-907, N-908, N-990, N-991, etc, and silica (precipitated and fumed) or clay, which are also used to make FGPNCs.
Another embodiment of the present invention comprises various polymer matrixes i.e., natural rubber, styrene-butadiene rubber, polybutadiene rubber, polyisoprene rubber, ethylene propylene rubber, butyl rubber, halobutyl rubber, nitrile rubber, polyacrylic rubber, neoprene rubber, hypalone rubber, silicone rubber, fluorocarbon rubber, polyurethane rubber, etc, which are used to make a novel FGPs and FGPNCs.
Another embodiment of the present invention comprises various mixed polymer matrixes i.e., combination of any two or more of the following rubbers, i.e., natural rubber, styrene-butadiene rubber, polybutadiene rubber, polyisoprene rubber, ethylene propylene rubber, butyl rubber, halobutyl rubber, nitrile rubber, polyacrylic rubber, neoprene rubber, hypalone rubber, silicone rubber, fluorocarbon rubber, polyurethane rubber, etc, which are used to make a novel FGPs and FGPNCs.
Another embodiment of the present invention is having various geometries i.e., rectangular, cylindrical, complex geometry, etc which are used to make a novel FGPs and FGPNCs using template.
Another embodiment of the present invention is having various hollow geometries i.e., rectangular, cylindrical including complex irregular geometry which are used to make a novel FGPNCs using template.
Another embodiment of the present invention is having the gradient in properties i.e., modulus, hardness, tensile strength, elongation at breaking point, tear strength, strain energy density, hysteresis loss, work released during retraction, etc which are made in both directions.

RIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
Further objects and advantages of this invention will be more apparent from the ensuing
description when read in conjunction with the accompanying drawings and wherein:
Fig. 1: Schematic diagrams of functionally graded polymers (FGPs) and functionally graded
polymer nanocomposites (FGPNCs), where concentration varies from one surface to the
opposite surface.
Fig. 2: (a) Variation of heat flow with temperature for different layers of functionally graded
polymers. The change in slope is the glass transition temperature, (b) Variation of glass
transition temperature with distance.
Fig. 3: Thermal stability of different layers of (a) unfilled FGP (functionally graded polymer) and (b) 40 wt% (with respect to 100 polymer) nano sized amorphous carbon filled FGPNCs (functionally graded polymer nanocomposites).
Fig. 4: Derivative of weight loss curve of different layers of (a) unfilled FGP and (b) 40 wt% (with respect to 100 polymer) nano sized amorphous carbon filled FGPNCs (functionally graded polymer nanocomposites). The peak will give the decomposition temperature:
Fig.5: Variation of hardness and specific gravity with distance of a) FGP and b) 40 wt% (based on 100 polymer) nano sized amorphous carbon.
Fig. 6: Variation of stress-elongation profile of a) graded polymer and b) 40 phr (%) nanosized amorphous carbon filled graded nanocomposites.
Fig. 7: Variation of strain energy-elongation profile of a) graded polymer and b) 40 phr (%) nanosized amorphous carbon filled graded nanocomposites.
Fig. 8: Variation of tensile strength and elongation at break profile with distance of a) graded polymer and b) 40 phr (%) nanosized amorphous carbon filled graded nanocomposites.
Fig. 9: Variation of modulus @100 % and 200 % with distance of a) graded polymer and b) 40 phr (%) nanosized amorphous carbon filled graded nanocomposites.
Fig. 10 Variation of tear strength and elongation at break profiles of the a) FGPs and b) 40 wt% (with respect to 100 polymer) carbon black filled FGPNCs due to varied oil content along thickness.
DETAILED DESCRIPTION OF THE INVENTION WITH REFERENCE TO ACCOMPANYING DRAWINGS:
The different steps for preparation of functionally graded polymeric materials are as follows: Conditioning of Materials
All materials except oil are kept in an oven at a temperature of 60-100°C for 1-6 hours to remove moisture. The polymers and nanomaterials are weighed within a tolerance of ±lg and all other chemicals are weighed within a tolerance of ±0.1 g accuracy.
Mixing
Mixing of all chemicals in polymer matrix is carried out using two-roll mill at a temperature of 50 to 125°C according to the type of polymer. The speed of front roll is in between 10 to 34 rpm and friction ratio between front and rear roll is 1:1.1 to 1: 1.5. The clearance between

(Table Removed)
In these formulations the amount of metal oxide(s), acid(s), antioxidant(s), accelerator(s) and curing agent(s) are in the range of 0.1 to 12 wt% (with respect to 100 polymer). Only the major variable is amount and type of nanomaterial(s) and processing oil(s). Nanomaterial(s) vary from 0 to 80 wt% (with respect to 100 polymer) and the processing oil(s) varies from 0 to 100 wt% (with respect to 100 polymer). During mixing, at first polymer is fed into the nip gap of two roll to get a thin sheet. Then antioxidant(s) in powder form is added slowly followed by acid. The batch is cut % of the distance across the roll with the help of a knife with the knife at this position until the bank just disappears. This process is continued for approx. 10 minutes. Then nanomaterial(s) are added evenly across the mill at a uniform rate. Processing oil(s) are added with and without nanomaterial(s) to get a good distribution of nanomaterial(s) into the matrix. The materials falling through the nip is collected carefully from the tray and returned back to the mix. The mixing cycle is concluded by passing the rolled batch endwise through the mill six to eight times with an opening of 0.2 mm to improve the dispersion. Finally the mixed compound is passed four times through the mill at a setting of 0.1 mm, folding it back on itself each time. The batch is removed and kept on the glass sheet, in a closed container to prevent absorption of moisture from the air for about 24 hours. After 24 hours accelerator followed by curing agent is added according to the procedure mentioned above.

A thin uncured layer -0.1 mm (even less than 0.1 mm) of the mix is prepared by pressing in between two teflon sheets in the hydraulic press (for few seconds). The inner surfaces of the teflon sheets are coated with coating agent for easy removal of the layer. The volume (thickness) of all the layers of different mixes is made equal by taking different amount of mixes according to the specific gravity of the chemicals. All these layers of different mixes are stacked sequentially with increasing/decreasing amount of nanomaterials in each layer to form green FGPs and FGPNCs.
Curing
Curing is carried out in the hydraulic press. The green FGPs and FGPNCs are cut into pieces according to the dimension of the mold cavity using template. Before putting the green FGPs and FGPNCs in the mould cavity, the molding surfaces are polished and cleaned with

distilled water and again coated with mould releasing agent. The mold is kept at a curing temperature of 100 to 250°C within ± 0.5°C depending on the type of base polymer in the closed press, held at this temperature for at least 20 minute before the green FGPs and FGPNCs are inserted. The temperature of the mold is controlled by means of the temperature controller attached with the press. The press is opened the green FGPs and FGPNCs are inserted into the mold, and the press is closed in the minimum time possible to prevent the excessive cooling of the mold by contact with cool metal surfaces or by exposure to air drafts. A pressure of 1 to 20 MPa is applied and three bumping is given to remove the air bubbles present, if any for equal time of 15 sec. Finally a desired pressure is applied and the mold is held for 10 minutes to 8 hours in the press. As soon as the press is opened the cured FGPs and FGPNCs from the mold is removed and cooled in water for 10 to 15 min. The cured FGPs and FGPNCs are conditioned at a temperature of 23±2°C for at least 16 hours before preparing the samples and testing.
This invention provides a functionally graded polymers (FGPs) and functionally graded polymer nanocomposites (FGPNCs) having a gradation of glass transition temperature, comprising a polymer(s) matrix, nanomaterial(s), processing oil(s) and other chemicals i.e., antioxidant(s), accelerators), accelerator activator(s), and curing agent(s).
A process for preparation of a FGPs and FGPNCs comprising the steps of: -oil(s) as per user requirement (varies from 1 to 100% by weight, with respect-to 100
polymer) and/or nanomaterial(s) as per user requirement (varies from 1 to 80% by weight,
with respect to 100 polymer) and all other chemicals (wt% percentage is constant for
these chemicals) are imbedded in the polymer(s) matrix at the semisolid state (i.e., above
the glass transition temperature but below the melting point of polymer) by the
conventional two roll mixing mill, -a thin layer -0.1 mm is prepared from the oil(s) imbedded polymer(s) matrix again by two
roll mill and hydraulic press at the semisolid state -this thin oil(s) imbedded polymer(s) matrix is optionally coated by coating agent (i.e.,
silicone spray, soap solution, silicone emulsion solution, stearic acid, polytetrafluoro
ethylene, polyvinyl alcohol, etc) - this thin coated/uncoated oil(s) imbedded polymer matrix is cut into the required size
using template -the cut piece is laminated either increasing or decreasing order as per requirement (shown
in Fig 1) to get green functionally graded polymers and/or functionally graded polymer
nanocomposites -the green graded sheet is kept in the coated mould (coating of the mould is done by any
one of these silicone spray, soap solution, silicone emulsion solution, stearic acid,
polytetrafluoro ethylene, polyvinyl alcohol) -the mould with green graded sheet is cured for a certain period of time at a specified
temperature and pressure to get a cure FGP and/or FGPNCs (temperature is applied from
one or both sides that depends on the type of FGP and/or FGPNCs as shown in Fig 1) -the cured FGP and/or FGPNCs is removed from the mould after curing and cooled in room
temperature and detained for 24 hours for further characterization.
The polymer matrix is selected from the group comprising of natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene rubber, ethylene-propylene diene-monomer rubber, butyl rubber, halobutyl rubber, nitrile rubber,
hydrogenated nitrile rubber, polysulfide rubber, polyacrylic rubber, neoprene rubber, hypalon rubber, silicone rubber, fluorocarbon rubber, polyurethane rubber, thermoplastic elastomer, and mixture thereof.
The polymer matrix natural rubber is selected from the group comprising of standard malaysian rubber (SMR) L, SMR CV, SMR WF, SMR GP, SMR LV, SMR 5, SMR 10, SMR 20, SMR 50, technically specified rubbers (TSR) 5, TSR 10, TSR 20, TSR 50, technically classified rubber, oil extended natural rubber, deproteinized natural rubber, peptized natural rubber, skim natural rubber, superior processing natural rubber, heveaplus MG rubber, epoxidized natural rubber, thermoplastic natural rubber, and mixture thereof; the polymer matrix styrene-butadiene rubber is selected from the group comprising of solution styrene-butadiene rubber i.e., SBR 2305, SBR 2304, emulsion styrene-butadiene rubber i.e., cold SBR 1500, cold SBR 1502, hot SBR 100, and mixture thereof; the polymer matrix polybutadiene rubber is selected from the group comprising of cisamer-01, cisamer!220, BR 9000, BR 9004A, BR 9004B, low molecular weight 1, 3 polybutadiene, and mixture thereof; the polymer matrix butyl rubber is selected from the group comprising of IIR-1751, IIR-1751F, IIR-745, Exxon butyl 007, Exxon butyl 065, Exxon butyl 068, Exxon butyl 165, Exxon butyl 268, Exxon butyl 269, Exxon butyl 365, polysar butyl 100, polysar butyl 101, polysar butyl 101-3, polysar butyl 301, polysar butyl 402, and mixture thereof; the polymer matrix ethylene-propylene rubber is selected from the group comprising of dutral-CO-034, dutral-CO-038, dutral-CO-043, dutral-CO-054, dutral-CO-058, dutral-CO-059, dutral-CO-055, and mixture thereof; the polymer matrix ethylene-propylene-diene-monomer rubber is selected from the group comprising of ethylene-propylene-dicyclopentadiene rubber, ethylene-propylene-ethylidenenorbornene rubber, ethylene-propylene-1,4 hexadiene rubber, and mixture thereof; the polymer matrix halobutyl rubber is selected from the group comprising of Exxon chlorobutyl 1065, Exxon chlorobutyl 1066, Exxon chlorobutyl 1068, Polysar chlorobutyl 1240, Polysar chlorobutyl 1255, Exxon bromobutyl 2222, Exxon bromobutyl 2233, Exxon bromobutyl 2244, Exxon bromobutyl 2255, Polysar bromobutyl X2, Polysar bromobutyl 2030, and mixture thereof; the polymer matrix nitrile rubber is selected from the group comprising of Krynac-2750, Nipol-1053, Nipol-1032, Paracril-C, Chemigum-N-3, Krynac-5075, and mixture thereof; the polymer matrix hydrogenated nitrile rubber is selected from the group comprising of zetpol-1010, zetpol-1020, zetpol-2010, zetpol-2020, and mixture thereof; the polymer matrix polyacrylic rubber is selected from the group comprising of hycar-4051, hycar-4052, hycar-4054, vamac-B-124, and mixture thereof; the polymer matrix neoprene rubber is selected from the group comprising of neoprene-AC, neoprene-AD, neoprene-ADG, neoprene-AF, neoprene-AG, neoprene-FB, neoprene-GN, neoprene-GNA, neoprene-GRT, neoprene-GS, neoprene-GW, neoprene-W, neoprene-W-MI, neoprene-WB, neoprene-WD, neoprene-WHY, neoprene-WHY-100, neoprene-WHV-200, neoprene-WHV-A, neoprene-WK, neoprene-WRT, neoprene-WX, neoprene-TW, neoprene-TW-100, neoprene-TRT, and mixture thereof; the polymer matrix hypalon rubber is selected from the group comprising of hypalon-20, hypalon-30, hypalon-LD-999, hypalon-40S, hypalon-40, hypalon-4085, hypalon-623, hypalon-45, hypalon-48S, hypalon-48, and mixture thereof; the polymer matrix silicone rubber is selected from the group comprising of silicone MQ, silicone MPQ, silicone MPVQ, silicone FVQ, and mixture thereof; the polymer matrix fluorocarbon rubber is selected from the group comprising of viton-LM, viton-C-10, viton-A-35, viton-A, viton-A-HF, viton-E-45, viton-E-60, viton-E-60C, viton-E403, viton-B-50, viton-B, viton-B-70, viton-910, viton-GLT, viton-GF, viton-VTR-4730, DAI-EL-G-101, DAI-EL-701, DAI-EL-751, DAI-EL-702, DAI-EL-704, DAI-EL-755, DAI-EL-201,
DAI-EL-501, DAI-EL-801, DAI-EL-901, DAI-EL-902, tecnoflon-FOR-LHF, tecnoflon-NMLB, tecnoflon-NML, tecnoflon-NMB, tecnoflon-NM, tecnoflon-NH, tecnoflon-FOR-45-45BI, tecnoflon-FOR-70-70BI, tecnoflon-FOR-45-C-CI, tecnoflon-FOR-60K-KI, tecnoflon-FOR-50E, tecnoflon-TH, tecnoflon-TN-50, tecnoflon-TN, tecnoflon-FOR-THF, tecnoflon-FOR-TF-50, tecnonon-FOR-TF, fluorel-2145, fluorel-FC-2175, fluorel-FC-2230, fluorel-FC-2178, fluorel-FC-2170, fluorel-FC-2173, fluorel-FC-2174, fluorel-FC-2177, fIuorel-FC-2176, fluorel-FC-2180, fluorel-FC-81, fluorel-FC-79, fluorel-2152, fluorel-FC-2182, fluorel-FC-2460, fluorel-FC-2690, fluorel-FC-2480, and mixture thereof, the polymer matrix polyurethane rubber (poJyether and polyester type) is selected from the group comprising of FMSC-1035, FMSC-1035T, FMSC-1040, FMSC-1050, FMSC-1060, FMSC-1066, FMSC-1070, FMSC-1075, FMSC-1080-SLOW, FMSC-1080-FAST, FMSC-1085, FMSC-1090-FAST, FMSC-1090-SLOW, and mixture thereof; the polymer matrix thermoplastic elastomer (polyurethane, polyester, polyamide, styrene-butadiene-styrene, blends, etc) is selected from the group comprising of SBS 1401, SBS 4402, SBS 4452, SBS 1301, SBS 1401-1, SBS 4303, estane-55103, hytrel-40xy, hytrel-63xy, hytrel-72xy, gaflex-547, pebax-2533, pebax-6333, TPR-1600, TPR-1900, TPR-2800, TELCAR-340, SOMEL-301, SOMEL-601, santoprene, cariflex-TR, solprene-400, stereon, and mixture thereof; the polymer matrix polysulfide elastomer is selected from the group comprising of thiakol-A, thiakol-B, thiakol-FA, thiakol-ST, and mixture thereof;
The polymer matrix natural rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, diurethane, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix styrene-butadiene rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, diurethane, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix polybutadiene rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, diurethane, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix butyl rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, diurethane, p-quinone dioxime, p-quinone dioxime dibenzoate, phenol-formaldehyde resin, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix ethylene-propylene rubber is cured by vulcanizing agent selected from the group comprising of hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane, bis(2,4-dichloro-benzoyl) peroxide, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix ethylene-propylene-diene-monomer rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, diurethane, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix halobutyl rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, zinc oxide, p-quinone dioxime, p-quinone dioxime dibenzoate, phenol-formaldehyde resin, amine, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix nitrile rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix hydrogenated nitrile rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide,

dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane, bis(2,4-dichloro-benzoyl) peroxide, tertiary butyl perbenzoate, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix polyacrylic rubber is cured by vulcanizing agent selected from the group comprising of amine, diamine, activated thiol, sulphur, thiourea, trithiocyanuric acid, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix neoprene rubber is cured by vulcanizing agent selected from the group comprising of magnesium oxide, zinc oxide, lead oxide, iron oxide, titanium oxide, amine, phenol, sulfenamide, thiazoles, thiuram, thiourea, guanidine, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix hypalon rubber is cured by vulcanizing agent selected from the group comprising of magnesium oxide, zinc oxide, lead oxide, iron oxide, titanium oxide, sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, N,N'-m-phenylenedimaleimide, amine, phenol, sulfenamide, thiazoles, thiuram, thiourea, guanidine, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix silicone rubber is cured by vulcanizing agent selected from the group comprising of hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane, bis(2,4-dichloro-benzoyl) peroxide, tertiary butyl perbenzoate, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix fluorocarbon rubber is cured by vulcanizing agent selected from the group comprising of hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane, bis(2,4-dichloro-benzoyl) peroxide, tertiary butyl perbenzoate, hexamethylenediamine carbamate, bis(cinnamylidene) hexamethylenediamine, hydroquinone, 4-4'-isopropylidene bisphenol or mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix polyurethane rubber (polyether and polyester type) is cured by vulcanizing agent selected from the group comprising of 1,4-butanediol, 1,4-cyclohexanedimethanol, l,4-bis(2-hydroxyethoxy) benzene, 4,4'methylene-bis(2-chloroaniline), and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix thermoplastic elastomer (polyurethane, polyester, polyamide, styrene-butadiene-styrene, blends, etc) is cured by vulcanizing agent selected from the group comprising of lead oxide, cadmium oxide, zinchydroxide, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane, bis(2,4-dichloro-benzoyl) peroxide, tertiary butyl perbenzoate, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); and the polymer matrix polysulfide elastomer is cured by vulcanizing agent selected from the group comprising of lead oxide, cadmium oxide, zinchydroxide, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane, bis(2,4-dichloro-benzoyl) peroxide, tertiary butyl perbenzoate, hexamethylenediamine carbamate, bis(cinnamylidene) hexamethylenediamine, hydroquinone, 4-4'-isopropylidene bisphenol, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer).
The polymer matrix comprising of either natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene rubber, ethylene-propylene diene monomer rubber, butyl rubber, halobutyl rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide elastomer, polyacrylic rubber, neoprene rubber, hypalon rubber, silicone rubber, fluorocarbon rubber, polyurethane rubber, thermoplastic elastomer and/or mixture thereof is graded by carbon nanoparticles selected from the group comprising of N-l10, N-l 15, N-120,

N-121, N-125, N-134, N-135, N-212, N-220, N-231, N-234, N-293, N-299, N-315, N-326, N-330, N-335, N-339, N-343, N-347, N-351, N-356, N-358, N-375, N-539, N-550, N-5S2, N-630, N-642, N-650, N-660, N-683, N-754, N-762, N-765, N-772, N-774, N-787, N-907, N-908, N-990, N-991, and mixture thereof which is in the range of 0 to 80 wt% (with respect to 100 polymer).
The polymer matrix comprising of either natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene rubber, ethylene-propylene diene monomer rubber, butyl rubber, halobutyl rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide elastomer, polyacrylic rubber, neoprene rubber, hypalon rubber, silicone rubber, fluorocarbon rubber, polyurethane rubber, thermoplastic elastomer and/or mixture thereof is further graded by various silica nanoparticles i.e., precipitated silica (i.e., HS-200, HS-500, HS-700, etc), fumed silica and mixture thereof which is in the range of 0 to 80 wt% (with respect to 100 polymer).
The polymer matrix comprising of either natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene rubber, ethylene-propylene diene monomer rubber, butyl rubber, halobutyl rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide elastomer, polyacrylic rubber, neoprene rubber, hypalon rubber, silicone rubber, fluorocarbon rubber, polyurethane rubber, thermoplastic elastomer and/or mixture thereof is further graded by clay nanoparticles which is in the range of 0 to 80 wt% (with respect to 100 polymer).
The polymer matrix comprising of either natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene rubber, ethylene-propylene diene monomer rubber, butyl rubber, halobutyl rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide elastomer, polyacrylic rubber, neoprene rubber, hypalon rubber, silicone rubber, fluorocarbon rubber, polyurethane rubber, thermoplastic elastomer and/or mixture thereof is further graded by mixed carbon nanoparticles, nanosilica and nanoclay in a volume ratio of 5:2:1 to 1:2:5 selected from the group comprising of N-l 10, N-115, N-120, N-121, N-125, N-134, N-135, N-212, N-220, N-231, N-234, N-293, N-299, N-315, N-326, N-330, N-335, N-339, N-343, N-347, N-351, N-356, N-358, N-375, N-539, N-550, N-582, N-630, N-642, N-650, N-660, N-683, N-754, N-762, N-765, N-772, N-774, N-787, N-907, N-908, N-990, N-991, precipitated silica (i.e., HS-200, HS-500, HS-700, etc), fumed silica, clay and mixture thereof.
The polymer matrix comprising of either natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene rubber, ethylene-propylene diene monomer rubber, butyl rubber, halobutyl rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide elastomer, polyacrylic rubber, neoprene rubber, hypalon rubber, silicone rubber, fluorocarbon rubber, polyurethane rubber, thermoplastic elastomer and/or mixture thereof is further graded by mixed carbon nanoparticles having same concentration gradient but different particle size i.e 5 to 85 nm and selected from the group comprising of N-l 10, N-115, N-120, N-121, N-125, N-134, N-135, N-212, N-220, N-231, N-234, N-293, N-299, N-315, N-326, N-330, N-335, N-339, N-343, N-347, N-351, N-356, N-358, N-375, N-539, N-550, N-582, N-630, N-642, N-650, N-660, N-683, N-754, N-762, N-765, N-772, N-774, N-787, N-907, N-908, N-990, N-991.
The curing of polymer matrix comprising of either natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene rubber, ethylene-propylene diene monomer rubber, butyl rubber, halobutyl rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide elastomer, polyacrylic rubber, neoprene rubber, hypalon rubber, silicone rubber, fluorocarbon rubber, polyurethane rubber, thermoplastic elastomer and/or mixture thereof is further accelerated by accelerator selected from the group comprising of tert-buttylbenzthiazyl sulphonamide, benzthiazyl 2-sulphenmorpholide, dicyclohexyl benzthiazyl sulphonamide, N-cyclohexyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole, 2,2'dibenzothiazyl disulfide, tetramethylthiuram disulfide, zinc dimethyldithiocarbamate, zinc dibutyldithiocarbamate, 4,4'dithiodimorpholine, tellurium diethyldithiocarbamate, dipentamethylene thiuramhexasulfide, tetramethylthiuram monosulfide, ferricdimethyldithiocarbamate, zinc mercaptobenzthiazole, zinc 0,0 dibutylphosphorodithioate, zinc diethyldithiocarbamate, 4-4'dithio dimorpholine, which is in the range of 0.1 to 12 wt% (with respect to 100 polymer) and , and mixture thereof in a ratio of 1 : 9 to 9:1 (by weight).
The curing of polymer matrix comprising of either natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene rubber, ethylene-propylene diene monomer rubber, butyl rubber, halobutyl rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide elastomer, polyacrylic rubber, neoprene rubber, hypalon rubber, silicone rubber, fluorocarbon rubber, polyurethane rubber, thermoplastic elastomer and/or mixture thereof is further accelerated by accelerator activator selected from the group comprising of metal oxide and acid which is in the range of 10:1 to 1:10 wt% (with respect to 100 polymer).
The metal oxide used in accelerator activator is selected from the group comprising of zinc oxide, lead oxide, calcium oxide, magnesium oxide, lead oxide, etc which is in the range of 0.1 to 12 wt% (with respect to 100 polymer).
The acid used in accelerator activator is selected from the group comprising of stearic acid, palmitic acid, oleic acid, etc which is in the range of 0.1 to 12 wt% (with respect to 100 polymer).
The FGPs and FGPNCs further comprises an antioxidant selected from the group comprising of condensation product of acetone and diphenyl-amine, phenyl-beta-napthylamine, blends of diphenyl-p-phenylene diamine and selected arylamine derivatives, blend of arylamines, polymerized 1,2 dihydro 2,2,4-trimethyl quinoline, N-(l,3-dimethylbutyl)-N'-phenyl-p-phenylene-diamine, diaryl para phenylene diamines, 2 mercaptobenzimidazole, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer). The FGPs and FGPNCs further comprises a process oil selected from the group comprising of paraffinic oil, naphthenic oil, aromatic oil, vegetable oil, and mixture thereof which is in the range of 0 to 100 wt% (with respect to 100 polymer).
The nanoparticles and other chemicals imbedded polymer matrix is prepared by mixing the polymer and other compounding ingredients by conventional methods such as open roll mixing using two roll mill and internal mixing kneader, intermix and banbary mixer. Thin polymer layer (before curing) is prepared by two roll mill at a temperature range from about 50°C to about 125°C depending on the type of rubber, and at a friction ratio from about 1:1.1 to about 1:1.5 to selectively produce a thin layer within the range of 0.1 to 10 mm in thickness.

The thin polymer layer is coated by one or more coating agent selected from the group comprising of polytetrafluoro ethylene, polyvinyl alcohol, silicone emulsion and detergent/soap solution.
The green graded material is prepared by laminating of thin polymer layer to produce a rectangular sheet having a thickness within the range of 2 to 1000 mm or unlimited in higher side, or cylindrical shape having a diameter within the range of 10 to 100 mm or unlimited in higher side
The green graded material of rectangular/cylindrical shape as Claimed in 20 is cured by hydraulic press in the temperature range of 100°C to about 250°C, time in the range of 10 minutes to about 8 hours and pressure in the range of 1 MPa to about 20 MPa. The wt fraction of oils is varied within the range of 1 to 100% from the inner surface to outer surface (Figl) or from outer surface to inner surface (Figl) or from outer surface to outer surface i.e., opposite surface (Fig 1).
The orifice both regular and irregular, i.e., complex geometry including its dimension (as shown in Figl) are made from one surface to the opposite surface using template; and the concentration of oils at the inner surface could be varied from 0 to 100% by wt% (with respect to 100 polymer) (maximum) depending on the requirement; and the dimension of orifice could be varied using template.
Specific gravity
Specific gravity of FGPs and FGPNCs is measured by the specific gravity balance.
Hardness
Shore A type durometer is used to measure the hardness of FGPs and FGPNCs. The method adopted is the same as that of ASTM D2240-81.
Modulus, Tensile Strength and Elongation at Break
Modulus, tensile Strength and elongation at break are determined according to the ASTM D412-80 test method using dumbbell shaped specimens. Samples are punched along the mill grain direction from the cured sheet using ASTM type dumbbell cutting die. The thickness of the narrow portion of the specimen is measured using a bench thickness guage. The tests are carried out in Zwick Universal Testing Machine (UTM) interfaced with a computer. All tests are carried out at 500 mm/min. cross head speed. The tests at elevated temperatures are done using a temperature cabinet equipped with a temperature controller. The modulus and tensile strength are reported in MPa and the elongation break in percentage.
Tear Strength
Tear strength is measured in Zwick (UTM) using unnotched 90° angled tear test specimen (die C) as per ASTM D 624-73. The samples are punched out from the molded sheet of FGPs and FGPNCs. The speed of crosshead is adjusted to 500 mm/min.
Thermal Analysis and Glass Transition Temperature
Thermal analyses of FGPs and FGPNCs are done with Perkinelmer Diamon DSC instrument to calculate the glass transition temperature (Tg). The scanning rate is 10°C/miri from -90 to 200°C. Nj gas is used as an inert atmosphere. Before, DSC run, instrument is calibrated from 30 to 250°C using indium (T°m=156.6°C and ∆H°f=28.5 J/g) and zinc (T°m=419.47°C and

∆H°f=23.01 J/g). All the samples are encapsulated inside the Al pan and lid with mass of-5±0.1 mg for each experiment.
Thermogravimetric Analysis
The FGPs and FGPNCs are dried for 72 hrs in vacuum drier at 40°C before doing TGA. The TGA thermograms are obtained by using Perkin-Elmer TGA instrument (Pyris Diamond TG/DTA) under a dynamic nitrogen gas atmosphere of 200ml/min flow rate, with heating rate of 5°C, 10°C and 15°C/min from 35°C to 600°C. The sample weights are kept 2.5 ± 0.2 mg and a-A^Os is used as reference materials.
As the glass transition temperature is sensitive to the molecular interactions, measurement of the glass transition can therefore be used to determine the structural changes occurring in the material by changing the oil content in it. So in order to obtain a clear understanding of glass transition temperature of the vulcanizates, differential scanning calorimetry is performed as it measures the amount of energy absorbed during the glass transition. Nanomaterials hardly affects the glass transition. So the glass transition temperatures of unfilled functionally graded materials along the thickness is preferred to measure and the DSC scans show the shift in the glass transition temperatures for vulcanizates containing various oil content as shown in Fig.2(a). With increasing oil concentration, the glass transition temperature is decreasing. With the variation of oil from 0 to 80% by weight (with respect to 100 polymer), .the glass transition decreases in styrene butadiene polymer from -58 to -77°C. Glass transition temperature values of functionally graded materials due to the various oil contents in SBR are shown in Table 2.
Fig. 2(b) shows the dependence of the glass transition temperature on the oil content in SBR vulcanizates. As the oil content in SBR is increased, glass transition temperature is decreased. With the increment of oil content from 0 to 100 wt% (with respect to the 100 polymer), glass transition decreases from -57 to -80°C respectively.

decomposition temperature of the functionally graded materials containing different amounts of oil is not known. To know the thermal limits of the compound to prevent the thermal aging, thermo-gravimetric analysis (TGA) is performed using Perkin Elmer Instruments Pyris Diamond TG/DTA. Samples are extracted from the sheeted compound with a mass ranging
(Table Removed)

from 7 to 14 mg. The tests are run in a nitrogen atmosphere from room temperature to 520°C with a heating rate of 10°C/min. The results of the TGA are shown in Fig 3. The Fig. 3(a) shows the percentage mass retention as a function of temperature for unfilled functionally graded materials containing different amounts of oil. The curve that looks separate from all other curves corresponds to the oil used. The thermal decomposition of the compounds begins at around 135°C (can be clearly visible in Fig. 3(a)) and completes at around 480°C. Mass retention of the pure SBR (styrene butadiene rubber) without oil at 500°C is the highest and is 6.4 %. With increasing oil content, mass retains less. With 100 wt% oil (with respect to 100 polymer) addition, mass retention at 500°C is 3.2 %. The mass loss values at 350°C corresponding to pure SBR without oil and SBR with 100 wt% (with respect to 100 polymer) oil are 8.8 % and 43 % respectively. Oil decomposes completely at 400°C. Oil present in SBR starts decomposing at 135°C and mass loss of SBR with higher amounts of oil is higher at a given temperature. Pure SBR vulcanizate without oil retains it's mass till 200°C.
Similarly, the Fig. 3(b) shows the percentage mass retention as a function of temperature for 40 wt% (with respect to 100 polymer) nanosized carbon black filled FGPNCs containing varied amounts of oil. The thermal decomposition of the compounds begins at around 135°C and completes at around 500°C. Mass retention of the SBR without oil at 500°C is the highest and is 29.2%. With increasing oil content, mass retains less. With 100 wt% (with respect to 100 polymer) oil addition, mass retention at 500°C is 18.3 %. The mass loss values at 350°C corresponding to SBR without oil and SBR with 100 wt% (with respect to 100 polymer) oil are 9 % and 36.3 % respectively. Oil decomposes completely at 400°C. Oil present in SBR starts decomposing at 135°C and mass loss of SBR with higher amounts of oil is higher at a given temperature. SBR vulcanizate without oil retains it's total mass till 200°C.
The first derivative of a real time weight curve for unfilled FGPCs is shown in Fig. 4(a). The maximum rate of mass loss of the oil is 8.25 %/min at 318.5°C. The maximum rate of pure SBR decomposition is 12.86 %/min at 453°C. With increasing oil content in SBR from 10 to 100 wt% (with respect to 100 polymer), the temperature at maximum mass loss rate due to oil decomposition in the vulcanizates is changing from 260 to 300°C and the corresponding values of mass loss rate values are 1.35%/min and 3.6%/min. The maximum rate of SBR decomposition in the vulcanizates containing 0 and 100 wt%(with respect to 100 polymer) oil is 12.86 and 6.6 %/min at 451°C. The mass loss rate of SBR containing 100 wt% (with respect to 100 polymer) oil is less as the mass fraction of oil in the vulcanizate is high and oil in SBR decomposes totally at 400°C.
Similarly, the first derivative of a real time weight curve for filled FGPNCs is shown in Fig. 4(b). The maximum rate of decomposition of SBR with 40 wt% (with respect to 100 polymer) nanosized carbon black is 10.3 %/min at 452°C. With increasing oil content in SBR from 10 to 100 wt% (with respect to 100 polymer), the temperature of maximum mass loss rate due to oil decomposition is shifting from 261 to 302°C and the corresponding values of maximum loss rate are 1.05 %/min and 3.0 %/min. The maximum rate of SBR decomposition containing 100 wt% (with respect to 100 polymer) oil is 5.8 %/min at 453°C.
Hardness of the functionally graded polymer is measured (shown in Fig (5)) along the thickness direction to understand its performance in structural applications. The gradation is made with increasing oil content in SBR along the thickness direction. The wt% of oil is varied from 0 to 80wt% (with respect to 100 polymer) along the distance. Fig. 5(a)

demonstrates that hardness decreases with increasing distance from one end to the opposite end in the unfilled functionally graded polymer. Its magnitude drop-offs from 51 to 13 shore A. The decrease in hardness is attributed to the increase in oil content along the distance. Because of the increase in the oil content along the thickness, specific gravity also decreases as the specific gravity of oil (0.86) is lesser than SBR (0.93). To understand the effect of hardness, specific gravity is also computed along the thickness direction. Specific gravity decreases linearly along distance from 0.98 to 0.92. Hardness decreases significantly by 75 % while the decrease in specific gravity is only 8%. As many applications involve the particulate reinforcement, uniformly dispersed nanosized carbon black filled FGPNCs are also prepared with oil content varied from 0 to 100 wt% (with respect to 100 polymer) along the thickness. Fig. 5(b) demonstrates the change in hardness and specific gravity of the filled FGPNCs along the thickness of the sheet. Both the parameters decrease with increasing distance from one end to the opposite end. The magnitude of hardness steps down from 74 to 14 shore A. The decrease in hardness is attributed to the increase in oil content along the distance. Because of the increase in the oil content along the thickness, specific gravity also decreases as the specific gravity of oil (0.86) is lesser than SBR (0.93). To understand the effect of hardness, specific gravity is also computed along the thickness direction. Specific gravity decreases along distance from 1.12 to 1. Hardness decreases significantly by 81 % while the decrease in specific gravity is only 11%.
Now it is necessary to know the variation of mechanical properties i.e. strain energy at various deformations/elongations, tensile strength, elongation at breaking point, tear strength, hysteresis loss, strain energy during deformation, etc in FGPNCs for evaluation of these graded materials in structural applications.
With variation of the oil content along the thickness direction, all these mechanical properties vary. One can see the stress-strain/elongation profile of unfilled FGPs at different distances from one end to the opposite end as shown in Fig. 6(a). With increasing oil content along the thickness in FGPs, tensile strength decreases but % elongation increases. The layer at a distance of 0.25 mm extends to 235 %, which is much lesser than the opposite layer (more than 900 %) at a distance of 2.25 mm while the stress decreases from 1.7 to 0.48 MPa along distance. This attributes to increased oil content in the vulcanizate. Tensile strength of the opposite layer having maximum oil content (80 wt%, with respect to 100 polymer) decreases by 72 % corresponding to the layer containing 0 wt% (with respect to 100 polymer) oil while elongation at break increases by 389 %. When the oil content increased to 100 wt% (with respect to 100 polymer), both the properties i.e. tensile strength and % elongation at break decrease due to higher plasticization of the SBR. Tensile strength and % elongation at break for 100 wt% (with respect to 100 polymer) oil are 0.35 MPa and 430 % respectively. Similarly, in the filled FGPNCs as shown in Fig. 6(b), the layer at an average distance of 0.25 mm extends to 210 %, which is much lesser than the opposite layer (more than 1500 %) at a distance of 2.75 mm. The stress increases from 9.5 to 20.5 MPa with increasing oil content to a certain extent and decreases again to 1.8 MPa along distance. This attributes to the increased oil content in the vulcanizates. With increasing oil content along the thickness in FGPNCs, tensile strength increases till the optimum oil content is reached and decreases further with increasing oil content but % elongation at break increases continuously. Tensile strength of the layer containing 10 wt% (with respect to 100 polymer) oil (18.7 MPa) increases by 216 % corresponding to the layer containing 0 wt% (with respect to 100 polymer) oil. The tensile strength of the layer having maximum oil content (100 wt%, with respect to 100 polymer) is 1.82 MPa and its value drops down by 81 % corresponding to the

layer containing 0 wt% (with respect to 100 polymer) oil while elongation at break increases by 729 %.
Similar trends as shown in Fig. 7 are also observed when strain energy is plotted against deformation/elongation. The strain energy of the layer at an average distance of 2.25 mm is marginally higher than that of opposite layer at a distance of 0.25 mm. The values of the strain energy at 0.25 and at 2.25 mm along thickness direction are 1.68 x 105 and 1.93 x 10s J/m2 respectively. Similarly Fig. 7(b) shows the strain energy of the layer at an average distance of 2.75 mm is marginally higher than that of opposite layer at a distance of 0.25 mm. The values of the strain energy at 0.25 and at 2.75 mm along thickness direction are 6 x 105 and 7.3 x 105 J/m2 respectively.
Now the tensile strength and elongation at breaking point are measured and shown in Fig. 8 to characterize these FGPs and FGPNCc from the corner of mechanical properties. Both parameters i.e., tensile strength and elongation at breaking point vary along thickness as the oil content varies. The tensile strength of the unfilled FGPs is continuously decreasing along thickness from 1.7 to 0.48 MPa and elongation at breaking point is continuously increasing along thickness from 235 to 900 % respectively within the span of 2.5 mm. The tensile strength of gum SBR compound itself is much less as it lacks the self reinforcing characteristics of NR. Tensile strength at breaking point decreases continuously by 72 % while elongation increases continuously by 83 % within the span of 2.5 mm. This variation of tensile strength and elongation at breaking point is attributed to the variation of oil in the SBR matrix along distance. When the extra layer containing 100 wt% (with respect to 100 polymer) oil is added to the existing FGPs, it is observed that the elongation at break also reduces to 430 %. Reduction in the elongation is attributed to the superfluous addition of oil to the SBR matrix. The entangled chains can easily get broken with excessive amount of plasticizer addition.
For the filled FGPNCs shown in Fig. 8(b) the tensile strength at breaking point is increasing along thickness from 9.5 to 20.5 MPa till the optimum amount of oil content is reached and decreases to 1.8 MPa with further increasing oil content along distance. Elongation at breaking point is continuously increasing along thickness from 210 to 1530 % respectively within the span of 3 mm. Tensile strength at breaking point increases firstly by 216 % and again decreases by 60 % of the value corresponding to the layer present at 0.25 mm while the elongation increases continuously by 729 % within the span of 3 mm. This variation of tensile strength and elongation at breaking point is attributed to the variation of oil in the SBR matrix filled with carbon black nanoparticles along distance.
With increasing oil content, elongation at breaking point increases, but the slope of the stress-strain curve decreases at each and every point. Again tensile strength and elongation at breaking point are failure parameters. Generally designers are least interested about these two parameters. In this context modulus at 100% (the required stress at 100% strain) and at 200% (similarly the required stress at 200% strain) elongations are measured for this FGPs. Modulii at 100 and 200 % elongations decrease along thickness as shown in Fig. 9. The values of moduli! at 100 and 200 % elongations are decreasing from 1.1 to 0.18 and 1.55 to 0.25 MPa respectively. Modulus at 100% as well as at 200 % elongation decreases by 84% in the span of 2.5 mm. For the filled FGPNCs shown in Fig. 9(b), the values of moduli! at 100 and 200 %

elongations are decreasing from 4.0 to 0.14 and 8.82 to 0.22 MPa respectively within the span of 3 mm. Modulus at 100 % as well as at 200 % elongation decreases by 96.5 % in the span of 3 mm.
The FGPs are characterized by another mechanical property i.e., tear strength (the amount of stress required to break the specimen having a pre imbedded crack as per ASTM standard) and shown in Fig. 10. For the unfilled FGPs shown in Fig. 10(a), the tear strength decreases as the oil content increases along the distance. The tear strength goes down continuously from 15 to 3.97 kN/m along the 2.5 mm span. Tear elongation at break enhances from 165% to 945 % and again goes down to 620 %. The decrease in tear strength is 74 %. For the filled FGPNCs, the tear strength firstly increases from 32 to 44 kN/m and then goes down continuously along distance to 10 kN/m within the span of 3 mm. Tear elongation at break enhances continuously from 93 % to 1270 %. Tear strength increases to 137 % and decreases further continually by 69 % corresponding to the layer at 0.25 mm. Tear Elongation increases by 1365 % while moving from one end to the other end along distance.
EXAMPLES
Example A: 33 gm metal oxide/s, 20 gm acid/s, 20 gm antioxidant/s, 1 to 1200 gm (interval of 10 gm) processing oil/s (variable), 32 gm curing agent/s and 22 gm accelerator/s are mixed in 1200 gm polymer/s at a temperature of 50 to 125°C for 10 to 150 minutes and at friction ratio of 1:1.1 to 1:1.5 by two roll mixing mill. After uniform mixing of all these chemical ingredients in to the matrix, a thin sheet of thickness in the range of 0.1 to 10 mm is prepared at a temperature of 50 to 125°C, and friction ratio of 1:1.1 to 1:1.5 in a same two roll mixing mill. The both sides of this thin sheet/s are optionally coated with coating agents. The coated/uncoated thin sheet is kept in hydraulic press in between two teflon sheet and pressed it again to make a very thin sheet of thickness less than 0.1 mm. The coated/uncoated thin sheets are laminated to the desired thickness to make a green functionally graded polymers either in increasing or decreasing order of nano particles and/or using template. The split steel die is preheated before putting these green functionally graded polymerss in it. The preheating is done in a hydraulic press at a temperature of 100 to 250°C. After temperature is reached close to the desired temperature, the green functionally graded polymers are filled in the die and the other half is placed over it. The temperature of 100 to 250°C and pressure of 1 to 20 MPa and time of 10 minutes to 8 hours are selected in such a way to get cured functionally graded polymers.
Example B: 42 gm metal oxide/s, 20 gm acid/s, 31 gm antioxidant/s, 1 to 700 gm processing oil/s (variable, interval of 10 gm), 1 to 560 gm nano material/s (variable, interval of 10 gm), 25 gm processing oil/s, 20 gm curing agent/s and 11 gm accelerator/s are mixed in 700 gm polymer/s at a temperature of 50 to 125°C for 10 to 150 minutes and at friction ratio of 1:1.1 to 1:1.5 by two roll mixing mill. The green functionally graded polymeric nanocomposites are prepared as per method described in example 1. The green functionally graded polymeric nanocomposites are filled in the die and the other part of the die is placed over it at a temperature of 100 to 250°C. The pressure is 1 to 20 MPa. The temperature and pressure are maintained for 10 minutes to 8 hours. Then, the cured functionally graded polymeric nanocomposites are taken out from the mould.
ADVANTAGES OF THE PRESENT FGPS/FGPNCS
Advantage 1) The novel functionally graded polymers and its nanocomposites can be used in wider range of temperature.
Advantage 2) It is possible to grade the glass transition temperature of the FGMs and FGPNCs both in increasing and decreasing order i.e. from inner surface to outer surface and from outer surface to inner surface and in radial direction.
Advantage 3) When the oil concentration is changed from 0 to 100 wt% (with respect to 100 polymer) in SBR, glass transition temperature changes from -57 to -80 °C. The change in the glass transition temperature is 40 % along the thickness.
Advantage 4) Hardness changes from 51 to 13 shore A when the oil concentration in SBR (in absence of nano sized carbon black) is increased from 0 to 100 wt% (with respect to 100 polymer) along thickness and the hardness value changes by 75 %. As specific gravity of the oil is marginally lesser than the matrix, it decreases from 0.982 to 0.92 when varied from 0 to 100 wt% (with respect to 100 polymer). The decrease in specific gravity is 6% only.
Advantage 5) In presence of nanosized carbon black, hardness changes from 74 to 14 shore A when the oil concentration in SBR is changed from 0 to 100 wt% (with respect to 100 polymer) along thickness and the hardness value changes by 81%. The specific gravity also changes from 1.12 to 1. The % change in specific gravity is slightly higher than the composite without carbon black and is 11 only.
Advantage 6) With changing concentration of this oil from 0 to 80 wt% (with respect to 100 polymer) in FGP, tensile strength changes from 1.8 to 0.52 MPa. The change in tensile strength is 71 %. Elongation @ break changes from 255 to 945. The elongation @ break increases by 270 %. (With further increase in the oil concentration to 100 wt% (with respect to 100 polymer), both tensile strength and elongation @ break change to 0.34 MPa and 425 respectively).
Advantage 7) With changing concentration of oil in FGPNCs from 0 to 100 wt% (with respect to 100 polymer), tensile strength changes from 9.8 to 1.8 MPa. The change in tensile strength is 81 %. Elongation @ break changes from 220 to 1530%. The elongation @ break changes by 600%.
Advantage 8) With changing oil, modulus changes in FGP. Modulus @ 100 % changes from 1.1 to 0.17 MPa when oil content is varied from 0 to 100 wt% (with respect to 100 polymer). The change in modulus is 84 %. Similarly, modulus @ 200 % decreases by 80 % when varied from 1.55 to 0.23 MPa along the sheet thickness.
Advantage 9) Modulus @ 100 % changes from 4 to 0.14 MPa when oil content is varied from 0 to 100 wt% in FGPNCs. The chnge in modulus is 96 %. Similarly, Modulus @ 200 % changes by 97 % along the sheet thickness.
Advantage 10) Tear strength changes from 15 to 2.5 kN/m with changing oil content from 0 to 100 wt% (with respect to 100 polymer). The change in tear strength is 83 %. (Tear elongation @ break increases from 165 to 310. The enhancement in tear elongation is 88 %.)
Advantage 11) Tear strength changes from 32 to 10 kN/m with increasing oil content from 0 to 100 wt% in FGPNCs. The change in tear strength is 69%. (Tear elongation @ break increases from 93 to 1275. The enhancement in tear elongation is 1275%.)
Commercial potential
Various types of composite materials, i.e., polymer matrix including thermoplastic and thermosetting, ceramic'matrix, carbon matrix, metal matrix, etc have many advantages over the conventional materials like high strength to weight ratio properties, exceptional temperature and corrosion resistance, high fatigue strength, excellent impact resistance,

excellent solvent and wear resistance, very low internal friction coefficient, ability to engineer for use of structural, mechanical and thermal response, very good thermoformability, large-volume production capabilities, no harmful emission during production, etc. These are widely used through out our daily life including construction industries. But very few items are used in aerospace, automobile and medical industries due to the specified mechanical properties, which are not sufficient in these high tech applications. At the same time the inexpensive production techniques suitable for down to earth industries are not available. This new hybrid nanocomposites has promise for wide range of applications, viz., automobile, aircraft, space craft, sports, etc.
It is to be noted that the formulation of the present invention is susceptible to modifications, adaptations and changes by those skilled in the art. Such variant formulations are intended to be within the scope of the present invention, which is further set forth under the following claims:

WE CLAIM
1. A functionally graded polymers (FGPs) and functionally graded polymer
nanocomposites (FGPNCs) having a gradation of glass transition temperature,
comprising a polymer(s) matrix, nanomaterial(s), processing oil(s) and other chemicals
i.e., antioxidant(s), accelerator(s), accelerator activator(s), and curing agent(s).
2. A process for preparation of functionally graded polymers (FGPs) and functionally
graded polymer nanocomposites (FGPNCs) having a gradation of glass transition temperature comprising steps of:-
mixing of processing oil(s), nanomaterial(s) and other chemicals in polymer matrix such as herein described,
preparation of a thin layer out of the mixture thus obtained followed by lamination of the cut piece to obtain green functionally graded polymers and/or functionally graded polymer nanocomposites, and curing of the green graded sheet in a mould.
3. A process as claimed in claim 2 wherein the mixing is carried out using two-roll mill at
a temperature of 50-125°C wherein the speed of front roll is 10-34 rpm and friction
ratio between front and rear roll is 1:1.1-1:1.5 to obtain a thin layer of 0.1-10 mm in
which the thin layer and the mould is coated with a coating agent such as silicone spray,
detergent/soap solution, silicone emulsion solution, stearic acid, polytetrofluoro
ethylene, polyvinyl alcohol etc.
4. A functionally graded polymers (FGPs) and functionally graded polymer
nanocomposites and a process for preparation of the same as claimed in claim 1 or 2
wherein the processing oil(s), is 0-100% by wt., nanosized material is 0-80% by wt. and
antioxidant(s), acid(s), metal oxide (s), accelerator(s) and curing agent(s) is 0.1-12% by
wt. with respect to 100% by wt. of the polymer.
5. The FGP and/or FGPNCs as claimed in Claim 1 wherein the polymer matrix is selected
from the group comprising of natural rubber, polyisoprene rubber, styrene-butadiene
rubber, polybutadiene rubber, ethylene-propylene rubber, ethylene-propylene diene-
monomer rubber, butyl rubber, halobutyl rubber, nitrile rubber, hydrogenated nitrile
rubber, polysulfide rubber, polyacrylic rubber, neoprene rubber, hypalon rubber,
silicone rubber, fluorocarbon rubber, polyurethane rubber, thermoplastic elastomer, and
mixture thereof wherein the polymer matrix natural rubber rs selected from the group
comprising of standard malaysian rubber (SMR) L, SMR CV, SMR WF, SMR GP,
SMR LV, SMR 5, SMR 10, SMR 20, SMR 50, technically specified rubbers (TSR) 5,
TSR 10, TSR 20, TSR 50, technically classified rubber, oil extended natural rubber,
deproteinized natural rubber, peptized natural rubber, skim natural rubber, superior
processing natural rubber, heveaplus MG rubber, epoxidized natural rubber,
thermoplastic natural rubber, and mixture thereof; the polymer matrix styrene-butadiene
rubber is selected from the group comprising of solution styrene-butadiene rubber i.e.,
SBR 2305, SBR 2304, emulsion styrene-butadiene rubber i.e., cold SBR 1500, cold
SBR 1502, hot SBR 100, and mixture thereof; the polymer matrix polybutadiene rubber
is selected from the group comprising of cisamer-01, cisamerl220, BR 9000, BR
9004A, BR 9004B, low molecular weight 1, 3 polybutadiene, and mixture thereof; the
polymer matrix butyl rubber is selected from the group comprising of IIR-1751, IIR-
175IF, 1IR-745, Exxon butyl 007, Exxon butyl 065, Exxon butyl 068, Exxon butyl 165,
Exxon butyl 268, Exxon butyl 269, Exxon butyl 365, polysar butyl 100, polysar butyl'

101, polysar butyl 101-3, polysar butyl 301, polysar butyl 402, and mixture thereof; the polymer matrix ethylene-propylene rubber is selected from the group comprising ofdutral-CO-034, dutral-CO-038, dutral-CO-043, dutral-CO-054, dutral-CO-058, dutral-CO-059, dutral-CO-055, and mixture thereof; the polymer matrix ethylene-propylene-diene-monomer rubber is selected from the group comprising of ethylene-propylene-dicyclopentadiene rubber, ethylene-propylene-ethylidenenorbornene rubber, ethylene-propylene-1, 4 hexadiene rubber, and mixture thereof; the polymer matrix halobutyl rubber is selected from the group comprising of Exxon chlorobutyl 1065, Exxon chlorobutyl 1066, Exxon chlorobutyl 1068, Polysar chlorobutyl 1240, Polysar chlorobutyl 1255, Exxon bromobutyl 2222, Exxon bromobutyl 2233, Exxon bromobutyl 2244, Exxon bromobutyl 2255, Polysar bromobutyl X2, Polysar bromobutyl 2030, and mixture thereof; the polymer matrix nitrile rubber is selected from the group comprising of Krynac-2750, Nipol-1053, Nipol-1032, Paracril-C, Chemigum-N-3, Krynac-5075, and mixture thereof; the polymer matrix hydrogenated nitrile rubber is selected from the group comprising of zetpol-1010, zetpol-1020, zetpol-2010, zetpol-2020, and mixture thereof; the polymer matrix polyacrylic rubber is selected from the group comprising of hycar-4051, hycar-4052, hycar-4054, vamac-B-124, and mixture thereof; the polymer matrix neoprene rubber is selected from the group comprising of neoprene-AC, neoprene-AD, neoprene-ADG, neoprene-AF, neoprene-AG, neoprene-FB, neoprene-GN, neoprene-GNA, neoprene-GRT, neoprene-GS, neoprene-GW, neoprene-W, neoprene-W-MI, neoprene-WB, neoprene-WD, neoprene-WHY, neoprene-WHY-100, neoprene-WHV-200, neoprene-WHY-A, neoprene-WK, neoprenerWRT, neoprene-WX, neoprene-TW, neoprene-TW-100, neoprene-TRT, and mixture thereof; the polymer matrix hypalon rubber is selected from the group comprising of hypalon-20, hypalon-30, hypalon-LD-999, hypalon-40S, hypalon-40, hypalon-4085, hypalon-623, hypalon-45, hypalon-48S, hypalon-48, and mixture thereof; the polymer matrix silicone rubber is selected from the group comprising of silicone MQ, silicone MPQ, silicone MPYQ, silicone FVQ, and mixture thereof; the polymer matrix fluorocarbon rubber is selected from the group comprising ofviton-LM, viton-C-10, viton-A-35, viton-A, viton-A-HF, viton-E-45, viton-E-60, viton-E-60C, viton-E403, viton-B-50, viton-B, viton-B-70, viton-910, viton-GLT, viton-GF, viton-VTR-4730, DA1-EL-G-101, DAI-EL-701, DAI-EL-751, DAI-EL-702, DAI-EL-704, DAI-EL-755, DAI-EL-201, DAI-EL-501, DAI-EL-801, DAI-EL-901, DAI-EL-902, tecnoflon-FOR-LHF, tecnoflon-NMLB, tecnoflon-NML, tecnoflon-NMB, tecnoflon-NM, tecnoflon-NH, tecnoflon-FOR-45-45BI, tecnoflon-FOR-70-70BI, tecnoflon-FOR-45-C-Cl, tecnoflon-FOR-60K-KI, tecnoflon-FOR-50E, tecnoflon-TH, tecnoflon-TN-50, tecnoflon-TN, tecnoflon-FOR-THF, tecnoflon-FOR-TF-50, tecnoflon-FOR-TF, fluorel-2145, fluorel-FC-2175, fluorel-FC-2230, fluorel-FC-2178, fluorel-FC-2170, fluorel-FC-2173, fluorel-FC-2174, fluorel-FC-2177, fluorel-FC-2176, fluorel-FC-2180, fluorel-FC-81, fluorel-FC-79, fluorel-2152, fluorel-FC-2182, fluorel-FC-2460, fluorel-FC-2690, fluorel-FC-2480, and mixture thereof, the polymer matrix polyurethane rubber (polyether and polyester type) is selected from the group comprising of FMSC-1035, FMSC-1035T, FMSC-1040, FMSC-1050, FMSC-1060, FMSC-1066, FMSC-1070, FMSC-1075, FMSC-1080-SLOW, FMSC-1080-FAST, FMSC-1085, FMSC-1090-FAST, FMSC-1090-SLOW, and mixture thereof; the polymer matrix thermoplastic elastomer (polyurethane, polyester, polyamide, styrene-butadiene-styrene, blends, etc) is selected from the group comprising of SBS 1401, SBS 4402, SBS 4452, SBS 1301, SBS 1401-1, SBS 4303, estane-55103, hytrel-40xy,

hytrel-63xy, hytrel-72xy, gaflex-547, pebax-2533, pebax-6333, TPR-1600, TPR-1900, TPR-2800, TELCAR-340, SOMEL-301, SOMEL-601, santoprene, cariflex-TR, solprene-400, stereon, and mixture thereof; the polymer matrix polysulfide elastomer is selected from the group comprising of thiakol-A, thiakol-B, thiakol-FA, thiakol-ST, and mixture thereof.
6. The FGP and/or FGPNCs as claimed in Claim 5 wherein the polymer matrix natural rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, diurethane, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix styrene-butadiene rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, diurethane, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix polybutadiene rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, diurethane, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix butyl rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, diurethane, p-quinone dioxime, p-quinone dioxime dibenzoate, phenol-formaldehyde resin, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix ethylene-propylene rubber is cured by vulcanizing agent selected from the group comprising of hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane, bis(2,4-dichloro-benzoyl) peroxide, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix ethylene-propylene-diene-monomer rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, diurethane, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix halobutyl rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, zinc oxide, p-quinone dioxime, p-quinone dioxime dibenzoate, phenol-formaldehyde resin, amine, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix nitrile rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix hydrogenated nitrile rubber is cured by vulcanizing agent selected from the group comprising of sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane, bis(2,4-dichloro-benzoyl) peroxide, tertiary butyl perbenzoate, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix polyacrylic rubber is cured by vulcanizing agent selected from the group comprising of amine, diamine, activated thiol, sulphur, thiourea, trithiocyanuric acid, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix neoprene rubber is cured by vulcanizing agent selected from the group comprising of magnesium oxide, zinc oxide, lead oxide, iron oxide, titanium oxide, amine, phenol, sulfenamide, thiazoles, thiuram, thiourea, guanidine, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer

matrix hypalon rubber is cured by vulcanizing agent selected from the group comprising of magnesium oxide, zinc oxide, lead oxide, iron oxide, titanium oxide, sulphur, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, N,N'-m-phenylenedimaleimide, amine, phenol, sulfenamide, thiazoles, thiuram, thiourea, guanidine, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix silicone rubber is cured by vulcanizing agent selected from the group comprising of hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyI-2,5-bis (t-butyl peroxy) hexane, bis(2,4-dichloro-benzoyl) peroxide, tertiary butyl perbenzoate, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix fluorocarbon rubber is cured by vulcanizing agent selected from the group comprising of hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane, bis(2,4-dichloro-benzoyl) peroxide, tertiary butyl perbenzoate, hexamethylenediamine carbamate, bis(cinnamylidene) hexamethylenediamine, hydroquinone, 4-4'-isopropylidene bisphenol or mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix polyurethane rubber (polyether and polyester type) is cured by vulcanizing agent selected from the group comprising of 1,4-butanediol, 1,4-cyclohexanedimethanol, l,4-bis(2-hydroxyethoxy) benzene, 4,4'methylene-bis(2-chloroaniline), and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); the polymer matrix thermoplastic elastomer (polyurethane, polyester, polyamide, styrene-butadiene-styrene, blends, etc) is cured by vulcanizing agent selected from the group comprising of lead oxide, cadmium oxide, zinchydroxide, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane, bis(2,4-dichloro-benzoyl) peroxide, tertiary butyl perbenzoate, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer); and the polymer matrix polysulfide elastomer is cured by vulcanizing agent selected from the group comprising of lead oxide, cadmium oxide, zinchydroxide, hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane, bis(2,4-dichloro-benzoyl) peroxide, tertiary butyl perbenzoate, hexamethylenediamine carbamate, bis(cinnamylidene) hexamethylenediamine, hydroquinone, 4-4'-isopropylidene bisphenol, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer).
7. The FGPNCs as claimed in Claim 1 wherein the polymer matrix comprising of either natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene rubber, ethylene-propylene diene monomer rubber, butyl rubber, halobutyl rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide elastomer, polyacrylic rubber, neoprene rubber, hypalon rubber, silicone rubber, fluorocarbon rubber, polyurethane rubber, thermoplastic elastomer and/or mixture thereof is graded by carbon nanoparticles selected from the group comprising of N-110, N-115, N-120, N-121, N-125, N-134, N-135, N-212, N-220, N-231, N-234, N-293, N-299, N-315, N-326, N-330, N-335, N-339, N-343, N-347, N-351, N-356, N-358, N-375, N-539, N-550, N-582, N-630, N-642, N-650, N-660, N-683, N-754, N-762, N-765, N-772, N-774, N-787, N-907, N-908, N-990, N-991, and mixture thereof which is in the range of 0 to 80 wt% (with respect to 100 polymer) wherein the polymer matrix comprising of either natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene rubber, ethylene-propylene diene monomer rubber, butyl rubber,

halobutyl rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide elastomer,
polyacrylic rubber, neoprene rubber, hypalon rubber, silicone rubber, fluorocarbon
rubber, poiyurethane rubber, thermoplastic elastomer and/or mixture thereof is further
graded by various silica nanoparticles i.e., precipitated silica (i.e., HS-200, HS-500, HS-
700, etc), fumed silica and mixture thereof which is in the range of 0 to 80 wt% (with
respect to 100 polymer) wherein the polymer matrix comprising of either natural
rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-
propylene rubber, ethylene-propylene diene monomer rubber, butyl rubber, halobutyl
rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide elastomer, polyacrylic
rubber, neoprene rubber, hypalon rubber, silicone rubber, fluorocarbon rubber,
poiyurethane rubber, thermoplastic elastomer and/or mixture thereof is further graded
by clay nanoparticles which is in the range of 0 to 80 wt% (with respect to 100
polymer) wherein the polymer matrix comprising of either natural rubber, polyisoprene
rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene rubber,
ethylene-propylene diene monomer rubber, butyl rubber, halobutyl rubber, nitrile
rubber, hydrogenated nitrile rubber, polysulfide elastomer, polyacrylic rubber, neoprene
rubber, hypalon rubber, silicone rubber, fluorocarbon rubber, poiyurethane rubber,
thermoplastic elastomer and/or mixture thereof is further graded by mixed carbon
nanoparticles, nanosilica and nanoclay in a volume ratio of 5:2:1 to 1:2:5 selected from
the group comprising of N-l 10, N-l 15, N-120, N-121, N-125, N-134, N-135, N-212,
N-220, N-231, N-234, N-293, N-299, N-315, N-326, N-330, N-335, N-339, N-343, N-
347, N-351, N-356, N-358, N-375, N-539, N-550, N-582, N-630, N-642, N-650, N-660,
N-683, N-754, N-762, N-765, N-772, N-774, N-787, N-907, N-908, N-990, N-991,
precipitated silica (i.e., HS-200, HS-500, HS-700, etc), fumed silica, clay and mixture
thereof wherein the polymer matrix comprising of either natural rubber,
polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene rubber, ethylene-propylene diene monomer rubber, butyl rubber, halobutyl rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide elastomer, polyacrylic rubber, neoprene rubber, hypalon rubber, silicone rubber, fluorocarbon rubber, poiyurethane rubber, thermoplastic elastomer and/or mixture thereof is further graded by mixed carbon nanoparticles having same concentration gradient but different particle size i.e 5 to 85 nm and selected from the group comprising of N-l 10, N-l 15, N-120, N-121, N-125, N-134, N-135, N-212, N-220, N-231, N-234, N-293, N-299, N-315, N-326, N-330, N-335, N-339, N-343, N-347, N-351, N-356, N-358, N-375, N-539, N-550, N-582, N-630, N-642, N-650, N-660, N-683, N-754, N-762, N-765, N-772, N-774, N-787, N-907, N-908, N-990, N-991.
8. The FGPs and FGPNCs as claimed in Claim 1 wherein the curing of polymer matrix comprising of either natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene rubber, ethylene-propylene diene monomer rubber, butyl rubber, halobutyl rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide elastomer, polyacrylic rubber, neoprene rubber, hypalon rubber, silicone rubber, fluorocarbon rubber, poiyurethane rubber, thermoplastic elastomer and/or mixture thereof is further accelerated by accelerator selected from the group comprising of tert-buttylbenzthiazyl sulphonamide, benzthiazyl 2-sulphenmorpholide, dicyclohexyl benzthiazyl sulphonamide, N-cyclohexyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazote, 2,2'dibenzothiazyl disutfide, tetramethylthiuram disulfide, zinc dimethyldithiocarbamate, zinc dibutyldithiocarbamate, 4,4'dithiodtmorpholine, tellurium diethyldithiocarbamate, dipentamethylene thiuramhexasulfide,

tetramethylthiuram monosulfide, ferricdimethyldithiocarbamate, zinc
mercaptobenzthiazole, zinc 0,0 dibutylphosphorodithioate, zinc diethyldithiocarbamate, 4-4'dithio dimorpholine, which is in the range of 0.1 to 12 wt% (with respect to 100 polymer) and , and mixture thereof in a ratio of 1 : 9 to 9:1 (by weight) wherein the curing of polymer matrix comprising of either natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylehe rubber, ethylene-propylene diene monomer rubber, butyl rubber, halobutyl rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide elastomer, polyacrylic rubber, neoprene rubber, hypalon rubber, silicone rubber, fluorocarbon rubber, polyurethane rubber, thermoplastic elastomer and/or mixture thereof is further accelerated by accelerator •activator selected from the group comprising of metal oxide and acid which is in the range of 10:1 to 1:10 wt% (with respect to 100 polymer).
9. The metal oxide used in accelerator activator as claimed in Claim 8 is selected from the
group comprising of zinc oxide, lead oxide, calcium oxide, magnesium oxide, lead oxide, etc which is in the range of 0.1 to 12 wt% (with respect to 100 polymer) and the acid used in accelerator activator is selected from the group comprising of stearic acid, palmitic acid, oleic acid, etc which is in the range of 0.1 to 12 wt% (with respect to 100 polymer), and the FGPs and FGPNCs further comprises an antioxidant selected from the group comprising of condensation product of acetone and diphenyl-amine, phenyl-beta-napthylamine, blends of diphenyl-p-phenylene diamine and selected arylamine derivatives, blend of arylamines, polymerized 1,2 dihydro 2,2,4-trimethyl quinoline, N-(l,3-dimethylbutyl)-N'-phenyl-p-phenylene-diamine, diaryl para phenylene diamines, 2 mercaptobenzimidazole, and mixture thereof which is in the range of 0.1 to 12 wt% (with respect to 100 polymer).
10. The FGPs and FGPNCs as claimed in Claim 1 further comprises a process oil selected
from the group comprising of paraffmic oil, naphthenic oil, aromatic oil, vegetable oil, and mixture thereof which is in the range of 0 to 100 wt% (with respect to 100 polymer) wherein the nanoparticles and other chemicals imbedded polymer matrix is prepared by mixing the polymer and other compounding ingredients by methods such as open roll mixing using two roll mill and internal mixing kneader, intermix and banbary mixer.
11. The FGPs and FGPNC as claimed in Claim 1 wherein the green graded material is cured
by hydraulic press at temperature of 100°C to about 250°C for 10 minutes to about 8 hours and at pressure of 1 MPa to about 20 MPa.