Tecnaro GmbH produces biopolymer pellets and compounds. It was founded in 1998 as a spin-off from Fraunhofer Institute of Chemical Technology and currently has 30 employees. The document discusses Tecnaro's product families including biobased, biodegradable, and conventional polymers. It also summarizes the properties and applications of materials developed through the Bio4Self project, which aimed to improve the hydrolytic stability and mechanical properties of PLA. Reinforced PLA formulations showed good mechanical properties but require further work to enhance thermal resistance through blending and processing methods.

1. Co-funded by the
European Union
Pellet production-
Compounding technology-
Properties and applications
Plastindustrien Event, Copenhagen 04.06.2019
Tecnaro GmbH, Erna Muks

2. 04/06/2019 2
Company data of Tecnaro GmbH
 Foundation of Tecnaro GmbH as a spin-off from Frauenhofer Institute of Chemical
Technology (ICT) Pfinstal in 1998.
 Staff: 30
 Production lines: 3
 Capacity of production: 12.000 to/a
 Annual turnover: 4 Mio €
 Patents: 16
Our products: Granules made of
renewable raw materials for the
plastics processing industry.

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Formulation
and compound development
ValidationR&D
Conception
Manufacturing
first batch
Industrialization

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Polymers and biopolymers
Biopolymers
(Bio-based / non-biodegradable):
- Bio-based polyethylenes
=> e.g. Bio-HDPE, Bio-LLDPE and Bio-LDPE
- Biobased polyester
=> e.g. Bio-PET, Bio-PTT
- Biobased polyamides
=> e.g. Bio-PA6.10, Bio-PA10.10,
Bio-PA10.12
Biopolymers
(Bio-based / biodegradable):
- Thermoplastic starch (TPS)
- Cellulose
- Lignin
- Polylactide (PLA)
- Polybutylene succinate (PBS-A)
- Polyhydroxyalkanoates (PHA: PHB, PHV, PHBV)
Conventional plastics
(Petroleum-based / non-biodegradable):
- Petroleum-based polyolefins
=> e.g. PP, HDPE, LLDPE, LDPE
- Petroleum-based polyesters
=> e.g. PET, PBT
- Petroleum based polyamides
=> e.g. PA6, PA6.6
- PVC etc.
Polymers
(Petroleum-based / biodegradable):
- Polybutylene adipate phthalate (PBAT)
- Polycaprolactone (PCl)
not biodegradable
petroleum-basedbio-based
biodegradable

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Proportion of renewable raw materials
A R B O B L E N D ®
( 6 0 – 1 0 0 % )
A R B O F O R M ® ( 1 0 0 % )
A R B O F I L L ®
( 3 0 – 8 0 % )
not biodegradable biodegradable
20 %
40 %
60 %
80 %
100 %
ARBOBLEND®- ARBOFILL®-ARBOFORM®:
The three product families

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Mechanical properties
ARBOBLEND®
ARBOFORM®
PA-GF
ABS
20 40 60 80
PP
PE-
HDTPE
10.000
7.500
5.000
2.500
E-modulus [MPa]
Tensile strength [MPa]

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Bio4Self targets
2 Manufacturing routes
Compounds for
Injection moulding
 non-reinforced PLA formulations
 reinforced PLA formulations
Cowl Interior
top fascia
support
Compounds for
Self-reinforced PLA composites
Thermoforming
Suitcase shells
Tm,1 < Tprocess < Tm,2

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PLA ageing
 Main degradation mechanism: random
hydrolysis of ester linkages along
polymer backbone.
Approaches to improve durability/eliminate hydrolysis:
 Inhibition of diffusion kinetics (e.g. by intercalating nanoclays)
 Modification of polymer crystallinity (e.g. by nucleating agents)
 Capping of polar end groups and/or water (anti-hydrolysis agents)
BIO4SELF approach
 Hydrolysis can be autocatalyzed by any
carboxylic end group initially present or
formed during the process.

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Materials: PLA grades
and anti-hydrolysis agents
 In BIO4SELF we aimed for hydrolytic stabilization of both low and high Tm PLA
materials (matrix and reinforcement).
 Target: minimize the decrease of Mw under accelerated ageing compared to
the non-stabilized compounds.
Two PLA grades:
 High Tm PLA
 Low Tm PLA
Four anti-hydrolysis agents:
 Epoxy-based chain extender
 Aliphatic polycarbodiimide
 Aromatic carbodiimide
 Aromatic polycarbodiimide
 PLA / anti-hydrolysis agents compounds were prepared by twin screw
extrusion at technical scale and evaluated @ Fraunhofer ICT
 Hydrolysis tests were performed and evaluated @ MIRTEC
 Up-scaling of selected compounds at industrial scale @ Tecnaro

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From lab scale to industrial scale
Stepwise adjustment and continuous
improvement
*
* https://www.gala-industries.com/de/pelletizing_systems-d.php

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Industrial processing guidelines
 Important processing parameters: processing temperature, screw design, screw speed,
throughput rate (material residence time)
 Prevent material degradation/ ensure a good mixing/distribution quality:
Optimization of the process technology:
 Intensive pre-drying (<250 ppm)
 Modified extruder design (effective degassing units)
 Tailor-made screw design (compounding step)
Optimizations of the process parameters:
 Low processing temperatures (degradation ↓)
 Low shear rates (degradation ↓)
 Max. throughput rates (shear rate ↓)

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Properties of non-reinforced Bio4Self
compounds
• non-reinforced BIO4SELF formulations don’t meet the thermal resistances if processed with
conventional production equipment/ similar parameters: stereo-complex PLA/ nucleated PLA
compounds, if tempered (80°C_1h) or injection moulded in a hot tool/mould can increase the
thermal resistance from 50 °C up to 100 °C (HDT-B/0,45MPa).
4385 V 4386 V 4387 V 4510 V 4511 V 4390 V 4576 V
Melt volume-flow rate, MVR ISO 1133 cm
3
/10min
Temperature 190 ºC
Load 2,16 Kg
Moulding shrinkage (parallel) 60 x 60 x 2 mm ISO 294 % 0,39 0,33 0,34 0,67 0,67 0,33
Flexural modulus ISO 178 MPa 2500 2900
Flexural stress ISO 178 MPa 70 80
Tensile modulus ISO 527 MPa 3200 3600 3300 3500 2900 2700 2500
Yield stress 50 mm/min ISO 527 MPa 67 55 70 64 56 54 54
Yield strain ISO 527 % 2,7 2,4 2,7 2,4 2,5 2,4 2,4
Stress at break ISO 527 MPa 59 51 60 60 35
Strain at break 50 mm/min ISO 527 % 5,8 2,7 5,2 4,1 8,4 5,3
Charpy impact strength 23ºC ISO 179 kJ/m
2
21,4 P240 22,8 P26,44 P210 58,1
Temp. of deflection under load 0.45 MPa ISO 75 ºC 53 52 52 54 52 51
Vicat softening temperature 50ºC/h 10 N ISO 306 ºC 63 63 63
Density ISO 1183 kg/m
3
1,25 1,22 1,25 1,23 1,21 1,20
low Tm high Tm high Tm
ARBOBLEND
4,1 2,4 10 8,5 7 7

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Properties of reinforced Bio4Self
compounds for injection molding
Melt volume-flow rate, MVR ISO 1133 cm
3
/10min
Temperature 190 ºC
Load 2,16 Kg
Moulding shrinkage (parallel) 60 x 60 x 2 mm ISO 294 % 0,13 0,13 0,33 0,13
Flexural modulus ISO 178 MPa 5500 7000 6200 6200
Flexural stress ISO 178 MPa 95 94 110 110
Tensile modulus ISO 527 MPa 5700 8100 6200 6800
Yield stress ISO 527 MPa 65 70 81 79
Yield strain ISO 527 % 1,6 1,1 2,2 2,0
Stress at break ISO 527 MPa 58 81 80
Strain at break ISO 527 % 4,1 2,2 1,9
Charpy impact strength 23ºC ISO 179 kJ/m
2 19,2±1,7 20,8±1,5 20,9±0,8
Temp. of deflection under load 0.45 MPa ISO 75 ºC 53,8± 0,8 55,7 55,3± 0,7 59,7± 0,4
Vicat softening temperature 50ºC/h 10 N ISO 306 ºC 68,1 71,4 77,9
Density ISO 1183 kg/m
3
1,4 1,4 1,4 1,4
4392 V 4393 V 4552 V 4553 V
high Tm reinforced compounds
5,7±0,1 5,8±0,1 1,9±0,3

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Comparison to conventional polymers
ECO2.3 ECO2.4
ABS PC+ABS PP PP GF30 4511 V 4576 V 4552 V 4393 V
Melt volume-flow rate, MVR cm3
/10min 25 20 15 3,7 4,3 7 5,8
Temperature ºC 220 260 230 190 190 190 190 190 190
Load Kg 10 5 2,16 2,16 2,16 2,16 2,16 2,16 2,16
Moulding shrinkage (parallel) 60 x 60 x 2 mm % 0,5 - 0,7 0,5 - 0,7 0,67 0,67 0,67 0,33 0,13
Flexural modulus MPa 2.400 2.200 1.350 3300 4300 2900 6200 7000
Flexural stress MPa 72 82 81 92 80 110 94
Tensile modulus MPa 2.400 2.200 6.500 3400 3900 2900 2500 6200 8100
Yield stress MPa 47 54 26 80 44 50 56 54 81 70
Yield strain % 2,5 4,5 2,5 2,4 2,5 2,4 2,2 1,1
Stress at break MPa 56 27 22 20 81
Strain at break % >15 100 600 >2 52 15 8,4 2,2
Charpy impact strength 23ºC kJ/m2
90,0 NB 25,0 P250 70,0 P210 21
Temp. of deflection under load 0.45 MPa ºC 102 126 83 52 55 56
Vicat softening temperature 50ºC/h 10 N ºC 101 115 115 63 71
Density kg/m3
1,1 1,1 0.91 1,14 1,3 1,4 1,2 1,2 1,4 1,4
B4S compounds
standard
Arboblend high Tm high Tm reinforced
 Variothermal mould temperature control to increase thermal resistance and improve
crystallization during injection moulding.
 With variothermal process control in injection molding, high mold temperatures during
the injection phase and low temperatures at the time of demoulding can be combined.
 Temperature can be controlled variothermally without a significant increase in cycle time.

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Conclusions on hydrolytic stabilization
and material properties
Hydrolytic stabilization:
 The hydrolytic stability of PLA was substantially improved by the use of anti-hydrolysis agents. The
results were validated also on industrially produced compounds and fibres.
 The concentration of the stabilisers has a significant effect on the hydrolytic stability (higher
concentrations needed to stabilize the material under harsher hydrolysis conditions).
Material properties:
 PLA-based reinforced formulations developed during BIO4SELF have good mechanical properties.
 Due to the thermal properties of neat PLA, the thermal resistances of BIO4SELF formulations still have to
be improved. This can be done by blend-polymers/additives/PLA stereo-complex, and variothermal
process control.
 UV-stabilized non-reinforced formulations meets the requirement; mechanical properties are stable after
UV-curing and colour does not change significantly.
Processing:
 BIO4SELF materials can be dried and injection moulded or melt spun into multifilament fibre yarns on
conventional production equipment. For enhanced properties a variothermal process control is
recommended.

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Acknowledgement
This project has received funding from the
European Union’s Horizon 2020 research and
innovation programme under Grant
Agreement No 685614-2
Thank you for your attention!!!
Erna Muks
Tecnaro GmbH, erna.muks@tecnaro.de

17. Biopolymers
Reference:
European Bioplastics e.V.
und Nova Institut (2018)

18. Mental experiment:
Assumption that all conventional plastics today would be completely replaced by
biopolymers or biopolymer compounds:
Land requirements for the production of biopolymers with complete
Substitution of conventional plastics by biopolymers
is about 2 - 4 % of the global agricultural area.
70 % for animal feed production/meat industry
Land requirements for the production of biopolymers:
2018: 0,016 % of the global agricultural area
2023: 0,020 % of the global agricultural area
Biopolymers: land-use