Nicolangelo Peduto - R&D manager at Radici Chimica & Radici Plastics Anna De Sio - R&D and Technical Marketing at Radici Chimica 11th China International Polyamide & Intermediates Forum in Shanghai, 5-6 /12/2013

1. New Eco-Sustainable
Polyamide-Based Polymers
for Multipurpose Applications
Nicolangelo Peduto
Radici Chimica & Radici Plastics
Anna De Sio
Radici Chimica
11th China International Polyamide & Intermediates Forum
Shanghai, 5-6 /12/2013
1

2. RADICIGROUP & SUSTAINABILITY
LCA studies
GRI Certified
Sustainability
Report
sustainability
R&D for
sustainable
products
PCR-EPD
approach
2

3. R&D for sustainable products
Bio-sourced
polymers
Radilon® A HS144
“Green like”
performances
Ecosustainable
approach of
product
development
Heramid®
Post industrial
recycled
polymers
3

4. Pyramidal organization of
RadiciGroup bio–sourced polyamides
Renewable
source content
100%
Radici Chimica
polymerization know
how and flexibility
+
Radici Plastics
compound technology
60%
to design
high performance
polymers and polymer
blends
0%
Costs
4

5. Bio- polyamides – Main manufacturing routes
Castor oil seeds
Undecilenic acid
Decanodiamine
Ricinoleic acid
11-amino-undecanoic acid
PA 1010
HMDA
Sebacic acid
PA 610
PA 11
PA 410
5

6. 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).
6

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

8. PA property comparison according to the
fundamental parameter
4
5
5
7
8
9
10
11
 CH 2 
CO  NH
8

9. PA property comparison according to the
fundamental parameter
4
5
5
7
8
9
10
11
 CH 2 
CO  NH
9

10. RADIPOL DC PA6.10 KEY FEATURES:
TENSILE MODULUS
Tensile Modulus Comparison (ISO 527)
1100
1300
PA11
1100
PA12
1500
1100
PA6.10
2200
1200
PA6.12
Tensile Modulus (RH50))
2100
Tensile Modulus (DAM)
1700
PA66
3150
1100
PA6
3100
0
1000
2000
3000
4000
Tensile Modulus (MPa)
PA6.10 shows a lower tensile modulus variation caused by moisture
absorption than PA6 and PA66
10

11. RADIPOL DC PA6.10 KEY FEATURES:
TENSILE STRENGTH
Tensile Stress at Yield (ISO 527)
45
PA11
50
38
PA12
42
50
PA6.10
65
Tensile Stress at Yield (RH50)
50
PA6.12
60
Tensile Stress at Yield (DAM)
58
PA66
82
35
PA6
80
0
20
40
60
80
100
Tensile Stress at Yield (Mpa)
PA6.10 shows higher tensile strength at break than PA11 & PA12 and
better tensile strength retention after conditioning versus PA6 and PA66
11

12. RADIPOL® DC PA6.10 KEY FEATURES:
IMPACT RESISTANCE
Charpy Notched Impact (ISO 179, conditioned)
11
PA11
14
5
PA12
9
6
PA6.10
10
Charpy Notched Impact (- 30 °C)
6
PA6.12
7
Charpy Notched Impact
4
PA66
12
3
PA6
20
0
5
10
15
20
Charpy Notched Impact (KJ/m²
PA6.10 shows an impact resistance higher than PA6 and PA66 at -30°C
and slightly higher than PA12
12

13. RADIPOL® DC PA6.10 KEY FEATURES:
MELTING TEMPERATURE, HDT
Melting Temperature, HDT
PA11
145
189
135
PA12
178
165
PA6.10
218
140
PA6.12
225
PA66
PA6
HDT (0,45 Mpa)
215
260
170
Melting Temperature
220
0
100
200
Melting Temperature (°C), HDT (0,45 MPa, °C)
300
PA6.10 shows higher melting point and HDT than PA12 and PA11
leading to an improved thermal resistance
13

14. RADIPOL® DC PA6.10 KEY FEATURES:
SPECIFIC GRAVITY
PA6.10 specific gravity : intermediate between PA6 & 66 and PA11 & 12
14

15. PA 610 COPOLYMERS
RADIPOL® Dcopo
 50% bio-based
 Superior transaparency
and gloss
 Good flexibility and
tougheness
 Good termoforming and
shrink
15

16. RADIPOL® DC PA6.10 KEY FEATURES
 Best compromise between properties/costs/eco content
 Greater dimensional stability compared to PA6 and PA66,
due to less water and moisture uptake that lead to a superior
hydrolysis resistance
 Higher chemical resistance compared to PA6 and PA66
 Grater resistance at high temperature than PA11&PA12
 Superior resistance to peroxides
 Excellent elastic memory, superior to traditional polyamides,
i.e. better bending
16

17. PA 6.10 vs. PA 66 – Hydrolysis resistance of
compounds with 30% GF
*PA 6.10
*PA 6.6
*Courtesy of RadiciNovacips
17

18. Stress-cracking mechanism of PA’s in
solutions of road salts
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.
18

19. Effect of salts on Polyamide
Glass Transition Temperature
100 microns film plunged into water solution of ZnCl2 at different T
Tg variation
Material
20°C
40°C
60°C
PA 6
72
77
89
PA 66
70
75
90
PA 6.10
65
63
65
19

20. Radilon® D PA6.10 Approvals
 Pneumatic Pipes
 Truck Air Brake Pipes
 Fuel Line Connectors
 Several parts requiring dimensional stability
and superior chemical resistance
20

21. 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)
High stress fastening
area
PA 6
* 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
21

22. PA 6.10 – Case History
Radilon® D PA6.10 for pneumatic tubings
DIN 73378 : Basic Stress Comparison
35
Basic Stress (Mpa)
30
25
PA12-PHLY
PA12-PHL
20
Radilon D40EP35XK
Radilon D40P50K
15
10
5
0
0
20
40
60
80
100
120
140
Spiral-shaped pneumatic tubing
made of Radilon® D40P50K
Temperature (°C)
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)
22

23. 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
Truck brake tubes made of
Radilon® D E35ZW.
Radilon® D E35ZW (outer layer)
Radilon® D 40EP25ZW (inner layer) or
Radilon® D 40EP35XK (inner layer)
23

24. 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)
24

25. PA 6.10 – Case history
Radilon® D PA6.10 for fuel connectors
Ageing in E24 Fuel at 90 °C
Tensile Strength at Break (Mpa)
160
Radilon D RV300W 333 NER
140
PA12-GF30
120
100
80
60
40
20
0
0
500
1000
1500
2000
Time (h)
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
25

26. PA 6.10 – Case history
Radilon® D PA6.10 for fuel connectors
Ageing in E24 Fuel at 90 °C
Charpy Unnotched Impact (KJ/m2)
140
120
100
80
60
40
20
0
0
500
1000
Time (h)
1500
2000
Radilon D RV300W 333 NER
PA12-GF30
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
26

27. PA 6.10 – Case history
Radilon® D PA6.10 for fuel connectors
Ageing in E24 Fuel at 90 °C
10,0
9,0
Weight Change (%)
8,0
7,0
6,0
5,0
Radilon D RV300W 333 NER
4,0
PA12-GF30
3,0
2,0
1,0
0,0
0
500
1000
1500
2000
2500
Time (h)
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
27

28. PA 6.10 – Case history
Radilon® D PA6.10 for fuel connectors
Radilon D RV300W : Ageing in air at 130 °C
140%
Property Retention (%)
120%
100%
80%
60%
40%
Tensile Strength at Break
Tensile Deformation at Break
20%
Target
0%
0
500
1000
1500
2000
Time (h)
The graph shows that, after 2,000h heat ageing in air at 130°C, PA610-GF30 shows
no decline either in tensile strength at break or in deformation at break
28

29. Radilon® D PA6.10 for fuel connectors
Ageing in a 50:50 Zinc-Chloride solution at 23°C and 60 °C
100
Charpy Unnotched Impact (KJ/m2)
90
80
70
60
PA12 GF30 at 23 °C
50
PA12 GF30 at 60 °C
40
Radilon D RV300W 333 Ner at 23 °C
30
Radilon D RV300W 333 Ner at 60 °C
20
10
0
0
50
100
150
200
250
Ageing Time (hours)
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
29

30. PA 6.10 & Fibers –Property comparison
PROPERTIES
UNIT
PA6
PA66
PA6.10
POLYESTER
COTTON
MELTING POINT
°C
220
260
223
255
-
WATER ABS,
SATURATION
%
9,4
8.2
3,0
0,2
20
DENSITY
g/cm3
1,13
1.14
1,06
1.39
1.5
DIMENSIONAL
STABILITY
XX
XX
XXX
XXX
x
RENEWABLE SOURCE
-
-
XXX
-
XXXX
MECHANICAL
RESISTANCE
XXX
XXX
XXX
XX
X
THERMAL RESISTANCE
XXX
XX
XXX
XXX
X
DRYING SPEED DUE TO
LOW WATER PICK UP
XX
XX
XXX
XXXX
X
CHEMICAL RESISTANCE
XX
XX
XXX
XX
XXX
Source: RADICIGROUP AND EXISTING LITERATURE
30

31. FINDEISEN GmbH
DORIX® 6.10 CASE HISTORY
WHAT
Development of a «New Concept» Floor Covering Product ……
made in “Bio-Sourced Polyamide Fibre”
WHO
Partners :
Radici Chimica as Polymer Developer
Radici Yarn – Radici Chemiefaser as Fibre Developer
Findeisen GmbH as Floor Covering Developer
European Leader in the Production of «Needled Floor
Coverings»
31

32. FINDEISEN GmbH
DORIX® 6.10 CASE HISTORY
Evaluation of the Main Performances vs Regular Products …
Comparison
LIVE –Test
(six months)
PA610
PA6
PP
 Internal at Findeisen’s
 External at Customer’s
The Best Test ???
32

33. FINDEISEN GmbH
DORIX® 6.10 CASE HISTORY
Evaluation of the Main Performances vs Regular Products …
 Achieved Result : 33
Abrasion Resistance
(EN 1470)
 Best Class for Commercial
(similar to PA6, better than PP)
 Achieved Result : 3.8 – 4.5
Castor Chair
(EN 985)
 Best Result
(similar to PA6, better than PP)
33

34. FINDEISEN GmbH
DORIX® 6.10 CASE HISTORY
Evaluation of the Main Performances vs Regular Products …
Wolff -Test
(internal test for
evaluating the abrasion
resistance)
 Achieved Result : Good
 Similar to PA6, better then PP
(250 h of PA6 vs 100 h of PP)
34

35. FINDEISEN GmbH
DORIX® 6.10 CASE HISTORY
Evaluation of the Main Performances vs Regular Products …
Fire Behaviour
(ISO 9239-1)
 Textile Flooring
 Residential Flooring
Achieved result : Bfl – S 1
Comments: best possible result for Textile Floor Covering (similar to PA6)
35

36. FINDEISEN GmbH
DORIX® 6.10 CASE HISTORY
Evaluation of the Main Performances vs Regular Products …
 Important for installation of floor coverings
Dimensional Stability
(EN 986)
 The Limits are: • - 1.2% for Shrinkage
• + 0.5% for Elongation
Typical values
PA6.10
PA6
PP
Shrinkage
- 0.5%
- 1.0%
- 0.3%
Elongation
+ 0.2%
+ 0.4%
+ 0.1%
PA6.10 very close to PP : a CRUCIAL characteristic
(In particular for installation of rolls -->
easier installation, no influence of climate conditions)
Potential development for TILES : 100% PA6.10 (today PA6 blend with PP)
36

37. FINDEISEN GmbH
DORIX® 6.10 CASE HISTORY
Evaluation of the Main Performances vs Regular Products …
Tot VOC = 27 µg/m^3
Tot VOC = 13 µg/m^3
PA6.10 : NO emission of Caprolactam !
37

38. FINDEISEN GmbH
DORIX® 6.10 CASE HISTORY
Evaluation of the Main Performances vs Regular Products …
Comparison
PA610
PA6
PP
LIVE-Test
Good
Good
Good
Abrasion
resistance
***
***
*
Castor Chair
***
***
*
Fire Behaviour
*** (Bfl-S1)
*** (Bfl-S1)
** (Cfl-S1)
Dimensional
Stability
***
*
***
Eco- Friendly
***
**
**
Soiling and Staining Test: to be checked (pontentially better than PA6)
Low Water Pickup and Better Chemical Resistance
38

39. Acknowledgements
• Special thanks to:
– Findeisen GmbH
– A. Pezzoni & the polymerisation team of Radici
Chimica
– E. Spini of Radici Plastics
– R&D of Radici Chimica/Radici Plastics/Radici Yarn
– Corporate Marketing of RadiciGroup
– Maria Teresa Betti for revising this document
39

40. Thank You for your attention
Contact:
sustainability@radicigroup.com
40