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Rubber and Elastomers – Sustainably meeting tomorrow’s challenges – May 15, 2017, Manchester, United Kingdom

Phénix-Technologies,

29 rue de Champfroid, 28800 Sancheville

France

Alternative uses of devulcanised rubber

F. BARATIN, S. SEGHAR, J-P. BOUYSSET, M. ROLLAND-MONNET, M. GRUFFAT

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Presentation outline

Phénix-Technologies - Rubber and Elastomers – Sustainably meeting tomorrow’s challenges – May 15, 2017, Manchester, United Kingdom

➢ Phénix-Technologies : general presentation

➢ Recycling methods

o Micronisation

o Devulcanisation

➢ Characteristics of devulcanised rubber

➢ Uses of devulcanised rubber

➢ Experienced issues

➢ New developments

➢ Conclusion

3Phénix-Technologies - Rubber and Elastomers – Sustainably meeting tomorrow’s challenges – May 15, 2017, Manchester, United Kingdom



o Micronisation

o Devulcanisation





➢ Conclusion

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)



Granulation-Pulverisation-Micronisation

Granulator - Pulveriser - Microniser

Devulcanisation unit

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)



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



• 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


Phénix commercial activities


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Micronisation




o Micronisation

o Devulcanisation





➢ Conclusion

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Recycling methods


* For UHP technology 590 µm (30 mesh) instead of 425µm (40 mesh)

CLASSIFICATION BY PARTICLE SIZE DISTRIBUTION

Coarse Rubber Powders 425* – 2000 µm 40 – 10 mesh

Fine Rubber Powders< 425* µm

Typically 75 – 300 µm< 40 mesh

Typically 200– 50 mesh

Micronized RubberDesignation : Mc

Max 50 µm (to be discussed) Max 300 mesh

Active Rubber Powder Chemical activation rubber (CAR) Physical activation rubber (PAR) Bio activation (re Michelin TREC)

Micronisation

Incorporated in mixes and vulcanised(example with EPDM)

Direct compression moulded

Micronised powder~ 300µm (50 mesh)


Micronisation

Recycling methods

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Devulcanisation


or tentative to « break down » what

Mr GOODYEAR built in 1844



o Micronisation

o Devulcanisation





➢ Conclusion

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Production scraps or end-of-life products

Granulation

Devulcanisation

Extruder + scCO2

Devulcanised rubber

New rubber productsThe rubber cycle

+ thermoplastic (+ crosslinking agent)

+ Crosslinking agent+ cure


Recycling methods

Existing Methods:

• Mechanical (with or without chemicals)• Thermal (with or without chemicals)• Physical (Ultrasounds,micro-waves)• Chemical• Micro-biological

Carbon-Sulfur bond

Macromolecule

Some of these techniques are either (or both):

• 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


Recycling methods

Devulcanisation

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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)

2) Differences in shear, stiffness/elastic constant

3) Reactivity to chemical agents: “Devulcanising agents”4) Differences in susceptibility to biological attacks: 2 or 3 methods are commonly combined

C-C C-S S-S

100 310 270

C-C C-S S-S

-100 Medium value

-3


Devulcanisation

Recycling methods

Supercritical carbon dioxide (scCO2):

Tc= 31 °C

Pc= 72.9atm (1070 psi)

→ Non toxic, acts as a extender

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


Devulcanisation with scCO2

Recycling methods

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.

This process was developed in an autoclave by CHEN et al [1] and made continuous by M. Meysami andC. Tzoganakis (2013)

Rubber swelling (scCO2) before mechanically cutting the bonds


Devulcanisation with scCO2

Recycling methods

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Characteristics of devulcanised rubber




o Micronisation

o Devulcanisation





➢ Conclusion

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0.35

0.41

0.47

0.53

100 110 120 130 140 150 160

Ene

rgy

(kW

h/k

g)barrels temperatures (°C)

Energy consumption on GTR compounds

avec CO2

sans CO2

The CO2 function:

• The CO2 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



Sample 1: Obtained at high T°C without CO2

Entirely soluble

Sample 2: Obtained at low T°C with CO2

Insoluble

Comparison between 2 samples with the same viscosity and from the same initial material (butyl rubber)


𝑅 =% 𝑆𝑜𝑙𝑢𝑏𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛

% 𝑆𝑤𝑒𝑙𝑙𝑖𝑛𝑔

R1 > R2


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Temperature ↗R ↗Degradation ↗

HORIKX plot for analysis of the ratio of crosslink to main chain scission:


→ The devulcanised material behaves as a non-activated raw mix (flat MDR curve after devulcanisation)


MDR rheogram at 180°C

After devulcanisation After re-activation

+ Addition of curing agents


Red: TorqueGreen : Viscosity, visco-elastic behaviourBlue : Torque derivative

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Uses of devulcanised rubber




o Micronisation

o Devulcanisation





➢ Conclusion

1) Use of 100% devulcanised rubberExample: Ground Tyres Rubber (GTR)

Tensile strength (MPa) Stain at break (%)

GTR 1 10.5 315

GTR 2 11.6 246

Devulcanised GTRNew vulcanised GTR



✓ Low-cost materials✓ Adjustable mechanical properties according to the formulation✓ Can replace the virgin rubber in various applications (building, civil engineering…)

Reincorporation and revulcanisation as second material in master batches→ Good preservation of the mechanical properties

Regenerated EPDM reincorporated in an initial formulation Regenerated NR reincorporated in an initial formulation

2) Incorporated in a virgin rubber matrixExamples 1 and 2: EPDM and NR

0

0.2

0.4

0.6

0.8

1

HardnessIRHD

Ultimate TensileStrengh

Elongation atbreak

E100%

reference 5% 10% 20%

Phénix-Technologies - Rubber and Elastomers – Sustainably meeting tomorrow’s challenges – May 15, 2017, Manchester, United Kingdom 24

0

0.2

0.4

0.6

0.8

1

HardnessIRHD

UTS Elongation atbreak

E100%

reference 5% 10% 20%


✓ low degradation of the mechanical properties✓ Allows to reduce the costs

0

5

10

15

20

25

0 10 20 30

Stre

ss a

tb

reak

σ(M

Pa)

Devulcanised SBR content (% by weight)

0

100

200

300

400

500

600

0 10 20 30De

form

atio

nat

bre

ak ε

(%)

Devulcanised SBR content (% by weight)

Devulcanised SBR Raw SBR

New vulcanised SBR

Loss of properties at 30%

Tensile strength(Mpa)

22,8 %

strain at break (%)

5 %

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2) Incorporated in a virgin rubber matrixExample 3: Styrene Butadiene Rubber (SBR)



✓ 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

Devulcanised rubber Thermoplastic

Thermoplastic vulcanisates

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3) Incorporated in a thermoplastic matrixExample: Thermoplastic vulcanisates (TPEv)



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o Micronisation

o Devulcanisation





➢ Conclusion

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


Experienced issues

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New developments




o Micronisation

o Devulcanisation





➢ Conclusion

1. Collaboration with Artis

Reinforcement of dGTR with rCB* for the production of « Super Green compounds »

2. Collaboration with ASTM for determination of devulcanisatesstandards (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

New developments


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Conclusion




o Micronisation

o Devulcanisation





➢ 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 !


Conclusion

THANK YOU FOR YOUR ATTENTION

PHENIX -TECHNOLOGIES33

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