Nicolangelo Peduto - RadiciGroup Chemicals & Plastics Areas 10th Congress for Bio Based Materials, Natural Fibers and WPC - 24and 25 June, Stuttgart/Fellbach

1. New Eco-Sustainable
Polyamide-Based Polymers
and Compounds
for Multipurpose Applications
Nicolangelo Peduto
RadiciGroup
Chemicals & Plastics Areas
10th Congress for Bio Based Materials, Natural Fibers and WPC
24 and 25 June, Stuttgart/Fellbach
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2. Sustainability ad sustainable developments
Genesis of a concept
• «We do not inherit the Earth from our ancestors, we
borrow it from our children» - Proverb attributed to the
Natives of North America – 18th Century
• «Our work will influence not only the present generation
but also the future ones» - T. Roosevelt (1901):
• To create and maintain conditions under which human being and nature can exist in
productive harmony satisfying the special and economic needs for the present and
future generations (USA 1969).
• «Sustainable development is development that meets the
needs of the present without compromising the ability of
future generations to meet their own needs. (Bruntland
report, 1987).

3. RADICIGROUP & SUSTAINABILITY
3
sustainabilitysustainability
LCA studiesLCA studies
R&D for
sustainable
products
R&D for
sustainable
products
PCR-EPD
approach
PCR-EPD
approach
GRI Certified
Sustainability
Report
GRI Certified
Sustainability
Report

4. THE ENVIRONMENTAL LABELS (“Green Labels”):
RadiciGroup Project
• Why PCRs?
4
EPD
PCR
ISO14025
ISO14040 - 44

5. 5
THE ENVIRONMENTAL LABELS (“Green Labels”):
RadiciGroup Project
• EPD – the LCA information needs
Use of resources:
– Primary and secondary energy (from renewable and non-
renewable sources) (GER) [MJ]
– Water consumption [m3]
Environmental impact:
– Global Warming Potential (GWP) [kg CO2 equiv.
“Greenhouse gases” ]
– Ozone Depletion Potential (ODP) [kg CFC equiv.:
“Chlorofluorocarbons”]
– Acidification Potential (AP) [kg SO2 equiv.: “Sulfur dioxide” ]
– Eutrophication Potential (EP) [kg PO4(3-) equiv.:
“Phosphates” ]
– Photochemical Oxidant Potential (POCP) [kg “Ethylene”
equiv.]

6. Eco-
sustainable
approach of
product
development
Bio-sourced
polymers
Post industrial
recycled
polymers
“Green like”
performances
Radilon® A HS144
Heramid®
R&D for sustainable products
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Post consumer recycled polymers to come

7. Costs
Renewable
source content
100%
60%
0%
Pyramidal organization of
RadiciGroup bio–sourced polyamides
Radici Chimica
polymerization know
how and flexibility
+
Radici Plastics
compound technology
to design
high performance
polymers and polymer
blends
7

8. Bio- polyamides – Main manufacturing routes
8
Undecilenic acid
11-amino-undecanoic acid
PA 11
Ricinoleic acid
Sebacic acid
HMDA
PA 6.10 PA 4.10
Decanodiamine
PA 10.10
Castor oil seeds

9. RADIPOL® DC : PRODUCTION CHAIN
A new family of semi-crystalline polyamides 6.10 obtained from the
polycondensation of 1,6–hexamethylenediamine and 1.10-decanedioic
acid (sebacic acid).
9

10. RADIPOL® DC PA6.10: environmental benefit, reduced
carbon footprint
PA6.10: GWP much lower than technical polymers like PC, PA6, PA66 ….
Comparable to PA11 (Data collected from literature)
0
1
2
3
4
5
6
7
8
9
10
PA6.10 PA6 PA12 PC Epoxy
Resin
PA66 PA11
GWP
Global Warming Potential (Kg CO2 Eqv/Kg Polymer)
PA6.10
PA6
PA12
PC
Epoxy Resin
PA66
PA11
0
1
2
3
4
5
6
7
8
9
10
PA6.10 PA6 PA12 PC Epoxy
Resin
PA66 PA11
GWP
Global Warming Potential (Kg CO2 Eqv/Kg Polymer)
PA6.10
PA6
PA12
PC
Epoxy Resin
PA66
PA11
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11. PA property comparison according to the
fundamental parameter
NHCO
CH
−
−− 2
4 5 5 7 8 9 10 11
11

12. NHCO
CH
−
−− 2
4 5 5 7 8 9 10 11
12
PA property comparison according to the
fundamental parameter

13. RADIPOL DC PA6.10 KEY FEATURES:
TENSILE MODULUS
PA6.10 shows a lower tensile modulus variation than PA6 and PA6.6,
caused by moisture absorption
13

14. RADIPOL DC PA6.10 KEY FEATURES:
TENSILE STRENGTH
PA6.10 shows higher tensile strength at break than PA11 & PA12 and
better tensile strength retention after conditioning versus PA6 and
PA6.6

15. RADIPOL® DC PA6.10 KEY FEATURES:
IMPACT RESISTANCE
PA6.10 shows an impact resistance higher than PA6 and PA6.6 at -30°C
and slightly higher than PA12
15

16. RADIPOL® DC PA6.10 KEY FEATURES:
MELTING TEMPERATURE, HDT
PA6.10 shows higher melting point and HDT than PA12 and PA11
leading to an improved thermal resistance
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17. RADIPOL® DC PA6.10 KEY FEATURES:
SPECIFIC GRAVITY
PA6.10 specific gravity : intermediate between PA6 & 6.6 and PA11 & 12
17

18. PA 610 COPOLYMERS
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RADIPOL® Dcopo
50% bio-based
Superior transaparency
and gloss
Good flexibility and
tougheness
Good thermoforming and
shrinkage

19. RADIPOL® DC PA6.10 KEY FEATURES
Best compromise between properties/costs/eco-content
Greater dimensional stability compared to PA6 and PA6.6,
due to less water and moisture uptake that lead to a superior
hydrolysis resistance
Higher chemical resistance compared to PA6 and PA6.6
Grater resistance at high temperature than PA11&PA12
Superior resistance to peroxides
Excellent elastic memory, superior to traditional polyamides,
i.e. better bending
19

20. PA 6.10 vs. PA 66 – Hydrolysis resistance of
compounds with 30% GF
20
*PA 6.10
*PA 6.6
*Courtesy of RadiciNovacips

21. 21
Molecular structure of PA6.6.
The methylene carbon adiacent
to amide N-H is easy to be oxidated
Mechanisms of degradation of
polyamides exposed to hot water that
lowers mechanical performances
…A dilution of the methylene carbon adiacent to amide N-H
results in limiting the loss of mechanical properties
Polyamides – Degradation mechanism in hot water*
*

22. Stress-cracking mechanism of PA’s in
solutions of road salts
22
When in contact with PA, ZnCl2 makes a complex
compound with the amide groups and the reaction
takes place easily. The ultimate effect is the scission
of the amide groups and the degradation of molecular
weight and therefore mechanical properties. One of
the key parameter is then the amide groups
concentration.
Such a complex increases the stiffness of the
polymer that overcomes a stress concentration,
ultimate responsible for the stress cracking
phenomena. Modulus is the other key parameter.
Water plays a positive rule because it acts as a stress
relief. Stress cracking usually happens during the
firsts hours of the test.
Halide ions are very important to create this complex.
In fact other types of salts such as Zn acetate do not
cause stress cracking in PA.
For ZnCl2 salt solution, the pH of the mixture is < 2,
at 50 % concentration. The solution is therefore acid
and the PA parts in contact with the solution show an
extensive whitening phenomenon.

23. 23
Effect of salts on Polyamide
Glass Transition Temperature
Material 20°C 40°C 60°C
PA 6 72 77 89
PA 6.6 70 75 90
PA 6.10 65 63 65
100 microns film plunged into water solution of ZnCl2 at different T
Tg variation

24. Radilon® D PA6.10 Approvals
Pneumatic Pipes
Truck Air Brake Pipes
Fuel Line Connectors
Several parts requiring dimensional stability
and superior chemical resistance
24

25. PA 6.10 – Case History
Radilon® D PA6.10 Key Features:
Chemical Resistance
Two special grades that pass the most severe zinc-chloride test :
Radilon® D E35ZW (flexible) (dilution of amide groups + stress relief)
Radilon® D E50ZW (semi-flexible)
* PA6.10 Radilon® D E35ZW and Radilon® D E50ZW special grades : no damages after immersion in
zinc-chloride/water 50/50 solution for 200 h. Right side picture shows a typical stress cracking
damage on high stressed fastening area
High stress fastening
area
PA 6
25

26. PA 6.10 – Case History
Radilon® D PA6.10 for pneumatic tubings
Norm ref DIN 73378 : basic stress comparison from 23 to 130 °C
• Radilon® D 40P50K (translucent, UV resistant, semi-flexible)
• Radilon® D 40EP35XK (opaque, UV resistant, semi-flexible)
Spiral-shaped pneumatic tubing
made of Radilon® D40P50K
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27. PA 6.10 – Case History
Radilon® D PA6.10 for truck brake air lines
MAIN CTQ’S
• Properties retention after ageing in air
• Chemical resistance
• Norms DIN 74324, FVMSS 106, ISO 7628, DIN
73378, SAE J844
One layer solution
Radilon® D 40EP25ZW (flexible)
Radilon® D 40EP35XK (semi-flexible)
Radilon® D E35ZW (superior zinc-chloride
resistance)
Two layer solution
Radilon® D E35ZW (outer layer)
Radilon® D 40EP25ZW (inner layer) or
Radilon® D 40EP35XK (inner layer)
Truck brake tubes made of
Radilon® D E35ZW.
27

28. PA 6.10 – Case History
Radilon® D PA6.10 for fuel connectors
MAIN CTQ’S
•Good properties retention after fuel ageing
•Good dimensional stability
•Good chemical resistance
Available grades
Radilon® D RV300W (30% GF)
Radilon® D CF150W (conductive grade)
28

29. PA 6.10 – Case history
Radilon® D PA6.10 for fuel connectors
PA6.10 change over time in tensile strength after E24 fuel immersion : similar
trend as PA12-GF30, which has been used to manufacture fuel connectors up to
present
29

30. PA6.10 change over time in Charpy unnotched impact strength after E24 fuel
immersion : initial increase observed and no change from 1,500 to 1,000 h . For
PA12 after 1,000 h the impact strength begins to decrease; this could be a sign of
material degradation
PA 6.10 – Case history
Radilon® D PA6.10 for fuel connectors
30

31. The graph shows that, after 2,000 h of immersion in E24 fuel, the change in
weight for PA610-GF30 is 2% lower than for PA12-GF30
PA 6.10 – Case history
Radilon® D PA6.10 for fuel connectors
31

32. The graph shows that, after 2,000 h heat ageing in air at 130°C, PA610-GF30 shows
no decline either in tensile strength at break or in deformation at break
PA 6.10 – Case history
Radilon® D PA6.10 for fuel connectors
32

33. Radilon® D PA6.10 for fuel connectors
The graph shows that, after 200 h immersion in zinc-chloride solution at 23°C and
60°C there is no significant change in the Charpy unnotched impact strength.
These results confirm the excellent chemical resistance of Radilon® D RV300W
(PA610-GF30) compared to PA12-GF30
33

34. Bio - Composites
Long chain biopolyamides (homopolymer and copolymer)
modified with natural fillers
Preliminary studies
• The addition of natural fillers to long chain biopolyamides
provides:
– Improvement of mechanical properties and thermal stability
vs. neat polymers
– Lower density vs. compounds modified with classical fillers
(GF)
– Eco – friendly compounds up to 100% of the composition
– Cost reduction vs. neat polymers
– Slight lost of fluidity vs. neat polymers
– Superior aesthetic quality of parts moulded thereof
– Barrier properties and electrical properties under evaluation
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35. • Materials used
– PA 6.10 – RADIPOL DC 45 (Melting point = 223°C)
– PA 6.10 COPO – RADILON DC/A 45 (Melting point = 210°C)
– PA 10.10 – RADIPOL DX 45 (Melting point = 203 °C)
• Compound conditions*
35
Bio Composites
Long chain biopolyamides (homopolymer and copolymer)
modified with natural fillers
Preliminary studies
* Courtesy of University of Turin

36. SEM micrographs of 20% filled biopolymides*
36
PA 10.10 + 20% FILLER PA 6.10 + 20% FILLER
• Good adhesion polymer matrix - filler
• Acceptable dispersion of filler
• Particle size distribution of filler to be improved (i.e. acting
on processing conditions and / or screw design)
*Courtesy of University of Turin

37. E – Modulus*
comparison of
biopolyamides and
biopolyamides filled
compounds
• At all test temperature
it was noticed a
significant
reinforcement effect for
all of the filled
biopolyamides
• Deepest descent of
modulus vs.
temperature noticed
for the copolymer
37
0
500
1000
1500
2000
2500
30 60 80
TensileModulus(MPa)
Temperatures
Tensile Modulus vs. Temperatures
PA10.10
PA10.10 + 20% FILLER
PA6.10
PA6.10+20% FILLER
PA66 COPO
PA 66 COPO +20% FILLER
*Courtesy of University of Turin

38. Acknowledgements
• Special thanks to:
– A. De Sio, A. Pezzoni & the polymerisation team of
Radici Chimica
– E. Spini of Radici Plastics
– R&D of Radici Chimica/Radici Plastics/Radici Yarn
– Corporate Marketing and Communication of
RadiciGroup
– Dipartimento di Scienza Applicata e Tecnologia
Politecnico di Torino
– Maria Teresa Betti for revising this document
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39. Thank You for your attention
Contact:
sustainability@radicigroup.com
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