Rubber compositions and uses thereof

Abstract

There are provided rubber compositions comprising an elastomer comprising a rubber chosen from acrylonitrile-butadiene, hydrogenated acrylonitrile-butadiene, carboxylated acrylonitrile-butadiene and mixtures thereof; reinforcing fibers chosen from aramid fibers, carbon fibers, polyester fibers, glass fibers, nylon fibers and mixtures thereof, and/or nanometric filamentary structures chosen from nanowires, nanorods, nanofibers, nanoribbons, nanotubes and mixtures thereof, the nanometric filamentary structures being functionalized or unfunctionalized; and a filler chosen from carbon black and silica. These compositions can be cured or uncured and they can be used for preparing various articles. Methods for preparing such compositions are also disclosed.

Claims

1. A rubber composition comprising: about 40 to about 70 wt. % of an elastomer comprising a rubber selected from the group consisting of acrylonitrile-butadiene, hydrogenated acrylonitrile-butadiene, carboxylated acrylonitrile-butadiene and mixtures thereof; about 0.1 to about 10 wt. % of reinforcing fibers that are aramid fibers; about 0.1 to about 10 wt. % of nanometric filamentary structures that are carbon nanotubes, said nanometric filamentary structures being functionalized or unfunctionalized; and about 15 to about 40 wt. % of a filler selected from the group consisting of carbon black, silica and a mixture thereof, wherein said rubber composition is a cured rubber composition having an elongation % of about 302 to about 650, measured according to ASTM D-412 standard.

2. The composition of claim 1, wherein in said composition, said elastomer, reinforcing fibers and/or nanometric filamentary structures and filler are substantially uniformly distributed.

3. The composition of claim 2, wherein said composition comprises about 45 to about 65 wt. % of said elastomer.

4. The composition of claim 2, wherein said composition comprises about 50 to about 60 wt. % of said elastomer.

5. The composition of claim 1, wherein said composition comprises about 0.25 to about 1.75 wt. % of said reinforcing fibers.

6. The composition of claim 5, wherein said composition comprises about 0.25 to about 1.75 wt. % of said nanometric filamentary structures.

7. The composition of claim 1, wherein said composition comprises about 0.5 to about 10 wt. % of said reinforcing fibers and/or nanometric filamentary structures.

8. The composition of claim 2, wherein said composition comprises about 1 to about 5 wt. % of said reinforcing fibers and/or nanometric filamentary structures.

9. The composition of claim 8, wherein said composition comprises about 20 to about 35 wt. % of said filler.

10. A rubber composition comprising: an elastomer comprising a rubber selected from the group consisting of acrylonitrile-butadiene, hydrogenated acrylonitrile-butadiene, carboxylated acrylonitrile-butadiene and mixtures thereof; reinforcing fibers that are aramid fibers; nanometric filamentary structures that are carbon nanotubes, said nanometric filamentary structures being functionalized or unfunctionalized; and a filler selected from the group consisting of carbon black, silica, and a mixture thereof, wherein said rubber composition is a cured rubber composition having an elongation % of about 302 to about 650, measured according to ASTM D-412 standard; and a 100% modulus of about 300 to about 1500 measured according to ASTM D-412 standard.

11. A rubber composition comprising: an elastomer comprising a rubber selected from the group consisting of acrylonitrile-butadiene, hydrogenated acrylonitrile-butadiene, carboxylated acrylonitrile-butadiene and mixtures thereof; reinforcing fibers that are aramid fibers; nanometric filamentary structures that are carbon nanotubes, said nanometric filamentary structures being functionalized or unfunctionalized; and a filler selected from carbon black, silica, and a mixture thereof, wherein said rubber composition is a cured rubber composition having an elongation % of about 302 to about 650, measured according to ASTM D-412 standard, a 100% modulus of about 300 to about 1500 psi measured according to ASTM D-412 standard, and a 300% modulus of about 1303 to about 3000 psi, measured according to ASTM D-412 standard.

12. The composition of claim 7, wherein said elastomer comprises hydrogenated acrylonitrile-butadiene.

13. The composition of claim 7, wherein said elastomer comprises carboxylated acrylonitrile-butadiene.

14. The composition of claim 1, wherein said composition has, prior to curing, a Mooney viscosity ML 145° C. of about 50 to about 100, measured according to ASTM D-1646 standard.

15. The composition of claim 1, wherein said composition has, prior to curing, a Mooney Scorch time t5 145° C. of about 4 to about 8 minutes, measured according to ASTM D-1646 standard.

16. The composition of claim 7, wherein said composition has, prior to curing, a specific gravity of about 1.0 to about 1.5 g/mL, measured according to ASTM D-297 standard.

17. The composition of claim 1, wherein said rubber composition has a 100% modulus of about 300 to about 1500 psi measured according to ASTM D-412 standard.

18. The composition of claim 7, wherein said rubber composition has a 100% modulus of about 400 to about 900 psi, measured according to ASTM D-412 standard.

19. The composition of claim 17, wherein said rubber composition has a 300% modulus of about 1500 to about 3000 psi, measured according to ASTM D-412 standard.

20. The composition of claim 1, wherein said rubber composition, when submitted to a fuel B immersion test according to ASTM D-471 standard, has an elongation % of about −10% to about 10%, measured according to ASTM D-412 standard, as compared to a sample measured before fluid immersion.

21. An article comprising a rubber composition as defined in claim 1.

Description

Example 1

Preparation of Rubber Composition 1

(1) The ingredients use for the Composition 1 with their amount in phr-mass (g) per hundred grams of elastomer are represented in Table 1. The equivalents in % by weight is also presented. The Acrylonitrile-Butadiene-Polymer (NBR) was produced by Khumo. The Merge 1F770™ is a 23.5% w/w dispersion of short pulp aramid Kevlar fibers in a NBR matrix processed in liquid phase by Dupont™ inc. It is a dispersion of aramid fiber. The PRO 7000™ used is a high aspect ratio Multi Wall Carbon nanotube from Nanocyl™ sa with average wall diameter of 9.5 nm and with an average length of 1.5 microns. The carbon blacks grades used were produced from Continental™ inc. and corresponds to a N550 grade with an Iodine adsorption value of 50 mg/g and a DBP absorption value of 120 mL/100 g and a N774 grade with an Iodine adsorption value of 35 mg/g and a DBP absorption value of 75 mL/100 g.

(2) Stearic acid and zinc oxide are used to promote reticulation of rubber during curing as well as process aids. 1,3-dimethylbutyl)-N′-phenyl-P-Phenylenediamine are used as anti-aging and anti-fatigue agents to capture free radicals. Parafin wax is used as a UV blocking agent. They were supplied by Ferguson Chemicals Inc.

(3) N-tertiary butyl-2-benzothiazole sulfenimide was used as rubber vulcanization accelerator agent. Sulfur was used as e crosslinking agent. It was supplied by Ferguson™ Chemicals Inc.

(4) TABLE-US-00001 TABLE 1 Formulation of Rubber Composition 1 Material phr (wt. %) First Stage Mix Kosyn KNB-35LM Acrylonitrile-Butadiene-Polymer 96.65 52.36 (NBR) MERGE 1F770 KEVLAR Engeneered Elastomer 4.35 2.36 (in NBR) PRO 7000 (NC 7000 MWCNT) 2.00 1.08 Carbon Black N-774 10 5.42 Second Stage Mix Masterbatch from first stage Carbon Black N-550 35 18.96 DBEEA (Dibutoxyethoxyethyl adipate plastisizer) 21 11.38 Stearic Acid 1 0.54 Zinc Oxide 5 2.71 6PPD/FLEXONE-7F N-(1,3-dimethylbutyl)-N′-phenyl-P- 2.5 1.35 Phenylenediamine) NOCHEK 4709A (Parafin Wax) 3 1.63 Third Stage Mix Masterbatch from second stage TBBS (N-tertiary butyl-2-benzothiazole sulfenamide) 2 1.08 SOUFRE H-10 (Sulfur) 2.1 1.14
Mixing and Processing Method

(5) All the mixing phases and stages were carried in a Farrell 1.5 L Banbury mixer with Tangential rotors blending the ingredients by friction with the chamber sidewall and an hydraulic ram to put pressure to the mix. It is equipped with an automated control box permitting variable mixing speeds and an accurate control over time, pressure, energy and temperature during all the mixing process. The batch produced is then processed in a Laboratory Two Roll Mill put into sheet form and then cooled down after each mix stage. If the mix is not final, it goes back to the mixer as a masterbatch for the next mixing step 24 hours later.

(6) The first stage mix (preparation of MasterBatch 1) was carried out as follow:

(7) 1) Add PRO 7000;

(8) 2) Add carbon black, polymer and Merge 1F770;

(9) 3) Mix Ram float at low speed (70 rpm) for 20 seconds;

(10) 4) Mix until temperature rise to 120 Celcius at 50 rpm;

(11) 5) Ram up;

(12) 6) Mix until temperature rise to 140 Celcius at low speed;

(13) 7) Ram Up; and

(14) 8) Drop

(15) 3 minutes mixing time total, thereby obtaining MasterBatch 1

(16) The aim of this first pass mix was to break down the viscosity of the nitrile rubber as well as to force the preliminary dispersion of MWCNT, carbon black and Kevlar which is a challenge to achieve completely. It is done at high sheer with a medium drop temperature.

(17) The second stage mix (preparation of MasterBatch 2) was done as follows:

(18) 1) Add MasterBatch 1 and chemicals (EMERY-400/VSTEARIN (Stearic Acid); ZINC OXYDE CR-4/ZOCO (Zinc Oxide); 6PPD/FLEXONE-7FN-(1,3-dimethylbutyl)-N′-phenyl-P-Phenylenediamine) and NOCHEK 4709A (Parafin Wax);

(19) 2) Add half carbon black; DBEEA (Dibutoxyethoxyethyl adipate plastisizer) and the rest of carbon black;

(20) 3) Mix to 105 Celcius at low speed;

(21) 4) Ram up;

(22) 5) Mix to 140 Celcius at low speed;

(23) 6) Drop;

(24) 4 minutes mixing time total, MasterBatch 2.

(25) The aim of this second pass is to force by high sheer the incorporation of the reinforcing carbon black and Plasticizer and to complete the dispersion of Kevlar, MWCNT and the other chemicals.

(26) The third stage, the finalization of mixing, was perform accordingly to the following:

(27) 1) Add MasterBatch 2 and curative chemicals (TBBS (N-tertiary butyl-2-benzothiazole sulfenamide); SOUFRE H-10 (Sulfur);

(28) 2) Mix ram down 55 sec at low speed;

(29) 3) Ram up;

(30) 5) Mix to 110 Celcius at low speed;

(31) 6) Drop;

(32) 2 minutes mixing time total, thereby obtaining composition 1 (uncured).

(33) The mixing of the finalization is done at low sheer and low temperature. It is meant to be done to finalize the dispersion of the curative agents without beginning the cure and to avoid scorching of the product.

Example 2

Use of Rubber Composition 1 for Preparing Articles

(34) The resulting uncured rubber Composition 1 can then be transformed in sheet form, profiles or lugs using a—two, three or four roll—calendar or an extruder equipped with a perform die, a roller head or without. The preformed material—for example a calendered uncured rubber sheet rolled of 15″×0.120″—may then be used downstream in the production process to be assembled uncured with other layers of itself, layers of other rubber compounds with different properties (hardness) and along with other reinforcing non rubber material, using the natural tack of the rubber or with the use of adhesives or tack cement. It is then cured in a final product by compression moulding, injection, transfer or autoclave. This operation consists of heating the rubber under a certain temperature (about 140° C. to about 180° C.) to make the sulphur creates crosslinks between polymer chains—the curing process that gives to the rubber its final stable elastic properties—at high pressure to remove gas in a product form directed by the moulds form. For example, these products can be used to in the manufacture of hoses, tank liners, power section stators designed for oil and gas prospection applications, but it may also be used to manufacture rubber pieces for other applications, like the mining industry, tank lining, tires (of all kind and sizes), hoses, gaskets and all other rubber goods.

(35) These compositions can thus be used, for example, in oil sands pipes. The interior is covered with a rubber liner that must be resistant to the immersion in oil as well as being resistant to excessive wear and abrasion. In addition, for powers stator applications, the resistance to excessive heat and pressure due to deep ground forencing. The technology claimed improves drastically all of them and moreover the final field performance. It is likely to do the same for all highly demanding applications were thermal, oil, chuncking and wear resistance like OTR tires, mining ball mills and conveyors, specialty hoses, etc.

Example 3

Preparation of Various Rubber Compositions

(36) Similarly to Composition 1, previously discussed, other compositions (Compositions 2 and 3) have been prepared by using the same method. Their ingredients are listed in Table 2 below.

(37) TABLE-US-00002 TABLE 2 Ingredients of Various Rubber Compositions Composition 1 Composition 2 Composition 3 (NBR 100, (HNBR 100, (XNBR 100, CNT, kevlar) CNT, kevlar) CNT, kevlar) Trade Name Chemical Formula phr % w/w phr % w/w phr % w/w Kosyn KNB-35LM Acrylonitrile-Butadiene-Polymer (NBR) 96.65 52.36% Therban 4364 VP Hydrogenated Acrylonitrile-Butadiene- 97.970 53.68% Polymer (HNBR) Nipol NX-775 Carboxylated Acrylonitrile-Butadiene-Polymer 96.650 53.83% (XNBR) MERGE 1F770 KEVLAR Engeneered Elastomer (in NBR) 4.35 2.36% MERGE 1F1598 KEVLAR Engeneered Elastomer (in HNBR) 3.030 1.66% 4.350 2.42% PRO 7000 NC 7000 MWCNT 2 1.08% 2.000 1.10% 2.000 1.11% Carbon Black N-330 Carbon Black 35.000 19.49% Carbon Black N-550 Carbon Black 35 18.96% Carbon Black N-774 Carbon Black 10 5.42% 35.000 19.18% Barythes 22 Barium Sulfate 10.000 5.48% DBEEA Dibutoxyethoxyethyl adipate plastisizer 21 11.38% 15.000 8.35% DOP Dioctyl Phtalate 17.000 9.32% Degussa Si-69 Bis (triethoxysilylpropyl) polysulfide 2.000 1.10% Nipol 1312 L/V Acrylonitrile-Butadiene-Polymer (NBR) Low 7.000 3.90% Molecular weight Stearic Acid Stearic acid 1 0.54% 1.000 0.55% 1.000 0.56% Zinc Oxide Zinc Oxide 5 2.71% 5.000 2.74% 5.000 2.78% Pluriol E4000 Polyethylene Glycol 1.000 0.55% TMQ 1,2-Dihydro-2,2,4-trimethylquinoline 1.000 0.56% 6PPD N-cyclohexyl-N′-phenyl-p-phenylenediamine 2.5 1.35% Naugard 445 4,4′-Bis-(a,a′-dimethylbenzyl) diphenylamine 1.500 0.82% Vanox ZMTI Zincmethylmercaptobenzimidazole 1.000 0.55% NOCHEK 4709A, Paraffin Wax 3 1.63% Blended Waxe Cumar P-25 DLD Coumarone Indene Resin 10.000 5.57% (KD-109) TMTD Tetramethyl thiuram disulfide 4.000 2.19% 0.300 0.17% TBBS N-tertiary butyl-2-benzothiazole sulfenamide 2 1.08% MBTS Benzothyazyl disulfide 1.500 0.84% Sulphur Sulphur 2.1 1.14% 2.000 1.10% 0.750 0.42% Total 184.60 100.00% 182.50 100.00% 179.55 100.00%

Example 4

Comparative Tests for Various Rubber Compositions

(38) Compositions 1 to 3 have been tested. The physical properties of Compositions 1 to 3 are listed in Table 3.

(39) TABLE-US-00003 TABLE 3 Physical Properties of Various Rubber Compositions Tested Compositions Compo- Compo- Compo- sition 1 sition 2 sition 3 (NBR (HNBR (XNBR 100, CNT, 100, CNT, 100, CNT, Tests kevlar) kevlar) kevlar) Specific Gravity (g/mL) 1.164 1.170 1.147 Hardness (dureté shore A) 66 72 71 Tensile (psi) 1863 3018 1959 Elongation (%) 302 436 428 Modulus 50% 496 592 465 Modulus 100% 823 846 706 Modulus 300% 1849 1731 1303 Tear (lbs, die C) 200 239 204 MDR 191C ML 0.65 0.36 0.93 MDR 191C t10 0.71 0.8 0.55 MDR 191C t95 1.86 3.33 3.12 MDR 191C MH 14.72 13.77 5.78 Viscosity ML 145 C. 18 12 24 Scorch T-5 145 C. 6.75 5.18 5.61 DIN Abrasion (mm3) 114 163 130

(40) Specific Gravity has been measured according to ASTM D-297 standard. Hardness has been measured according to ASTM D-2240 standard with a Bareiss Durometer. Tensile strength, elongation at break and modulus has been measured according to ASTM D-412 standard with a TensiData tensiometer. Tear propagation strength was measured according to ASTM standard D-624 die C with a TensiData tensiometer.

(41) MDR and viscosimetry have been tested using standards ASTM D-2084 and D-1646 respectively. The aim of these tests are to understand the processing behaviour of the uncured rubber paste to optimise calendering and extrusion as well as to understand and control the curing kinetics (slow curing or fast curing) during mould vulcanization.

(42) DIN abrasion test has been evaluated with a Bareiss DIN abrader instrument according to ASTM D-5963 method and was meant to measure the resistance of the material to wear with the presence of sands and mud. Heat aging have been tested using standard ASTM D-573 to measure the deterioration of the rubber into a hot air oven at 100° C. for a period of time of 70 hours. The aim of this test was to evaluate the thermal resistance and aging properties of the composition. Such a property is quite important to powersection stators application.

(43) Oil immersion have been evaluated in regards to ASTM D-412 and D-471 standards with a TensiData tensiometer. Immersions were performed using ASTM D-471 standard method with oil IRM903 (former oil ASTM 3) to evaluate the oil resistance properties. Variations in tensile-strain properties were then measured on dumbels that has been immersed. In oil and gas applications, resistance properties of the rubber compound to fluids is primordial.

(44) Aging (Heat and Oil) Test Results

(45) Further tests have been made on compositions 1 to 3 and are shown in Table 5. More particularly, comparatives tests have been made with Compositions 1 to 3 by comparing them with Compositions A, B and C. Compositions A, B and C are similar to compositions 1, 2 and 3, respectively, with the exception that they do not comprises the reinforcing fibers and the nanometric filamentary structures of the compositions 1, 2 and 3. The Compositions A, B and C are described in Table 4. In Table 5, the Compositions 1 to 3 and A to C have been compared. In order to do so, sheets have been made with these compositions. Sheet 1 has been made with Composition A, sheet 2 has been made with Composition 1, sheet 3 has been made with Composition B, sheet 4 has been made with Composition 2, sheet 5 has been made with Composition C and sheet 6 has been made with Composition 3.

(46) TABLE-US-00004 TABLE 4 Ingredients of Various Comparative Compositions Composition-A (NBR Composition-1 (NBR Composition-B (HNBR 100, Reference, Oil 100, CNT, kevlar, oil 100, Reference, Oil and Gas Product) and Gas Product) and Gas Product) Trade Name Chemical Formula phr % w/w phr % w/w phr % w/w Kosyn KNB-35LM Acrylonitrile-Butadiene-Polymer (NBR) 100 53.59% 96.65 52.36% Therban 4364 VP Hydrogenated Acrylonitrile-Butadiene- 100.000 55.71% Polymer (HNBR) Nipol NX-775 Carboxylated Acrylonitrile-Butadiene-Polymer (XNBR) MERGE 1F770 KEVLAR Engeneered Elastomer (in NBR) 4.35 2.36% MERGE 1F1598 KEVLAR Engeneered Elastomer (in HNBR) PRO 7000 NC 7000 MWCNT 2 1.08% Carbon Black N-330 Carbon Black Carbon Black N-550 Carbon Black 40 21.44% 35 18.96% Carbon Black N-774 Carbon Black 10 5.36% 10 5.42% 35.000 19.50% Barythes 22 Barium Sulfate 10.000 5.57% DBEEA Dibutoxyethoxyethyl adipate plastisizer 21 11.25% 21 11.38% DOP Dioctyl Phtalate 17.000 9.47% Degussa Si-69 Bis (triethoxysilylpropyl) polysulfide 2.000 1.11% Nipol 1312 L/V Acrylonitrile-Butadiene-Polymer (NBR) Low Molecular weight Stearic Acid Stearic acid 1 0.54% 1 0.54% 1.000 0.56% Zinc Oxide Zinc Oxide 5 2.68% 5 2.71% 5.000 2.79% Pluriol E4000 Polyethylene Glycol 1.000 0.56% TMQ 1,2-Dihydro-2,2,4-trimethylquinoline 6PPD N-cyclohexyl-N′-phenyl-p-phenylenediamine 2.5 1.34% 2.5 1.35% Naugard 445 4,4′-Bis-(a,a′-dimethylbenzyl) diphenylamine 1.500 0.84% Vanox ZMTI Zincmethylmercaptobenzimidazole 1.000 0.56% NOCHEK 4709A, Blended Paraffin Wax 3 1.61% 3 1.63% Waxe Cumar P-25 DLD Coumarone Indene Resin (KD-109) TMTD Tetramethyl thiuram disulfide 4.000 2.23% TBBS N-tertiary butyl-2-benzothiazole sulfenamide 2 1.07% 2 1.08% MBTS Benzothyazyl disulfide Sulphur Sulphur 2.1 1.13% 2.1 1.14% 2.000 1.11% Total 186.60 100.00% 184.60 100.00% 179.50 100.00% Composition-2 Composition-C (HNBR 100, CNT, (XNBR Composition-3 (XNBR kevlar, oil and Gas 100, Reference, Oil 100, CNT, kevlar, Oil Product) and Gas Product) and Gas Product) Trade Name Chemical Formula phr % w/w phr % w/w phr % w/w Kosyn KNB-35LM Acrylonitrile-Butadiene-Polymer (NBR) Therban 4364 VP Hydrogenated Acrylonitrile-Butadiene- 97.970 53.68% Polymer (HNBR) Nipol NX-775 Carboxylated Acrylonitrile-Butadiene-Polymer 100.000 55.08% 96.650 53.83% (XNBR) MERGE 1F770 KEVLAR Engeneered Elastomer (in NBR) MERGE 1F1598 KEVLAR Engeneered Elastomer (in HNBR) 3.030 1.66% 0.00% 4.350 2.42% PRO 7000 NC 7000 MWCNT 2.000 1.10% 0.00% 2.000 1.11% Carbon Black N-330 Carbon Black 40.000 22.03% 35.000 19.49% Carbon Black N-550 Carbon Black Carbon Black N-774 Carbon Black 35.000 19.18% Barythes 22 Barium Sulfate 10.000 5.48% DBEEA Dibutoxyethoxyethyl adipate plastisizer 15.000 8.26% 15.000 8.35% DOP Dioctyl Phtalate 17.000 9.32% Degussa Si-69 Bis (triethoxysilylpropyl) polysulfide 2.000 1.10% Nipol 1312 L/V Acrylonitrile-Butadiene-Polymer (NBR) Low 7.000 3.86% 7.000 3.90% Molecular weight Stearic Acid Stearic acid 1.000 0.55% 1.000 0.55% 1.000 0.56% Zinc Oxide Zinc Oxide 5.000 2.74% 5.000 2.75% 5.000 2.78% Pluriol E4000 Polyethylene Glycol 1.000 0.55% TMQ 1,2-Dihydro-2,2,4-trimethylquinoline 1.000 0.55% 1.000 0.56% 6PPD N-cyclohexyl-N′-phenyl-p-phenylenediamine Naugard 445 4,4′-Bis-(a,a′-dimethylbenzyl) diphenylamine 1.500 0.82% Vanox ZMTI Zincmethylmercaptobenzimidazole 1.000 0.55% NOCHEK 4709A, Blended Paraffin Wax Waxe Cumar P-25 DLD Coumarone Indene Resin 10.000 5.51% 10.000 5.57% (KD-109) TMTD Tetramethyl thiuram disulfide 4.000 2.19% 0.300 0.17% 0.300 0.17% TBBS N-tertiary butyl-2-benzothiazole sulfenamide MBTS Benzothyazyl disulfide 1.500 0.83% 1.500 0.84% Sulphur Sulphur 2.000 1.10% 0.750 0.41% 0.750 0.42% Total 182.50 100.00% 181.55 100.00% 179.55 100.00%

(47) TABLE-US-00005 TABLE 5 Tests made on Composition 1 Sheet 1- Sheet 2- Sheet 3- Sheet 4- Sheet 5- Sheet 6- Composition-A Composition-1 Composition-B Composition-2 Composition-C Composition-3 Compounds (NBR 100, (NBR 100, (HNBR 100, (HNBR 100, (XNBR 100, (XNBR 100, Tests Reference) CNT, kevlar) Reference) CNT, kevlar) Reference) CNT, kevlar) Specific Gravity (g/mL) 1.165 1.164 1.177 1.170 1.155 1.147 Hardness (shore A) 61 66 62 72 68 71 Tensile (psi) 1749 1863 3599 3018 1781 1959 Elongation (%) 321 302 452 436 423 428 Modulus 50% (psi) 108 496 209 592 244 465 Modulus 100% (psi) 398 823 333 846 377 706 Modulus 300% (psi) 1696 1849 1420 1731 1173 1303 Tear (lbs die C) 185 200 188 239 177 204 MDR 191 C. ML 0.32 0.65 0.1 0.36 0.69 0.93 t10 0.72 0.71 0.86 0.8 0.57 0.55 t95 1.85 1.86 3.31 3.33 3.15 3.12 MH 12.46 14.72 11.74 13.77 5.04 5.78 Viscosity ML Mooney 12 18 7 12 18 24 145 C. Scorch T-5 145 C. minutes 8.28 6.75 5.87 5.18 5.53 5.61 DIN Abrasion (mm3) 115 114 162 163 122 130 Heat Aging Hardness difference 6 6 7 5 10 9 (70 h/100 C.) Tensile difference (%) 8.3 −8.1 −26.8 −19.5 48.6 29.7 Elongation difference (%) −14.6 −28.5 −37.2 −46.3 −15.1 −19.4 Fluid Immersion Hardness difference 2 0 3 2 4 1 (IRM 903; Tensile difference (%) −22.6 −37.9 −55.3 −43 2.5 −2.3 70 h/100 C.) Elongation difference (%) −43 −58.6 −45.1 −52.5 −32.4 −32.5 Volume difference (%) 1.4 3.8 −1.1 −0.7 6.4 6.6 Weight difference (%) −0.1 2.1 −2.2 −1.8 4.1 4.4

(48) The comparison of Compositions A to C with the Compositions 1 to 3, their counterparts with the same ingredients plus PRO 7000 and Kevlar Fiber, show interesting behaviour of the materials. The fact of adding MWCNT and aramid fibers exhibit a significant increase in the hardness and modulus when performing the stress-strain test without losing much elongation and tensile strength. The integration of these results thus show that the material with these additives are stronger and tougher. Moreover, the other physical and dynamic properties are not negatively affected by the additives. The DIN abrasion resistances are unchanged as well as heat resistance and immersion-swell resistance properties. This was unexpected since, usually, increasing hardness and modulus with conventional means—polymers, fillers and curative chemicals—is known to be detrimental to these properties, especially abrasion resistance. Briefly, applicants have obtained and tested tougher and more rigid materials, but that surprisingly keep the advantages of softer materials with comparable matrix elastomer. This is usually required for the use in demanding oil and gas applications were resistance to wear, heat and pressure are needed, like the powersection stators.

Example 4

Fuel Immersion Test for Various Rubber Compositions

(49) Some tests have been made in order to verify the resistance properties of the compositions when submitted to liquids such as fuel. For example, such compositions can be used for making products that are in contacts with fuel. For example, such products can be fuel tank lining. These tests have been made in accordance with Fuel B immersion test according to ASTM D-471.

(50) Compositions 4, 5 and 6 have been prepared have been prepared by using the same method as previously described for Composition 1. Their ingredients are listed in Table 6 below and the results of such tests are shown in Table 7.

(51) TABLE-US-00006 TABLE 6 Ingredients of Various Comparative Compositions Composition-4 (NBR Composition-5 (NBR Composition-6 100,, CNT, kevlar, 100,, CNT, kevlar, (NBR 100,, CNT, military fuel tank military fuel tank kevlar, military fuel lining) lining) tank lining) Trade Name Chemical Formula phr % w/w phr % w/w phr % w/w Kosyn KNB-35LL Acrylonitrile-Butadiene-Polymer (NBR) 96.65 41.80% Paracril CJLT Acrylonitrile-Butadiene-Polymer (NBR) 96.63 50.26% Krynac 4975 Acrylonitrile-Butadiene-Polymer (NBR) 96.640 43.52% SBR 1502 Styrene-Butadiene Rubber 19.94 8.62% MERGE 1F770 KEVLAR Engeneered Elastomer (in NBR) 4.35 1.88% 4.37 2.27% 4.37 1.97% PRO 7000 NC 7000 MWCNT 2 0.86% 2 1.04% 2.02 0.91% Carbon Black N-550 Carbon Black 80 34.60% 67 34.85% 67.00 30.17% Mistron Vapor R Compacted Microcristalline talc 20.00 9.01% TP-90B Hexaoxatricosane 19.00 8.56% DOA Dioctyl Adipate 11 4.76% DBS Dibutyl Sebacate 9.2 4.79% Stearic Acid Stearic acid 1 0.43% 1 0.52% 1.00 0.45% Zinc Oxide Zinc Oxide 5 2.16% 4.2 2.18% 4.20 1.89% 6PPD N-cyclohexyl-N′-phenyl-p-phenylenediamine 2 0.86% 1.7 0.88% 1.70 0.77% NOCHEK 4709A, Blended Waxe Paraffin Wax 3 1.30% 2.5 1.30% 2.50 1.13% Struktol WB-222 Blend of proprietary fatty acids 2 0.86% TBBS N-tertiary butyl-2-benzothiazole sulfenamide 1.9 0.82% 1.6 0.83% 1.60 0.72% CTP-PVI Retarding agent 0.4 0.17% 0.35 0.18% 0.35 0.16% Sulphur Sulphur 2 0.86% 1.7 0.88% 1.70 0.77% Total 231.24 100.00% 192.25 100.00% 222.08 100.00%

(52) TABLE-US-00007 TABLE 7 Fuel Immersion Tests made on Compositions 4, 5 and 6 Sheet 4- Sheet 5- Sheet 6- Compo- Compo- Compo- sition-4 sition-5 sition-6 (NBR (NBR (NBR 100,, CNT, 100,, CNT, 100,, CNT, Tests kevlar) kevlar) kevlar) Specific (g/mL) 1.208 1.221 1.274 Gravity Hardness (shore A) 78 78 80 Tensile (psi) 2088 2701 2268 Elongation (%) 379 348 273 Modulus (psi) 1173 1328 1395 100% Modulus (psi) na 2575 na 300% Tear (lbs, die C) 222 266 201 MDR 191 C ML 1.54 1.71 2.20 t10 0.94 0.77 0.66 t95 2.62 2.25 1.62 MH 18.06 18.78 16.42 Viscosity Mooney 29 43 42 ML 145 C. Scorch T-5 minutes 10.49 6.55 6.87 145 C. Fuel Hardness −14 −6 0 Immersion difference (%) (Reference Tensile −37.5 −21.7 −4.9 Fuel B; difference (%) 72 h/23 C.) Elongation −39.2 −25.6 4.8 difference (%) Volume 33.9 9.0 0.1 difference (%) Weight 21.6 5.8 −0.6 difference (%)

(53) The results of Fuel B immersion test according to ASTM D-471 shown in Table 7 clearly demonstrate that the compositions of the present disclosure can be useful for preparing products that are resistant to fuel. In the present case, the Fuel B was a mixture of isooctane (70%) and toluene (30%). The different acrylonitrile-butadiene polymers used in Compositions 4, 5 and 6 had different concentrations of acrylonitrile. In fact, Kosyn KNB-35LL has an acrylonitrile concentration of about 34 wt %, while Paracril CJLT has an acrylonitrile concentration of about 40 wt %, and Krynac 4975 has an acrylonitrile concentration of about 49 wt %. Without wishing to be bound to such a theory, it seems that, at least within those results, higher quantity of acrylonitrile allowed for better results since the polar nitrile groups are efficient for preventing non-polar solvents from entering into the composition.

(54) For all these reasons, it was found that the compositions of the present disclosure were very durable in applications related to oil and gas industry and mining industry. Such compositions can thus be useful for manufacturing various rubber products used in such fields as well as in various other fields.

(55) The Applicant hereby submits that the person skilled in the art would clearly understand that the various embodiments presented in paragraphs [0024] to [00188], when applicable, can be combined in all possible manners and be applied to the compositions recited in paragraphs [0008] to [0020]. The embodiments of paragraphs [0024] to [00188] of the present disclosure are presented in such a manner in the present disclosure so as to demonstrate that every combinations of embodiments, when applicable, can be made. These embodiments have thus been presented in a manner equivalent to making dependent claims for all the embodiments that depend upon any of the preceding claims (covering the previously presented embodiments), thereby demonstrating that they can be combined together.

(56) While a description was made with particular reference to the specific embodiments, it will be understood that numerous modifications thereto will appear to those skilled in the art. Accordingly, the above description and accompanying drawings should be taken as specific examples and not in a limiting sense.