Rubber and Elastomers Sustainably meeting tomorrow s challenges May 15, 2017, Manchester, United Kingdom Alternative uses of devulcanised rubber F. BARATIN, S. SEGHAR, J-P. BOUYSSET, M. ROLLAND-MONNET, M. GRUFFAT Phénix-Technologies, 29 rue de Champfroid, 28800 Sancheville France 1
Presentation outline Phénix-Technologies : general presentation Recycling methods o Micronisation o Devulcanisation Characteristics of devulcanised rubber Uses of devulcanised rubber Experienced issues New developments Conclusion 2
Phénix-Technologies : general presentation Phénix-Technologies : general presentation Recycling methods o Micronisation o Devulcanisation Characteristics of devulcanised rubber Uses of devulcanised rubber Experienced issues New developments Conclusion 3
Phénix-Technologies : general presentation Phénix is located in Sancheville, France Member of various associations: Elastopôle (French cluster on Elastomers) AFICEP ( Rubber Engineers Association) ASTM (American Society for Testing Materials) Sustainable materials group (ARTIS) Active in elastomer recycling area Rubber granulation / pulverisation / micronisation Devulcanisation by reactive extrusion assisted or not by scco2 Consulting: secondary raw materials produced by ELT s Thermolysis Founder and single participant of the European project DEVULC (H2020, from April 2015 to April 2017) 4
Phénix-Technologies : general presentation Granulation-Pulverisation-Micronisation Devulcanisation unit Granulator - Pulveriser - Microniser 3 Twin screw extruders For devulcanisation testing (27 mm) : coupled with a CO2 pump For TPE-V testing (40 mm) For devulc processing at an industrial scale (to be installed Sept 2017) 5
Phénix-Technologies : general presentation Laboratory Material Characterisation: Viscometer Mooney MV 2000 - Alpha tech. Rheometer MDR Pioneer - Alpha tech. TGA2 - Mettler Toledo FTIR Is10 - Thermo Scientific Coupling line TGA-IR Mechanical testing (traction, compression, tear strength ) - AGS-X Shimadzu Hardness tester Shore A Rubber shaping: Lab Mixing mill (cylinders) Vulcanisation press Moulds 6
Phénix-Technologies : general presentation Phénix commercial activities Subcontracting work Granulation Pulverisation Micronisation Devulc processing (starting end of 2017) Devulcanisation trials Free trials < 50kg Sell of machines Granulator Pulveriser Microniser Devulcanisation units Lab services Mooney, MDR, TGA, FTIR, mechanical behaviours Consultancy services 7
Micronisation Phénix-Technologies : general presentation Recycling methods o Micronisation o Devulcanisation Characteristics of devulcanised rubber Uses of devulcanised rubber Experienced issues New developments Conclusion 8
Recycling methods Micronisation CLASSIFICATION BY PARTICLE SIZE DISTRIBUTION Coarse Rubber Powders 425* 2000 µm 40 10 mesh Fine Rubber Powders Micronized Rubber Designation : Mc Active Rubber Powder < 425* µm Typically 75 300 µm Max 50 µm (to be discussed) Chemical activation rubber (CAR) Physical activation rubber (PAR) Bio activation (re Michelin TREC) < 40 mesh Typically 200 50 mesh Max 300 mesh * For UHP technology 590 µm (30 mesh) instead of 425µm (40 mesh) 9
Recycling methods Micronisation Direct compression moulded Micronised powder ~ 300µm (50 mesh) Incorporated in mixes and vulcanised (example with EPDM) 10
Devulcanisation Phénix-Technologies : general presentation Recycling methods o Micronisation o Devulcanisation Characteristics of devulcanised rubber Uses of devulcanised rubber Experienced issues New developments Conclusion or tentative to «break down» what Mr GOODYEAR built in 1844 11
Recycling methods Granulation Production scraps or end-of-life products New rubber products The rubber cycle Extruder + scco 2 + Crosslinking agent + cure Devulcanised rubber Devulcanisation + thermoplastic (+ crosslinking agent) 12
Recycling methods Devulcanisation Existing Methods: Mechanical (with or without chemicals) Thermal (with or without chemicals) Physical (Ultrasounds,micro-waves) Chemical Micro-biological Macromolecule Some of these techniques are either (or both): Carbon-Sulfur bond leading to high material degradation (i.e excessive breaking of C-C bonds) not economically viable using harmful (and forbidden or about to be) chemical devulcanisation agents 13
Recycling methods Devulcanisation Principal links in the rubber matrix: C-S-C C-S-S-C C-Sx-C Devulcanisation methods are based on 4 fundamental properties of X links: 1) Differences in bond energies (kj/mol) C-C C-S S-S 100 310 270 2) Differences in shear, stiffness/elastic constant C-C C-S S-S -100 Medium value -3 3) Reactivity to chemical agents: Devulcanising agents 4) Differences in susceptibility to biological attacks: 2 or 3 methods are commonly combined 14
Recycling methods Devulcanisation with scco2 This process was developed in an autoclave by CHEN et al [1] and made continuous by M. Meysami and C. Tzoganakis (2013) Benefit of the process: Fast and continuous Low devulcanisation temperatures High-quality devulcanised material (best selectivity of bond breakage) No hazardous chemicals Low energy consumption Supercritical carbon dioxide (scco2): T c = 31 C P c = 72.9atm (1070 psi) Non toxic, acts as a extender 1. D. T. Chen, C. A. Perman, M. E. Riechert, J. Hoven, Depolymerization of tire and natural rubber using supercritical fluids, J. Hazard. Mater., vol. 44, no. 1, pp. 53 60, Nov. 1995. 15
Recycling methods Devulcanisation with scco2 Rubber swelling (scco2) before mechanically cutting the bonds 16
Characteristics of devulcanised rubber Phénix-Technologies : general presentation Recycling methods o Micronisation o Devulcanisation Characteristics of devulcanised rubber Uses of devulcanised rubber Experienced issues New developments Conclusion 17
Characteristics of devulcanised rubber Energy (kwh/kg) The CO2 function: The CO 2 acts as an extender, it: Facilitates the process Allows to proceed at lower T C with fewer energy The best devulcanised rubber is obtained at lower T C 0.53 0.47 0.41 Energy consumption on GTR compounds avec CO2 sans CO2 0.35 100 110 120 130 140 150 160 barrels temperatures ( C) 18
Characteristics of devulcanised rubber Comparison between 2 samples with the same viscosity and from the same initial material (butyl rubber) Sample 1: Obtained at high T C without CO 2 Sample 2: Obtained at low T C with CO 2 R = % Soluble fraction % Swelling Entirely soluble Insoluble R1 > R2 19
Characteristics of devulcanised rubber HORIKX plot for analysis of the ratio of crosslink to main chain scission: Temperature R Degradation 20
Characteristics of devulcanised rubber MDR rheogram at 180 C After devulcanisation After re-activation + Addition of curing agents Red: Torque Green : Viscosity, viscoelastic behaviour Blue : Torque derivative The devulcanised material behaves as a non-activated raw mix (flat MDR curve after devulcanisation) 21
Uses of devulcanised rubber Phénix-Technologies : general presentation Recycling methods o Micronisation o Devulcanisation Characteristics of devulcanised rubber Uses of devulcanised rubber Experienced issues New developments Conclusion 22
Uses of devulcanised rubber 1) Use of 100% devulcanised rubber Example: Ground Tyres Rubber (GTR) Devulcanised GTR New vulcanised GTR Tensile strength (MPa) Stain at break (%) GTR 1 10.5 315 GTR 2 11.6 246 Low-cost materials Adjustable mechanical properties according to the formulation Can replace the virgin rubber in various applications (building, civil engineering ) 23
Uses of devulcanised rubber 2) Incorporated in a virgin rubber matrix Examples 1 and 2: EPDM and NR Reincorporation and revulcanisation as second material in master batches Good preservation of the mechanical properties 1 1 0.8 0.8 0.6 0.6 0.4 0.4 0.2 0.2 0 Hardness IRHD UTS Elongation at break E100% 0 Hardness IRHD Ultimate Tensile Strengh Elongation at break E100% reference 5% 10% 20% reference 5% 10% 20% Regenerated EPDM reincorporated in an initial formulation Regenerated NR reincorporated in an initial formulation 24
Stress at break σ (MPa) Deformation at break ε (%) Uses of devulcanised rubber 2) Incorporated in a virgin rubber matrix Example 3: Styrene Butadiene Rubber (SBR) Devulcanised SBR Raw SBR 25 600 20 15 10 5 0 0 10 20 30 Devulcanised SBR content (% by weight) 500 400 300 200 100 0 0 10 20 30 Devulcanised SBR content (% by weight) New vulcanised SBR Loss of properties at 30% low degradation of the mechanical properties Allows to reduce the costs Tensile strength (Mpa) strain at break (%) 22,8 % 5 % 25
Uses of devulcanised rubber 3) Incorporated in a thermoplastic matrix Example: Thermoplastic vulcanisates (TPEv) Devulcanised rubber Thermoplastic Thermoplastic vulcanisates Simplified processing Can be processed by extrusion, injection molding, blow molding or thermoforming Ease of scraps and waste recycling Can be easily colored when there is no carbon black content 26
Experienced issues Phénix-Technologies : general presentation Recycling methods o Micronisation o Devulcanisation Characteristics of devulcanised rubber Uses of devulcanised rubber Experienced issues New developments Conclusion 27
Experienced issues Some problems remain and must be solved: Smelling process and materials Obtaining a heterogeneous material (even more when the input materials are also (GTR-PC) ) Difficult reuse in some sectors (medical and food industry..) Investigations are currently in progress
New developments Phénix-Technologies : general presentation Recycling methods o Micronisation o Devulcanisation Characteristics of devulcanised rubber Uses of devulcanised rubber Experienced issues New developments Conclusion 29
New developments 1. Collaboration with Artis Reinforcement of dgtr with rcb* for the production of «Super Green compounds» 2. Collaboration with ASTM for determination of devulcanisates standards (Task group 11-20-01) 3. Collaboration with academic laboratories to solve issues concerning the smelling on certain rubbers * r-cb: recovered CARBON BLACK produced by ELT s PYROLYSIS
Conclusion Phénix-Technologies : general presentation Recycling methods o Micronisation o Devulcanisation Characteristics of devulcanised rubber Uses of devulcanised rubber Experienced issues New developments Conclusion 31
Conclusion Phénix can send you samples of rubber : Granulates Micronisates High-quality devulcanisates and quotations for industrial units of these different technologies Even rubber scraps can have a second-life, test our samples and let s talk about it! 32
THANK YOU FOR YOUR ATTENTION PHENIX -TECHNOLOGIES 33