Engineering plastic composites with high sustainable content

Abstract

A biocomposite formulation comprising a polyamide, an engineering polyester and biocarbon. The biocomposite can be reinforced with various additives, including reactive compatibilizers, bio-sourced carbons, nanofillers and recycled carbon fibers.

Claims

1. A biocomposite formulation comprising a polyamide, an engineering polyester, biocarbon, a maleated polypropylene (MAPP) or maleated polyethylene (MAPE) compatibilizer, and a nanofiller other than biocarbon.

2. The biocomposite formulation of claim 1, wherein the engineering polyester is polytrimethylene terephthalate (PTT), neat polyethylene terephthalate (PET), recycled PET, polybutylene terephthalate (PBT), poly (lactic acid) (PLA) or any combination thereof.

3. The biocomposite formulation of claim 1, wherein the polyamide is neat PA6, neat PA6,6, recycled polyamide, or a combination thereof.

4. The biocomposite formulation of claim 1, wherein the nanofiller is nanoclay.

5. The biocomposite formulation of claim 1, wherein the biocomposite formulation further comprises ethylene/n-butyl acrylate glycidyl methacrylate (EBA-GMA).

6. The biocomposite formulation of claim 1, wherein the biocomposite formulation comprises 1 to 3 wt. % of MAPP or MAPE.

7. The biocomposite formulation of claim 1, wherein the biocomposite formulation further comprises recycled carbon fiber.

8. The biocomposite formulation of claim 1, wherein the biocomposite formulation further comprises pultruded long carbon fiber master batch.

9. The biocomposite formulation of claim 1, wherein the biocomposite formulation has a notched impact strength equal to or more than 60 J/m.

10. The biocomposite formulation of claim 1, wherein the biocomposite formulation has tensile strength equal to or more than 100 MPa and a tensile modulus equal to or more than 9000 MPa.

11. The biocomposite formulation of claim 1, wherein the biocomposite formulation has a density equal to or more than 1.26 g/cm3.

12. The biocomposite formulation of claim 1, wherein the biocarbon is a hybrid biocarbon comprising two or more different biomass sources.

13. The biocomposite formulation of claim 1, wherein the biocarbon is a hybrid biocarbon comprising a mixture of biomass sources of different temperatures of pyrolysis.

Description

5. EXAMPLE OF THE FORMULATIONS

Examples 1-Heat Aging Performance of Different Polyamides and Engineering Polyesters

(1) TABLE-US-00001 TABLE 1 Heat aged PA6, PA66, PET and PBT conditions. Polyamide/ Thermal treatment at 140? C. ID polyester (hours) 1 PA6 0 2 Aged PA6 1000 3 PBT 0 4 Aged PBT 1000 5 PA6, 6 0 6 Aged PA6, 6 1000 7 PET 0 8 Aged PET 1000

(2) TABLE-US-00002 TABLE 2 Mechanical properties of conditioned PA6, PA 6,6, PET and PBT. Notched Tensile Tensile Elongation Flexural Flexural Impact Modulus Strength at break, Modulus Strength Strength ID (GPa) (MPa) (%) (GPa) (MPa) (J/m) 1 2.78 83 50.01 2.96 116 52 2 3.46 28 1.00 3.62 41 17 3 2.51 54 117.43 2.59 94 37 4 3.04 66 4.14 3.10 107 13 5 3.53 87 22.50 3.08 120 44 6 4.32 14 0.43 3.46 20 14 7 2.54 60 161.00 2.63 95 32 8 3.11 81 4.54 3.33 134 17

(3) Conditioned PA6, PA6,6, PET and PBT are given in Table 1 and Table 2. After thermal aging at elevated temperature for 1000 hours following ASTM D3045, the change in mechanical properties is evident for PA6, PA66, PET and PBT. It is clear that engineering polyesters PET and PBT are far superior in maintaining its tensile and flexural strength after thermal aging (Table 2) as compared to polyamide. Where most of the mechanical properties of PA6 and PA6,6 were reduced, these properties are in fact enhanced in PET and PBT. On this basis, PET and or PBT was selected as a blending component to improve the overall durability and retention of the mechanical properties in PA6 during thermal aging.

Examples 2-Mechanical Properties and Toughness Improvement for PA6/PBT Blends with Different Compatibilizers

(4) TABLE-US-00003 TABLE 3 Polymer blends with multi-phase compatibilizers. Polymer Additives Heat PA 6 PBT Recycled PA 6 MAPP EBA-GMA stabilizer ID (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (phr) 9 90 10 0 0 0 0 10 80 20 0 0 0 0 11 85.5 9.5 0 0 5 0 12 76 19 0 0 5 0 13 59.9 9.5 25.7 0 5 1 14 53.2 19 22.8 0 5 1 15 64.1 9.5 18.8 2.6 5 1 16 57 19 16.7 2.3 5 1 *ID 9-12 were processed with DSM twin screw extruder micro-compounder. *ID 13-16 are carried out in Leistritz twin screw extrusion followed by injection moulding.

(5) TABLE-US-00004 TABLE 4 Mechanical properties of polymer blends with multi-phase compatibilizers. Notched Tensile Tensile Elongation Flexural Flexural Impact Modulus Strength at break, Modulus Strength Strength Density ID (GPa) (MPa) (% ) (GPa) (MPa) (J/m) (gm/cm.sup.3) 9 2.92 81.7 45.51 3.12 115.77 49.15 1.148 (0.02) (1.82) (8.29) (0.02) (0.23) (4.39) (0.005) 10 3.04 81.2 83.63 3.11 113.52 40.36 1.170 (0.13) (1.61) (4.42) (0.03) (0.82) (0.86) (0.005) 11 2.72 67.1 130.47 2.48 89.06 104.79 1.139 (0.19) (0.78) (18.61) (0.01) (0.49) (14.64) (0.004) 12 2.89 64.9 61.03 2.44 85.87 72.257 1.151 (0.22) (0.28) (3.84) (0.02) (0.70) (3.393) (0.002) 13 3.09 68.1 8.99 2.59 98.8 49.88 1.144 (0.15) (0.68) (3.73) (0.04) (0.936) (4.81) (0.004) 14 3.06 63.7 6.59 2.52 97.4 39.83 1.159 (0.10) (0.84) (1.59) (0.05) (1.24) (4.04) (0.001) 15 3.22 62.2 12.79 2.61 97.31 59.21 1.1325 (0.47) (1.04) (1.14) (0.03) (1.14) (5.036) (0.001) 16 2.81 64.0 7.49 2.78 102.24 47.72 1.146 (0.14) (0.91) (1.00) (0.07) (1.57) (1.06) (0.001)

(6) As showed in Table 4, the binary and ternary blends of the present invention, PA6, PBT and recycled nylon, have been effectively compatibilized to produce high toughness blends that exceeds the theoretical properties expected by the rule of mixture.

Examples 3-Mechanical Properties Enhancement with Biosourced Carbon Pyrolyzed from Different Biomasses

(7) TABLE-US-00005 TABLE 5 Effect of different types of biocarbon-reinforced PA6 (30/70). Notched Pyrolysis Ball- Tensile Tensile Elongation Flexural Flexural Impact Type of Temp. milling Modulus Strength at break, Modulus Strength Strength Density ID biocarbon (? C.) (hrs) (GPa) (MPa) (%) (GPa) (MPa) (J/m) (gm/cm.sup.3) 17 Miscanthus 650 1 3.97 80.2 15.54 4.02 134.11 45.20 1.19 (0.36) (0.92) (3.09) (0.04) (0.7) (1.13) (0.005) 18 Wood chips 650 1 4.55 83 4.34 4.11 131.99 26.30 1.195 (0.03) (2.73) (0.55) (0.02) (4.516) (0.77) (0.001) 19 Wood chips 650 4 4.26 77.5 13.37 4.01 128.93 38.06 1.22 (0.12) (0.72) (1.97) (0.10) (2.85) (3.63) (0.002) 20 Miscanthus 900 1 5.04 76.8 2.23 4.80 130.53 23.68 1.214 (0.15) (2.23) (0.29) (0.10) (3.92) (2.01) (0.004) 21 Lignin 900 1 4.60 76.9 2.36 4.47 120.10 21.48 1.239 (0.12) (0.47) (0.07) (0.04) (0.99) (1.45) (0.004) 22 Chicken 650 1 4.10 82.2 18 3.96 130.6 37.68 1.19 Feather (0.15) (0.98) (1.27) (0.04) (0.85) (3.2) (0.004) 23 Wood chips 350 1 3.29 63.2 2.24 3.18 117.21 25.28 1.179 (0.15) (1.81) (0.09) (0.06) (2.105) (2.37) (0.04) 24 Corn Cobs 500 2 3.58 75.1 2.70 3.51 124.14 26.36 1.223 (0.08) (1.13) (0.08) (0.07) (1.07) (2.63) (0.015) 25 Soyhull 500 2 3.30 60.5 2.08 3.33 106.81 23.45 1.182 BioC (0.10) (1.19) (0.08) (0.04) (3.08) (1.47) (0.015)

(8) In the example given in Table 5, the effect of biocarbon surface chemistry, source of biocarbon and pyrolysis temperature on the properties of PA 6-biocarbon biocomposites were investigated. These biocarbons are incorporated into the PA6 matrix at 30 wt. % loading to fabricate biocomposites. It was observed that the modulus was higher for biocarbon pyrolyzed at a higher temperature, while functional groups were absent in this biocarbon. The composite containing biocarbon pyrolyzed at a lower temperature revealed a higher strength and a greater affinity with the PA6.

Examples 4-Mechanical Performance of PA6 and PA66 Reinforced Biocarbon and Long Fibers

(9) TABLE-US-00006 TABLE 6 Composition of biocarbon/PA6 biocomposites and biocarbon/PA6,6 biocomposites with LCFMB and LGFMB. Polyamide Biocarbon Recycled Additives Miscanthus Wood Fiber PA6 PA6,6 PA 6 MAPP BC BC LGFMB LCFMB ID (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (phr) (phr) 26 80 0 0 0 0 20 0 0 27 75 0 0 5 0 20 0 0 28 80 0 0 0 20 0 5 0 29 80 0 0 0 20 0 0 5 30 80 0 0 0 0 20 5 0 31 80 0 0 0 0 20 0 5 32 80 0 0 0 0 20 2.5 2.5 33.sup.$ 80 0 0 0 0 20 5 0 34.sup.$ 80 0 0 0 0 20 0 5 35.sup.$ 80 0 0 0 0 20 2.5 2.5 36 0 80 0 0 20 0 0 0 37 0 75 0 5 20 0 0 0 38 0 80 0 0 0 20 0 0 39 0 75 0 5 0 20 0 0 40 0 80 0 0 20 0 5 0 41 0 75 0 5 20 0 5 0 42 0 80 0 0 0 20 5 0 43 0 75 0 5 0 20 5 0 44 0 80 0 0 20 0 0 5 45 0 75 0 5 20 0 0 5 46 0 80 0 0 0 20 0 5 47 0 75 0 5 0 20 0 5 48 0 0 100 0 0 0 0 0 49 0 0 80 0 0 20 0 0 50 0 0 80 0 0 20 5 0 51 0 0 80 0 0 20 0 5 *The above compounding formulation are carried out in Leistritz twin screw extrusion followed by injection moulding. *LGFMBLong glass fiber/PA6 master batch *LCFMBLong carbon fiber/PA6 master batch *Both Miscanthus and wood biocarbon used in the biocomposites formulations are produce with batch pyrolysis process at 650? C. and 4 hours ball-milling. *The long carbon fibers or long glass fiber master batch were introduce during injection moulding only. .sup.$The long carbon fibers or long glass fiber master batch were introduce during Leistritz twin screw extrusion.

(10) TABLE-US-00007 TABLE 7 Effect of MAPP compatibilizer on the mechanical properties of biocarbon/PA6 biocomposites with LCFMB and LGFMB. Notched Tensile Tensile Elongation Flexural Flexural Impact Modulus Strength at break, Modulus Strength Strength Density ID (GPa) (MPa) (% ) (GPa) (MPa) (J/m) (gm/cm.sup.3) 26 3.747 76.8 15.49 3.39 120.06 29.60 1.165 (0.309) (0.84) (1.69) (0.021) (1.35) (4.62) (0.003) 27 3.764 70.7 9.43 3.66 120.7 40.11 1.1513 (0.165) (0.53) (2.28) (0.0143) (0.59) (4.44) (0.0005) 28 4.436 80.8 4.94 3.88 130.61 38.64 1.1656 (0.204) (0.55) (0.52) (0.0977) (3.42) (3.91) (0.0005) 29 5.677 104.7 3.02 5.023 161.98 43.83 1.1576 (0.494) (3.88) (0.42) (0.150) (3.391) (4.529) (0.0025) *The long carbon fibers master batch were introduce during injection moulding only.

(11) TABLE-US-00008 TABLE 8 Effect of different processing techniques on the mechanical performance of biocarbon/PA6 biocomposites with LCFMB and LGFMB. Long Fiber Notched Master Tensile Tensile Elongation Flexural Flexural Impact Batch Modulus Strength at break, Modulus Strength Strength Density ID (phr) (GPa) (MPa) (% ) (GPa) (MPa) (J/m) (gm/cm.sup.3) 30 5 phr 4.08 84.5 8.26 3.733 132.67 29.10 1.1745 LGFMB (0.21) (1.31) (0.86) (0.038) (1.75) (3.86) (0.0007) 31 5 phr 5.99 113.6 3.22 4.659 166.47 30.36 1.173 LCFMB (0.42) (6.82) (0.27) (0.288) (7.54) (4.16) (0.0014) 32 2.5 phr 4.30 80.40 17.91 3.69 123.68 30.01 1.200 LGFMB (0.25) (2.32) (3.62) (0.13) (4.11) (0.88) (0.003) 2.5 phr LCFMB 33.sup.$ 5 phr 3.79 73.10 25.13 3.17 110.31 38.21 1.199 LGFMB (0.06) (0.31) (0.98) (0.07) (1.80) (3.42) (0.001) 34.sup.$ 5 phr 4.20 78.30 18.84 3.47 118.03 34.59 1.193 LCFMB (0.10) (0.37) (0.91) (0.06) (1.79) (6.78) (0.003) 35.sup.$ 2.5 phr 3.93 75.6 20.19 3.51 117.85 36.68 1.202 LGFMB (0.06) (0.36) (4.40) (0.10) (2.13) (4.86) (0.002) 2.5 phr LCFMB *The long carbon fibers or long glass fiber master batch were introduce during injection moulding only. .sup.$The long carbon fibers or long glass fiber master batch were introduce during Leistritz extrusion.

(12) The incorporation of long fiber master batch during injection moulding is more advantages (advantageous?) than addition of all the material in twin screw extruder. Moreover, long carbon fiber master batch composites showed higher mechanical properties compared to long glass fiber master batch composites as well as the hybrid of both fibers.

(13) TABLE-US-00009 TABLE 9 Mechanical properties of hybrid of PA6,6/biocarbon biocomposites with LCFMB and LGFMB. Tensile Tensile Elongation Flexural Flexural Notched Modulus Strength at break, Modulus Strength Impact Density ID (GPa) (MPa) (% ) (GPa) (MPa) Strength (gm/cm.sup.3) 36 4.42 92.8 5.19 3.95 146.95 32.53 1.181 (0.21) (1.37) (0.86) (0.02) (0.30) (0.852) (0.006) 37 3.57 72.6 6.20 3.45 117.62 35.18 1.175 (0.14) (0.69) (0.63) (0.036) (0.442) (1.316) (0.001) 38 4.34 82.5 2.54 4.10 144.35 26.49 1.177 (0.15) (2.51) (0.32) (0.08) (2.287) (2.67) (0.001) 39 4.10 70.0 3.95 3.56 118.02 35.33 1.1645 (0.17) (0.45) (0.27) (0.02) (0.63) (1.32) (0.001) 40 4.66 90.1 2.47 4.10 152.29 32.2 1.195 (0.16) (0.97) (0.07) (0.07) (3.30) (1.004) (0.0034) 41 3.76 79.1 3.78 3.57 124.77 36.20 1.188 (0.12) (1.75) (0.16) (0.06) (2.15) (3.56) (0.000) 42 4.76 88.9 2.75 4.14 149.4 27.24 1.184 (0.30) (2.33) (0.22) (0.05) (2.54) (3.28) (0.005) 43 4.33 77.6 3.22 3.78 126.90 35.01 1.174 (0.11) (1.00) (0.20) (0.05) (2.14) (0.93) (0.001) 44 5.55 120.8 3.02 4.70 175.06 34.242 1.1905 (0.41) (6.96) (0.34) (0.05) (2.40) (2.611) (0.0007) 45 4.96 98 3.20 4.03 135.89 36.482 1.182 (0.34) (2.78) (0.27) (0.09) (3.46) (2.245) (0.001) 46 5.82 109.6 2.68 4.96 177.45 27.67 1.181 (0.39) (5.56) (0.51) (0.10) (3.71) (5.75) (0.001) 47 5.17 93.8 2.72 4.24 140.11 35.82 1.166 (0.16) (1.89) (0.33) (0.21) (4.70) (1.60) (0.001) *The long carbon fibers master batch were introducing during injection moulding only.

(14) TABLE-US-00010 TABLE 10 Mechanical properties of PA6/recycled PA6/biocarbon-based biocomposites with LCFMB and LGFMB. Tensile Tensile Elongation Flexural Flexural Notched Modulus Strength at break, Modulus Strength Impact Density ID (GPa) (MPa) (% ) (GPa) (MPa) Strength (gm/cm.sup.3) 48 3.386 65.5 15.88 2.813 104.24 45.04 1.166 (0.246) (0.30) (0.87) (0.025) (1.69) (2.55) (0.001) 49 4.181 65.8 4.88 3.763 116.76 34.55 1.199 (0.216) (0.25) (1.02) (0.018) (0.61) (1.66) (0.002) 50 4.810 75.2 3.67 3.995 125.24 36.61 1.232 (0.152) (1.55) (0.38) (0.1007) (3.34) (1.70) (0.004) 51 5.827 92.9 2.84 4.64 141.33 41.16 1.205 (0.458) (5.82) (0.26) (0.225) (4.399) (2.02) (0.002) *The long carbon fibers master batch were introduce during injection moulding only.

Examples 5-Dimensional Stability Enhancement of PA6/PA66/PBT/PET/rPET Blends Hybrid Biocomposites by Addition of Small Amount of Nanoclay

(15) TABLE-US-00011 TABLE 11 Formulations for nano-enhanced biocomposites. Fiber Compatibilizer Fillers Recycled Polymer EBA- Bio- Carbon Heat PA6 PA 6,6 PBT PET rPET MAPP GMA Nanoclay carbon Fiber Stabilizer ID (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (phr) 52 100 0 0 0 0 0 0 0 0 0 0 53 70 0 0 0 0 0 0 0 30 0 0 54 70 0 0 0 0 0 0 1.5 28.5 0 0 55 48.0 0.0 12.0 0 0 3.0 5.0 0 19.0 13.0 0.0 56 45.2 0.0 11.3 0 0 3.0 7.0 1.5 23.0 9.0 0.0 57 44.8 0.0 11.2 0 0 3.0 7.0 2.0 23.0 9.0 0.0 58 44.8 0.0 11.2 0 0 3.0 7.0 1.5 24.0 8.0 0.0 59 44.8 0.0 11.2 0 0 3.0 7.0 1.5 24.0 8.0 1.0 60 44.8 0.0 11.2 0 0 3.0 7.0 1.5 25.0 7.0 1.0 61 36.2 9.0 11.3 0 0 3.0 7.0 1.5 25.0 7.0 1.0 62 40.7 4.5 11.3 0 0 3.0 7.0 1.5 26.0 6.0 1.0 63 40.7 4.5 11.3 0 0 3.0 7.0 1.5 27.0 5.0 1.0 64 41.4 4.6 11.5 0 0 3.0 6.0 1.5 26.0 6.0 1.0 65 41.4 4.6 0 11.5 0 3.0 6.0 1.5 26.0 6.0 1.0 66 41.4 4.6 0 0 11.5 3.0 6.0 1.5 26.0 6.0 1.0

(16) TABLE-US-00012 TABLE 12 Mechanical performance and coefficient of linear thermal expansion (CLTE) of nano- enhanced biocomposite formulations. Notched Tensile Tensile Flexural Flexural Impact CLTE Modulus Strength Modulus Strength Strength (?m/m, CLTE (GPa) (MPa) (GPa) (MPa) (J/m) normal (?m/m, flow ASTM D ASTM D ASTM D ASTM D ASTM D HDT direction, direction, ID 638 638 790 790 256 (? C.) ASTM E831 ASTM E831 52 2.68 80.8 2.46 100.0 62.1 146.8 88.5 77.2 53 4.37 84.9 3.55 122.5 30.5 175.4 65.6 52.0 54 4.65 87.1 5.04 155.5 26.0 190.3 64.1 50.2

(17) Table 12 shows the mechanical properties and coefficient of linear thermal expansion (CLTE) of the nanocomposites in this invention. Blend ID 52 shows the mechanical and thermal properties of neat PA6. In Blend 53, the addition of 30 wt. % biocarbon enhances the tensile/flexural strength and modulus, HDT, and CLTE compared to neat nylon. The hybridization of biocarbon (28.5 wt. %) and nanoclay (1.5 wt. %) in Blend 54 yields superior mechanical properties compared to Blend 53. The stiffness and flexural strength are both significantly enhanced by addition of only 1.5 wt % of nanoclay. The HDT is further improved from 175.4 to 190.3? C., and the CLTE is reduced significantly.

(18) The key finding is that through hybridization of biocarbon and nanoclay, polyamide composites can be produced with high bio-based content (?30 wt. %), using only a very small amount of nanoclay, which possess excellent thermomechanical properties. The necessity of only a small amount of nanoclay due to hybridization with biocarbon contributes to the cost-performance efficiency of the biocomposites. A small amount of nanoclay creates nanocomposites with improved properties, while remaining cost-effective. The combination of nanoclay with biocarbon provides superior CLTE than composites with nanoclay alone.

(19) TABLE-US-00013 TABLE 13 Mechanical performance of nano-enhanced polyamide blend biocomposite formulations with more than 30% sustainable and recycled content. Notched Tensile Tensile Elongation Flexural Flexural Impact Sustainable/ Modulus Strength at break, Modulus Strength Strength Density recycled ID (MPa) (MPa) (%) (MPa) (MPa) (J/m) (g/cm.sup.3) content (%) 55 12462 122 2.21 9810 201 73.6 1.237 32.0 56 9684 92 1.71 8070 160 47.6 1.232 32.0 57 10271 89 1.77 8108 147 46.7 1.235 32.0 58 9959 89 2.30 7922 157 46.6 1.223 32.0 59 9234 84 2.36 7336 145 47.0 1.235 32.0 60 8161 82 1.80 6543 139 48.1 1.223 32.0 61 8946 89 2.42 7609 156 44.7 1.232 32.0 62 7540 86 2.39 6425 144 54.5 1.233 32.0 63 7128 80 2.34 6058 136 49.1 1.233 32.0 64 8312 89 2.33 7054 150 41.4 1.235 32.0 65 7288 87 2.19 6927 148 29.9 1.248 32.0 66 7856 88 1.46 6937 139 32.4 1.246 32.0

(20) Polyamide blending with PBT is employed to preserve tensile properties during thermal aging. A maleated polypropylene (MAPP) compatibilizer in combination with EBA-GMA is used to promote miscibility as well as enhance toughness in this polymer blend. Around 3% of MAPP is used, and between 5-7% of EBA-GMA.

(21) Blend 55 demonstrates a PA6/PBT blend in which biocarbon is hybridized with recycled carbon fiber to create a biocomposite with high bio-based content (19%) and recycled content (13%). Due to the unique compatibilization with MAPP and modification with EBA-GMA, this blend maintains an impact strength of 73.6 J/m, superior to neat PA6, while also possessing very high tensile/flexural strength and modulus with a relatively low density of 1.237 g/cm3.

(22) Blends 56-60 demonstrate that by incorporating nanoclay as a hybrid reinforcement, a lower amount of recycled carbon fiber can be used while maintaining high mechanical properties. A tensile modulus greater than 8 GPa can be maintained while reducing the carbon fiber content to 7%. Further, 1.0 phr of a copper salt-based heat stabilizer is added to improve the thermal durability to counter the environmental aging.

(23) Blend 61 demonstrates that by replacing 20% of the PA6 content with PA6,6, the tensile strength is increased by 7 MPa, the tensile modulus by 800 MPa, the flexural strength by 17 MPa, and the flexural modulus by 1100 MPa compared to Blend 13, while maintaining the same amount of reinforcement as used in Blend 60.

(24) Blends 62 and 63 demonstrate a material in which the amount of recycled carbon fiber is reduced and replaced proportionally with biocarbon. This yields a material which can demonstrate tensile modulus greater than 7 GPa and flexural modulus greater than 6 GPa, while using only 5% recycled carbon fiber by weight, and containing 27% bio-based content.

(25) Blends 65 and 66 demonstrate that the same system can be produced in which the PBT phase is replaced by PET and recycled PET, while maintaining excellent tensile and flexural strength and modulus.

Example 6-Significant Reduction in Weight/Density of the Invented Nylon-Based Biocomposites in Comparison to Conventional Nylon Composites Formulations

(26) TABLE-US-00014 TABLE 14 Density comparison of Nylon 6-based biocomposite vs. conventional 40/60 glass and talc filled nylon composites. Filler loading Density ID (wt. %) (g/cm.sup.3) 58 32.0 1.223 71 32.0 1.250 10% Glass Fiber 30.0 20% Talc 1.32-1.45 70% PA6 15% Glass Fiber 40.0 1.45-1.50 25% Talc 60% PA6

(27) Our developed PA6/rPA6-based biocomposites showed relatively low densities (?20% reduction) as compared to the popular conventional PA6/talc/glass fiber composites. A blend of nylon/rPA6/rPET was designed with improved mechanical performance (>100 MPa tensile strength and >9000 MPa of tensile modulus, reduced density as compared to conventional 40/60 nylon composites with 15 wt. % glass fiber and 25 wt. % talc.

Example 7-Performance of High Sustainable and Recycled Plastic Content in PA6-Based Biocomposites

(28) TABLE-US-00015 TABLE 15 High sustainable and recycled plastic content in PA 6-based biocomposites with hybrid fillers formulations. PA 6 composites with hybrid fillers Polymer Additives Recycled Fusa Biocarbon Fiber PA 6 PBT PA 6 rPET PLA MAPP EBG-MA N493 SMA Miscanthus Wood BC rCF LCFMB HS ID (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) BC (wt. %) (wt. %) (wt. %) (phr) (phr) 67 49.5 12.4 0 0 3 0 6 0 0 26 6 0 1 68 49.5 12.4 0 0 3 0 6 0 0 26 6 7.5 1 69 49.5 12.4 0 0 3 6 0 0 0 26 6 0 1 70 49.5 12.4 0 0 3 6 0 0 0 26 6 7.5 1 71 33.6 0 14.4 12 0 0 3 3 2 0 26 6 7.5 1 72 33.6 0 14.4 12 0 0 3 3 2 0 26 Hybrid 6 7.5 1 73 61 0 0 0 1 0 3 3 2 0 20 Hybrid 0 10 1 (wt. %) 74 24.4 0 36.6 0 1 0 3 3 2 0 20 Hybrid 0 10 1 (wt. %) 75 30.5 0 0 30.5 1 0 3 3 2 0 20 Hybrid 0 10 1 (wt. %) 76 33.6 0 14.4 12 0 0 3 3 2 26 0 6 7.5 1 77 22.4 0 41.6 0 0 0 3 3 2 0 20 Hybrid 0 8 1 (wt. %) 78 21.7 0 40.3 0 0 0 3 3 2 0 20 Hybrid 4 6 1 (wt. %) 79 33.6 0 14.4 12 0 0 3 3 2 0 26 6 7.5 1 80 33.6 0 14.4 12 1 (phr) 0 3 3 2 0 26 6 7.5 1 81 33.6 0 14.4 12 1 (phr) 0 3 3 2 26 0 6 7.5 1 *The above compounding formulation are carried out in Leistritz twin screw extrusion followed by injection moulding except samples no. 73, 74, 75, 76 are carried out in DSM. *The biocarbon used are pyroloyzed from miscanthus or wood chips in the ranged from 350? C. to 900? C. with different milling time and particles size. *Hybrid: Two different biocarbon from low and high pyrolyzed temperature. *HS: heat stabilizers *Recycled carbon fibers was added in the side feeder of the twin screw extruder. *The long carbon fibers master batch were introduce during injection moulding only.

Examples 8-Effect of Long Fiber Master Batch in the PA6-Based Biocomposites

(29) TABLE-US-00016 TABLE 16 Addition of long carbon fiber/PA6 (40/60) master batch during injection moulding. Notched Notched Izod Charpy Tensile Tensile Flexural Flexural Impact Impact Modulus Strength Elongation Modulus Strength Strength Strength (MPa) (MPa) at break, (MPa) (MPa) (J/m) (J/m) Carbon Fiber ASTM ASTM % ASTM ASTM D ASTM ASTM D ASTM D ID Content D 638 D 638 D638 790 D 790 256 256 67 6 rCF wt % 6644 84.4 2.25 6653 143.2 38.80 5.45 (311.3) (1.51) (0.66) (419.26) (5.55) (5.78) (1.11) 68 6 rCF wt % + 8177 112.0 1.94 8223 178.29 49.46 6.57 7.5 phr (474.32) (6.08) (0.21) (559.57) (7.36) (1.42) (0.05) LCFMB 69 6 rCF wt % 6481 75.1 3.16 5464 125.01 35.61 5.17 (735.5) (1.76) (0.5) (296.7) (3.99) (2.03) (1.42) 70 6 rCF wt % + 7985 98.8 2.06 6704 149.12 49.54 6.34 7.5 phr (265.91) (5.07) (0.24) (483.74) (6.805) (2.91) (0.06) LCFMB *The biocarbon used in the biocomposites contain 26 wt % of wood biocarbon pyrolyzed at 650? C. *rCFRecycled carbon fiber, LCFMBLong carbon fiber master batch

(30) We incorporate long carbon fiber master batch into the different compatibilized nylon-based biocomposites to further enhance the mechanical strength of the developed biocomposites. The tensile and flexural strength increased approximately ?30%; tensile modulus and flexural modulus increased approximately ?20% with only 3% addition of long carbon fiber.

Examples 9-Effect of Hybridized Biosourced Carbon in the PA6/rPA6-Based Biocomposites Formulations

(31) TABLE-US-00017 TABLE 17 Effect of hybridized biosourced carbon in the PA6/rPA6-based biocomposites formulations. Notched Izod MFI BioC Tensile Tensile Flexural Flexural Impact (g/10 Content Modulus Strength Modulus Strength Strength min) and (MPa) (MPa) Elongation at (MPa) (MPa) (J/m) At Type of Fraction ASTM D ASTM D break, % ASTM D ASTM D ASTM D Density 250 C. ID Biocarbon (wt. %) 638 638 ASTM D638 790 790 256 (g/cm.sup.3) 2.16 kg 71 Biocarbon 26 8520 107.0 2.16 6318 148.32 37.11 1.250 11.15 Pyrolyzed at (100%) (519.39) (6.89) (0.08) (218.00) (2.84) (2.92) (0.001) (1.76) 900? C. 72 Biocarbon 26 10290 102.7 1.74 7486 145.33 32.43 1.249 8.370 Pyrolyzed at (45% + (101.32) (2.23) (0.04) (141.57) (5.92) (1.56) (0.000) (1.75) 900? C. and 55%) Wood Biocarbon Pyrolyzed at 650? C. * The biocarbon used in the biocomposites formulations are produce with batch pyrolysis process of wood biomass at different temperature.

(32) The PA6/rPA6-based biocomposites reinforced with hybridized biocarbon exhibited higher tensile modulus and flexural modulus as compared to single type biocarbon reinforcement.

Example 10-Mechanical Performance of High Sustainable and Renewable Content for PAG/rPA6-Based Hybrid Biocomposites

(33) TABLE-US-00018 TABLE 18 Mechanical properties of high sustainable and renewable content for PA6/rPA6-based hybrid biocomposites. Notched Tensile Flexural Flexural Impact MFI Tensile Strength Elongation Modulus Strength Strength (g/10 Modulus (MPa) at break, (MPa) (MPa) (J/m) min) Sustainable/ (MPa) ASTM D % ASTM ASTM D ASTM ASTM D Density At 250 C. recycled ID ASTM D 638 638 D638 790 D 790 256 (g/cm.sup.3) 2.16 Kg content (%) 71 8520 107.0 2.16 6318 148.32 37.11 1.250 11.15 58.4 (519.39) (6.89) (0.08) (218.00) (2.84) (2.92) (0.001) (1.76) 72 10290 102.7 1.74 7486 145.33 32.43 1.249 8.370 58.4 (101.32) (2.23) (0.04) (141.57) (5.92) (1.56) (0.000) (1.75) 73 9217 138.8 2.15 7018 193.34 55.15 1.198 15.48 21.0 (539.59) (9.28) (0.20) (1276.51) (21.44) (5.16) (0.008) (1.89) 74 9183 122.7 1.96 7158 182.52 45.07 1.226 26.07 57.6 (673.63) (6.19) (0.17) (369.68) (7.56) (3.85) (0.002) (9.28) 75 10045 130.6 1.65 7083 159.98 44.67 1.264 8.81 51.5 (333.85) (5.92) (0.09) (569.42) (9.37) (3.48) (0.003) (0.76) 76 8680 103.5 2.08 7188 156.10 37.33 1.25 3.661 57.4 (649.10) (1.50) (0.13) (167.93) (3.14) (2.54) (0.0028) (0.63) 77 7210 106.0 2.52 6059 163.61 53.0 1.21 5.184 61.6 (709.33) (6.99) (0.32) (354.98) (7.53) (5.39) (0.004) (0.52) 78 8368 121.3 2.28 7413 189.70 57.86 1.2106 4.15 64.3 (637.44) (8.43) (0.12) (299.49) (5.52) (4.14) (0.004) (0.162) * The biocarbon used in ID 73, 74, 77, 78 is hybridization of batch pyrolyzed wood biomass at 350? C. and continuous pyrolyzed wood biomass at 650? C. respectively. * The biocarbon used in ID 72 is hybridization of batch pyrolyzed wood biomass at 900? C. and continuous pyrolyzed wood biomass at 650? C. respectively. *The biocarbon used in ID 76 is from continuous pyrolysis of Miscanthus biomass at 650? C. *The biocarbon used in ID 71 is from batch pyrolysis of wood biomass at 900? C.

(34) As shown in Table 18, the incorporation of high sustainable/recycled content (>50 wt. %) in the hybrid biocomposites formulation with the presence of the compatibilizers exhibited exceptional mechanical properties (tensile strength >100 MPa, tensile modulus ?9000 MPa, flexural modulus >7000 MPa, notched impact strength ?35-60 J/m. In particular, for ID: 75, tensile strength showed >130 MPa, tensile modulus >10 GPa, flexural modulus ?7.0 GPa and notched impact strength ?45 J/m.

Examples 11-Melt Flow Enhancement of PA6/rPA6/rPET Hybrid Biocomposites by Addition of PLA

(35) TABLE-US-00019 TABLE 19 Improving the melt flow index of PA6/rPA6/rPET-based biocomposites by addition of PLA. Notched Izod Tensile Tensile Flexural Flexural Impact Modulus Strength Elongation Modulus Strength Strength MFI PLA (MPa) (MPa) at break, (MPa) (MPa) (J/m) (g/10 min) Content ASTM D ASTM D % ASTM ASTM D ASTM D ASTM D Density At 250 C. ID (phr) 638 638 D638 790 790 256 (g/cm.sup.3) 2.16 Kg 79 0.0 10995 95.8 1.41 8355 152.23 31.24 1.243 7.904 (582.40) (3.32) (0.17) (503.10) (2.19) (0.53) (0.005) (1.01) 80 1.0 10288 96.2 1.67 7923 153.79 33.90 1.2515 13.755 (311.23) (3.33) (0.13) (322.74) (2.76) (1.30) (0.002) (1.71) * The biocarbon used in the biocomposites formulations are produce with batch pyrolysis process of wood biomass at 900? C. temperature. *The biocomposites samples from ID79-ID80 were developed in the DSM twin screw mini compounder followed by injection moulding.

(36) The high loading of fillers in a composites could result in poor flowability of the matrix which is undesirable for injection moulding parts. Flow enhancer usually applied for high filler loading of injection moulding parts. We found that the incorporation of PLA in the formulation aid in the flowability of the composites. The melt flow index (MFI) value of the biocomposites increase almost 2?after incorporation of low amount of PLA in the formulation.

Examples 12-Comparison of Different Biocarbon Reinforcement in PA6/rPA6/rPET Biocomposites

(37) TABLE-US-00020 TABLE 20 Comparison of different biocarbon reinforcement in PA6/rPA6/rPET biocomposites. Notched Izod Tensile Tensile Flexural Flexural Impact MFI Modulus Strength Elongation Modulus Strength Strength (g/10 BioC (MPa) (MPa) at break, % (MPa) (MPa) (J/m) min) Type of Content ASTM D ASTM D ASTM ASTM D ASTM D ASTM D Density At 250 C. ID Biocarbon (wt. %) 638 638 D638 790 790 256 (g/cm.sup.3) 2.16 Kg 80 Wood 26 10288 96.2 1.67 7923 153.79 33.90 1.2515 13.755 (311.23) (3.33) (0.13) (322.74) (2.76) (1.30) (0.002) (1.71) 81 Miscanthus 26 9333 88.2 1.91 7639 140.5 30.34 1.2475 4.324 (1258.7) (2.46) (0.16) (284.53) (3.45) (1.71) (0.001) (0.43)

(38) As presented in Table 20, the biosourced carbon derived from wood biomass showed higher mechanical properties as compared to the biosourced carbon derived from Miscanthus biomass.

(39) Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification, improvement and variation of the inventions embodied therein herein disclosed may be resorted to by those skilled in the art, and that such modifications, improvements and variations are considered to be within the scope of this invention.

(40) In addition, where features or aspects of the invention are described in terms of Markush groups, those skilled in the art will recognize that the invention is also thereby described in terms of any individual member or subgroup of members of the Markush group.

(41) All publications, patent applications, patents, and other references mentioned herein are expressly incorporated by reference in their entirety, to the same extent as if each were incorporated by reference individually. In case of conflict, the present specification, including definitions, will control.

(42) It is to be understood that while the invention has been described in conjunction with the above embodiments, that the foregoing description and examples are intended to illustrate and not limit the scope of the invention. Other aspects, advantages and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains.

NON-PATENT REFERENCES

(43) 1. Tanaka, G.; Goettler, L. A., Predicting the binding energy for nylon 6,6/clay nanocomposites by molecular modeling. Polymer 2002, 43 (2), 541-553. 2. Wu, T.-M.; Liao, C.-S., Polymorphism in nylon 6/clay nanocomposites. Macromolecular Chemistry and Physics 2000, 2001 (18), 2820-2825. 3. Liu, L.; Qi, Z.; Zhu, X., Studies on nylon 6/clay nanocomposites by melt-intercalation process. Journal of Applied Polymer Science 1999, 71 (7), 1133-1138. 4. Chavarria, F.; Paul, D. R., Comparison of nanocomposites based on nylon 6 and nylon 66. Polymer 2004, 45 (25), 8501-8515. 5. Fornes, T. D.; Paul, D. R., Crystallization behavior of nylon 6 nanocomposites. Polymer 2003, 44 (14), 3945-3961. 6. Fornes, T. D.; Yoon, P. J.; Keskkula, H.; Paul, D. R., Nylon 6 nanocomposites: the effect of matrix molecular weight. Polymer 2001, 42 (25), 09929-09940. 7. Cho, J. W.; Paul, D. R., Nylon 6 nanocomposites by melt compounding. Polymer 2001, 42 (3), 1083-1094. 8. Gao, F., Clay/polymer composites: the story. Materials Today 2004, 7 (11), 50-55. 9. Auto applications drive commercialization of nanocomposites. Plastics, Additives and Compounding 2002, 4 (1), 30-33. 10. Behazin, E.; Ogunsona, E.; Rodriguez-Uribe, A.; Mohanty, A. K.; Misra, M.; Anyia, A. O., Mechanical, Chemical, and Physical Properties of Wood and Perennial Grass Biochars for Possible Composite Application. Bioresources 2015, 11 (1). 11. Behazin, E.; Misra, M.; Mohanty, A. K., Sustainable biocarbon from pyrolyzed perennial grasses and their effects on impact modified polypropylene biocomposites. Composites Part B: Engineering 2017, 118, 116-124. 12. Behazin, E.; Misra, M.; Mohanty, A. K., Sustainable biocomposites from pyrolyzed grass and toughened polypropylene: Structure-property relationships. ACS Omega 2017, 2 (5), 2191-2199. 13. Wang, T.; Rodriguez-Uribe, A.; Misra, M.; Mohanty, A. K., Sustainable carbonaceous biofiller from miscanthus: size reduction, characterization, and potential biocomposites applications. BioResources 2018, 13 (2), 3720-3739. 14. Codou, A.; Misra, M.; Mohanty, A. K., Sustainable biocarbon reinforced nylon 6/polypropylene compatibilized blends: Effect of particle size and morphology on performance of the biocomposites. Composites Part A: Applied Science and Manufacturing 2018, 112, 1-10. 15. Myllytie, P.; Misra, M.; Mohanty, A. K., Carbonized Lignin as Sustainable Filler in Biobased Poly(trimethylene terephthalate) Polymer for Injection Molding Applications. ACS Sustainable Chemistry & Engineering 2016, 4 (1), 102-110. 16. Ogunsona, E. O.; Misra, M.; Mohanty, A. K., Impact of interfacial adhesion on the microstructure and property variations of biocarbons reinforced nylon 6 biocomposites. Composites Part A: Applied Science and Manufacturing 2017, 98, 32-44. 17. Ogunsona, E. O.; Misra, M.; Mohanty, A. K., Sustainable biocomposites from biobased polyamide 6,10 and biocarbon from pyrolyzed miscanthus fibers. Journal of Applied Polymer Science 2017, 134 (4). 18. Ogunsona, E. O.; Misra, M.; Mohanty, A. K., Influence of epoxidized natural rubber on the phase structure and toughening behavior of biocarbon reinforced nylon 6 biocomposites. RSC Advances 2017, 7 (15), 8727-8739. 19. Jubinville, D.; Chang, B. P.; Pin, J.-M.; Mohanty, A. K.; Misra, M., Synergistic thermo-oxidative maleation of PA11 as compatibilization strategy for PA6 and PBT blend. Polymer 2019, 179, 121594. 20. Wakita, N., Melt elasticity of incompatible blends of poly(butylene terephthalate)(PBT) and polyamide 6 (PA6). Polymer Engineering & Science 1993, 33 (13), 781-788. 21. Han, M. S.; Lim, B. H.; Jung, H. C.; Hyun, J. C.; Kim, S. R.; Kim, W. N., Reactive blends of poly(butylene terephthalate)/polyamide-6 with ethylene glycidyl methacrylate. Korea-Aust. Rheol. J. 2001, 13 (4), 169-177. 22. Cie?lak, M.; Schmidt, H., Possibilities of utilising textile floor covering wastes. 2002, 10 (2), 69-73. 23. Lievana, E.; Karger-Kocsis, J., Impact modification of PA-6 and PBT by epoxy-functionalized rubbers. Macromolecular Symposia 2003, 202 (1), 59-66. 24. Chiou, K.-C.; Chang, F.-C., Reactive compatibilization of polyamide-6 (PA 6)/polybutylene terephthalate (PBT) blends by a multifunctional epoxy resin. Journal of Polymer Science Part B: Polymer Physics 2000, 38 (1), 23-33. 25. Kim, S.-J.; Kim, D.-K.; Cho, W.-J.; Ha, C.-S., Morphology and properties of PBT/nylon 6/EVA-g-MAH ternary blends prepared by reactive extrusion. Polymer Engineering & Science 2003, 43 (6), 1298-1311.

PATENT REFERENCES

(44) [1] China Patent CN103087515B. [2] China Patent CN103073853B [3] U.S. Patent Application Publication No. 2018/0022921. [4] U.S. Pat. No. 9,809,702. [5] U.S. Pat. No. 8,877,338. [6] China Patent CN105086328B. [7] China Patent CN104693606B. [8] U.S. Pat. No. 8,541,001.