Fully Bio-Based Thermoplastic

Lignin Composites
22.5.2013
Biomaterials - Towards Industrial Applications
Kalle Nttinen, Antti Ojala, Lisa Wikstrm,
VTT Technical Research Centre of Finland
2 23/05/2013
Content
VTT and plastics
processing
Materials
Processing
Results
Conclusions
3 23/05/2013
Customer sectors
Biotechnology, pharma-
ceutical and food industries
Chemical industry and
environment
Electronics
Energy
Forest industry
ICT
Machine, vehicle and metal
industries
Real estate and
construction
Services and logistics
Focus areas of research
Applied materials
Bio- and chemical
processes
Energy
Information and
communication
technologies
Industrial systems
management
Microtechnologies and
electronics
Services and the built
environment
Business research
VTTs operations
Research and Development
Strategic Research
Business Solutions
Business Development
Group Services
VTTs companies
- VTT Expert Services Ltd
(incl. Labtium Ltd and Enas
Ltd)
- VTT Ventures Ltd
- VTT International Ltd (incl.
VTT Brasil LTDA)
- VTT Memsfab Ltd
VTT Group in brief
Turnover 316 M (2012) Personnel 3,206 (31.12.2012)
4 23/05/2013
Plastics processing
Micro-scale melt processing
Small Scale Processing
Pilot Scale Processing
Injection Molding
Extrusion
Pre- and Post-processing
Collin(30 x 25D) blown film extruder Injection moulding
Thermo-Haake MiniLab
Micro Compounder
5 23/05/2013
Thermoplastic lignin composites
Materials
Lignin: Softwood kraft lignin from Metso (LignoBoost)
Plasticizers: Starch acetate (Ac-starch) and triethyl citrate (TEC)
Fiber: Softwood TMP
6 23/05/2013
Melt processable starch acetate
Effect of acetylation
reduces hygroscopicity
improves thermal processability by
lowering Tg
Plasticisation with triethyl citrate (TEC)
Iower Tg
improves ductility
Tensile performance
1
1
K. Nttinen et al., Polym Comp., 2010.
7 23/05/2013
Processing steps
Wood fiber reinforced thermoplastic lignin composites
Cellulose
fibers
Extraction
of lignin
Plasticization
Compounding
with fibers
Injection molding
Lignin
Plasticized
lignin
Pellets
8 23/05/2013
Thermoplastic lignin composites
Processing steps in laboratory scale
Injection molding
(Thermo-Haake Mini-
Jet)
Plasticization and melt
compounding (Brabender Plasti-Corder
50 cm
3
batch)
Tensile testing
(Instron 4505)
9 23/05/2013
Thermoplastic lignin composites
Processing steps in pilot scale
Twin-screw extruder
Berstorff ZE 25 x 48 D
High-speed twin-screw extruder
KrausMaffei Berstorff Ze25A x 49D UTX
Compounding
Engel ES 200/50 HL
Instron 4505
Injection molding
Tensile testing
Advanced
materials
12 23/05/2013
Contents of the thermoplastic lignin composites
0 50 100
Content / wt%
SW
lignin
Ac-
starch
TEC
30-60% 15-30% 10-20% 0-40%
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Ac-starch/TEC plasticised lignin composites
Effect of TMP fiber content
Fixed lignin/Ac-starch/TEC ratios
2,5
3,5
4,5
5,5
0
5
10
15
20
25
30
35
0 5 10 15 20 25 30 35
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M
P
a
TMP fibre / wt-%
0 50 100
Content / wt%
SW lignin
Ac-starch
TEC
TMP
16 23/05/2013
Effect of processing on TMP fiber lengths
Finnish Bioeconomy Cluster FIBIC Oy 23.5.2013
1
FiberLab, R. Korpela, bo Akademie University, 2013.
2
X-ray computed microtomography, A. Miettinen, M. Kataja, University of Jyvskyl, 2012.
1 980
1
156
2
0
500
1000
1500
2000
Native TMP fiber Lignin composite (20% TMP)
M
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a
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f
i
b
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/

m
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Fiber-matrix compatibility
Tensile fracture surfaces of Ac-starch/TEC
plasticised composites (SEM)
Finnish Bioeconomy Cluster FIBIC Oy 23.5.2013
Good compatibility
Uniform dispersion of fibers
18 23/05/2013
Thermoplastic lignin composites
Ac-starch/TEC vs PEG plasticisation
30 wt% TMP fiber content
Optimised lignin / plasticiser ratios
30 29
4,8
5,9
0,6 0,5
1,7
4,2
Ac-starch/TEC PEG
Tensile Strength (MPa)
Young's modulus (GPa)
Strain at break (%)
Impact Strenght (kJ/m2)
19 23/05/2013
Water absorption of thermoplastic lignin composites
Ac-starch/TEC vs PEG
20 wt% TMP reinforcement
PEG dissolves from the composites
0
10
20
30
40
50
0,0 0,5 1,0 1,5 2,0 2,5
W
e
i
g
h
t

c
h
a
n
g
e

/

%
Time / weeks
Ac-
starch/TEC
PEG
20 23/05/2013
Property PP +
Wood
1
Lignin + PEG +
TMP
Lignin + starch
acetate + TMP
Tensile strength
(MPa)
37 29 30
Stiffness (GPa) 3.0 6.5 5.4
Impact strength
(kJ/m
2
)
15 4.4 2.0
1
Ichazo et al., Compos. Struct., 2001
Comparison:
40% Wood fibers + PP
vs
30% TMP + lignin + starch acetate + TEC
vs
30% TMP + lignin + PEG
21 23/05/2013
FuBio JR2 23.5.2013
Evaluation of TECNAROs
thermoplastic lignin composites
Arboforms consist of
thermoplastic lignin, natural additives and
fibres (flax, hemp etc.)
Odour of the composites:
F45: typical
ZE50: low
V3: very low
Application areas:
Automotive interiors
Electronics
Consumer articles
Furniture industry etc
Composition of FUMO 74:
Ac-lignin 41%
Ac-starch 23%
TEC 16%
TMP 20%
The pic and the tensile properties are extracted from the web page:
http://www.tecnaro.de/english/willkommen.htm?section=we
18
29
61
60
33
6,3
4,9
6,7
3,6
5,3
0,3
0,7
1,3
4,8
0,7
2,0
5,0
8,5
15,0
2,6
Arboform F45 Arboform ZE50 Arboform L, V3 PLA 3051D FUMO74
Tensile strength (MPa) Modulus (GPA)
22 23/05/2013
Conclusions
Thermoplastic lignin composites based on
fully renewable materials have been
fabricated
Kraft lignin can be efficiently plasticised
with Ac-starch-TEC mixtures
TMP fiber loading improves processability
and mechanical performance of the
composites
Composites are very rigid yet brittle
PEG improves ductility of the lignin
composites
Heavy breakage of TMP fibers during
processing of the composites
Northern lights in Tampere, Finland (17.3.2013)
23 23/05/2013
Acknowledgements
Funding from TEKES and Finnish bioeconomy cluster (FIBIC)
within FuBio Joint Research 2 (FuBio JR2) project
24 23/05/2013
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