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2 0 1 5;4(3):283296
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Original Article
Hendrik Mainka a, , Olaf Tger a , Enrico Krner a , Liane Hilfert b , Sabine Busse b ,
Frank T. Edelmann b , Axel S. Herrmann c
a Volkswagen AG, Wolfsburg, Germany
b Otto von Guericke Universitt Magdeburg, Universittsplatz 2, Magdeburg, Germany
c Faserinstitut Bremen e.V., Bremen, Germany
a r t i c l e i n f o a b s t r a c t
Article history: Lightweight design is an essential part of the overall Volkswagen strategy for reducing
Received 9 January 2015 the CO2 emission. The use of carbon ber reinforced polymers (CFRP) offers an enormous
Accepted 19 March 2015 lightweight potential in comparison to aluminum, enabling a weight reduction, if a load-
Available online 8 May 2015 adapted (unidirectional) CFRP-design is used, of up to 60% in automobile parts without a
degradation of the functionalities. Today, the use of CFRP is limited in mass series appli-
Keywords: cations of the automotive industry by the cost of the conventional carbon ber precursor
Carbon ber Poly-Acrylic-Nitrile (PAN). Fifty percent of the cost of a conventional carbon ber already
Alternative precursor belongs to the cost of the PAN precursor.
Lignin The analysis of lignin as an alternative precursor shows clearly a signicant reduction in
the cost of CFRP and reduction of CO2 emission during carbon ber production. This fact is
essential to make carbon bers ready for a mainstream use within the automotive industry.
Key aspects are: the examination and quantication of lignin as an alternative precursor,
the optimization of the manufacturing processes, the characterization and quantication
of the properties of the novel carbon bers within an established material pre-validation
process and a nal economic efciency and sustainability analysis.
Furthermore, the process ability and demonstrators as well as the suitability for high vol-
ume production of the developed processes are main issues for successful implementation
in future lightweight vehicle concepts.
2015 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier
Editora Ltda. All rights reserved.
Corresponding author.
E-mail: hendrik.mainka@googlemail.com (H. Mainka).
http://dx.doi.org/10.1016/j.jmrt.2015.03.004
2238-7854/ 2015 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier Editora Ltda. All rights reserved.
284 j m a t e r r e s t e c h n o l . 2 0 1 5;4(3):283296
Emission
source Green house gas emissions
in Germany per car1)
123g
CO2/km
+ kg
Large tank
volume High-performance
engine
Body Heavy
Convenience adjustment chassis
Safety
Quality
Legislation
Interior
100% 25
20
Qualitative costs
75%
15
Lightweight steel
15% 20%
construction
Steel
50%
10
Magnesium
Aluminium
quasi-isotropic
60%
CFRP
25%
unidirectional
CFRP 5
50% [9]. That is the reason for the investigation in lignin based as a precursor will especially be considered as an alternative
carbon bers in the research of the Volkswagen Group. Hard- for the production of carbon bers. Hardwood Lignin is also a
wood Lignin is as a waste product of the paper mill cheap sustainable, renewable resource. The use of Hardwood Lignin
in huge amounts available. For this reason Hardwood Lignin offers signicant cost savings potential in the production of
Body
Componenet-/ adjustment
functional integration
New materials and
processes
Cost-/ weight
optimization
Lightweight
chassis
Reduced tank Less
volume performance
kg Next
vehicle generation
2.1.1. Experimental
Spool Sizing The investigations of the contained elements in the used
7% 4% Hardwood Lignin for carbon ber production are done with
the Vario ELcube CHNS from Elementar. The sulfur-carbon-
analyzer CS230 and the CHN-analyzer from LECO were used.
Fig. 5 Cost distribution for the production of PAN based All measurements were repeated at least three times and the
carbon ber [4]. average of the results is shown.
7 . 215
7 . 191
7 . 153
6 . 989
6 . 976
6 . 935
6 . 822
6 . 792
6 . 740
6 . 682
6 . 599
6 . 582
6 . 573
3 . 787
3 . 687
6 . 502
4 . 291
4 . 142
3 . 878
3 . 865
3 . 850
3 . 837
3 . 820
3 . 799
3 . 783
3 . 770
3 . 744
3 . 732
3 . 723
3 . 714
3 . 693
3 . 661
3 . 502
2 . 483
1 . 200
1 . 128
7 . 117
1 . 115
DMSO-d6
Aromatic region
Side-chain
Aliphatic region
10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
ppm
Side-chain 1.0
1.5
2.0
2.5
3.0
3.5
4.0
Aliphatic region
4.5
5.0
Aromatic region 5.5
6.0
6.5
7.0
7.5
8.0
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
CH3O O
HO CH3O O
HO
O
HO OCH3
O CH3O O O OCH3
OCH3 O
O CH
CH3O
CH3O OCH3
O
O OCH3
CH3O
OCH3
O
OH O
OH OH
1
6 2
3
5
CH3O OCH3
4 OCH3 CH3O OCH3
O O
O O
Table 4 Assignment of 13 C 1H correlation signals of aromatic region in the HSQC spectra of Hardwood Lignin.
13 1
Label C in ppm H in ppm Assignment
ppm
R B C
MeO
55
60
A
B
65
A 70
R
75
A(G) 80
R
85
B
A(S)
4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 ppm
H
ppm
C
B2/6
S2/6 105
S 2/6
110
G2
115
G5
120
G6
125
H 130
7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0 5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 ppm
H
ppm
50 C
B
60
70
A, B, R
80
90
100
S2/6
110
G6 120
S1, G1 130
S 1, G1 140
150
S3/5, S4,
160
G3, G4
170
180
C=O 190
7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00 6.95 6.90 6.85 6.80 6.75 6.70 6.65 6.60 6.55 6.50 6.45 ppm
H
The investigated samples were produced from Hard- vibrations of atoms and based on this it is possible to deter-
wood Lignin powder which typically contains guaiacyl G and mine the functional groups of Hardwood Lignin [20].
syringyl S units (Fig. 10). Infrared spectroscopy is used to determine the structures
The syringyl S and guaiacyl G could be assigned in the of molecules and the molecules characteristic absorption
aromatic region ranging from 100 to 140 ppm for 13 C and of infrared radiation. Infrared spectrum is molecular vibra-
5.0 to 7.5 ppm for 1 H. The S units showed different corre- tional spectrum. When exposed to infrared radiation, sample
lations for C2/6 H2/6 C /H 103.4105.3/6.586.87 ppm depend molecules selectively absorb radiation of specic wavelengths,
on the different inter-unit linkages at C4 and C1 . The which causes the change of dipole moment of sample
C2/6 H2/6 correlations in C -oxidized S units were found at molecules. Consequently, the vibrational energy levels of sam-
C /H 106.6108.3/7.127.22 ppm. The G units revealed dom- ple molecules transfer from ground state to excited state. The
inant signals for the C2 H2 at C /H 109.6/7.12, for C5 H5 frequency of the absorption peak is determined by the vibra-
broad signal at C /H 115.2115.5/6.66.8 ppm and C6 H6 at tional energy gap. The number of absorption peaks is related
C /H 119.6/6.93 ppm. Signals for H were detected at C /H to the number of vibrational freedom of the molecule. The
126.2126.5/6.826.93 ppm. intensity of absorption peaks is related to the change of dipole
Table 4 now illustrate the details of the signals shown is the moment and the possibility of the transition of energy levels.
spectra of Fig. 12. Therefore, by analyzing the infrared spectrum, it is possible
The HMBC spectra (Fig. 13) are examples for the efciency to obtain abundant structure information of Hardwood Lignin
of NMR as an analytical technique for the characterization of [20,21].
lignins. This spectra allowed the assignment of quaternary
carbons C1 , C3/5 , C4 in S units, the carboxyl groups in oxidized
syringyl groups in S and the C1 , C3 and C4 in G units. Strong
2.3.1. Experimental
Infrared spectra were recorded on a Perkin Elmer FT/IR 2000.
long range correlations for the aromatic protons in S and G
The samples were measured using an ATR unit. The spectral
units were observed between H2/6 , H5 and the inter-unit link-
resolution was 4 cm1 . The relative ratios of the interesting
ages C in B and R, C in A and B is dominant (for chemical
functional groups were analyzed.
structure compare Figs. 9 and 10).
100 PAN based carbon ber production process. This will also help
98
to lower the investment cost for future production facilities
96
because conventional conversion equipment can be used for
94
92
lignin carbon ber production.
90 Compared to the conventional PAN based carbon ber pro-
88 duction process two steps were added to prepare the ber
86
spinning process. These steps are washing of lignin powder
84
and drying as the rst step and pelletizing of the lignin powder
82
80
as the second step.
4400 3400 2400 1400 This leads to ve main steps, which illustrate the use of
Hardwood Lignin as a precursor for carbon ber production:
Fig. 14 FT-IR spectrum Hardwood-Lignin.
The following section will show the possibility to make a 3.2. Compounding and pelletizing
lignin-based carbon ber in laboratory scale [4,24].
The conventional carbon ber production process of a PAN The Hardwood Lignin powder cannot be used for ber spin-
based carbon ber contains ber spinning, ber stabilization ning. The main reason is the bad ow ability of the Hardwood
and ber carbonization as the mayor steps. For a future scale Lignin powder. The reason for bad ow ability is high compo-
up of the lignin based carbon ber production it is necessary nents of moisture (water content: 6.1%) and volatiles, which
to create a process which is comparable to the conventional can be detected in the hydrophilic Hardwood Lignin powder.
j m a t e r r e s t e c h n o l . 2 0 1 5;4(3):283296 293
pellets NMR and FTIR studies were made. The results of the
characterization can be found in our paper in the magazine
Carbon. The changes of the chemical structure compared to
the Hardwood Lignin powder is shown as well as the reactions
which lead to these changes and are also shown in this paper.
The in laboratory scale pelletized Hardwood Lignin with a
better ow ability, less contents of moisture and volatiles is
shown in Fig. 17.
this is available in literature and publications) and will help to Stabilization must be accelerated to achieve acceptable
dene a prole of properties for lignin producers, how and in process economics. A simple tuning of the thermal pro-
which for their lignin is useful for carbon ber production. le semi-production scale reduced the residence time from
150 h to 100 h. That means a reduction of more than 33%
3.4. Fiber stabilization was realized.
ORNL stabilized bers using a 100-h batch thermal treat-
The ber stabilization is like in the conventional carbon ber ment in a large (>5.5 m3 ) oven (Fig. 20). 75 kg of lignin bers
production process the most critical step during conversion. were stabilized for further processing. This is the rst world-
The oxidation process must be handled very carefully to pre- wide reported stabilization of lignin bers at a scale exceeding
vent any damage of the ber. If the oxidation conditions are 1 kg and shows the possibility to scale up the stabilization in
too harsh, a complete oxidation of the ber is possible, which industrial scale. The material darkens in color from brown to
means re in the oxidation oven and CO2 and ash as the result
of this step. To prevent such issues the stabilization time in
laboratory scale was chosen extremely long with very soft
temperature ramp.
Stabilization time was and remains a signicant challenge.
For the Hardwood Lignin in laboratory scale, the stabilization
time requires several days. It was possible to show that a
successful stabilization is possible at temperatures between
200 and 300 C by using an extremely soft temperature ramp
(Fig. 19) [4].
Fig. 17 Pellets made from Hardwood Lignin. Fig. 18 Melt blow process for producing lignin ber.
j m a t e r r e s t e c h n o l . 2 0 1 5;4(3):283296 295
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