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Cellulose-Based Carbon Fibers: Increasing Tensile Strength and Carbon Yield

Conference Paper · July 2018

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 CELLULOSE-BASED CARBON FIBERS: INCREASING TENSILE STRENGTH AND
CARBON YIELD

Christoph Unterweger1*, Andreas Hinterreiter2, David Stifter2, Christian Fürst1

1
Wood K plus (Kompetenzzentrum Holz), Area Biobased Composites & Processes, Linz, Austria
2
Johannes Kepler University Linz, Center for Surface and Nanoanalytics (ZONA), Linz, Austria

*Presenting author’s e-mail: c.unterweger@kplus-wood.at

Introduction
Cellulose is the oldest known carbon fiber (CF) precursor material. Today, petrochemical-based
poly(acrylonitrile) (PAN) is by far the most important precursor. Nevertheless, during pyrolysis of
PAN, large amounts of toxic gases are formed, requiring subsequent exhaust-gas treatment. In
addition, CF quality PAN fibers are quite expensive. Precursor fiber costs contribute to about half
of the total cost for CF production. Due to economic and ecological reasons, interest in producing
bio-based CFs is increasing nowadays. In order to assure a constant quality of the bio-based
precursor, man-made regenerated cellulose fibers, like viscose or Lyocell, are mainly used.
One of the main challenges regarding cellulose-based CFs is the low carbon yield compared to
commercial PAN-based CFs. The maximum theoretical carbon yield for a cellulose precursor is
44.4 %. Without any pre-treatment, the actual yields in carbonization of cellulose are much lower,
usually around 15 %. Another challenge is the mechanical performance of cellulose-based CFs
which is generally inferior to commercial PAN-based CFs.1-3
This study is focused on increasing the carbon yield of cellulose-based CFs by oxidative pre-
treatment as well as the use of carbonization aids. Furthermore, first results on the improvement of
the mechanical performance by variation of process parameters are presented.

Materials and Methods

Two types of continuous cellulose filament yarns (viscose, 2700 filaments, 4880 dtex, T0 and
non-viscose, 900 filaments, 1840 dtex, T0) were used. 2 respectively 6 yarns were joined to achieve
5400 filaments (~10.000 dtex) for each type.
For discontinuous oxidation trials, 5 g of the filament yarns were put in a pre-heated drying
chamber in air atmosphere. After heat treatment the mass change and the tensile strength of the
yarns were determined. Furthermore, the changes in the chemical structure of the cellulose
filaments were analyzed using FTIR. For determination of the carbon yield, the yarns were
carbonized in chamber furnace at a heating rate of 5 °C/min and a maximum temperature of 900 °C
As alternative method for improvement of the carbon yield, the filament yarns were impregnated
with diammonium hydrogen phosphate (DAHP). The filament yarns were continuously dipped into
an aqueous solution of DAHP and subsequently dried in tube furnace at 130 °C to achieve a
homogeneous loading of 1 wt% P. Both, the impregnated and the untreated filament yarns were
analyzed using TGA at a heating rate of 10 °C/min. For determination of the carbon yield, the
impregnated yarns were carbonized at a maximum temperature of 900 °C.

Results and Discussion

By thermal pre-treatment in oxidative atmosphere, the carbon yield could be increased for both
filament yarns. For the viscose filament, the optimum treatment temperature was found to be
275 °C with a mass loss during oxidation of 21.3 %. The total carbon yield after carbonization
could be increased from 15.4 to 20.9 % by the additional oxidation step. For the non-viscose yarn,
 the optimum oxidation temperature was 290 °C. The mass loss during oxidation was 25.6 %, the
total carbon yield could be increased from 12.9 to 19.2 %. FTIR spectra revealed that new C=O
functional groups are formed during oxidation (see Figure 1). The intensity of the new peak at
approximately 1710 cm-1 increases with increasing treatment temperature. Furthermore, the peaks
of O-H (~3290 cm-1) and C-H (~2890 cm-1) groups decrease at higher oxidation temperatures.
Even higher carbon yields could be achieved with DAHP impregnation. In discontinuous trials, the
carbon yield could be increased from 15.4 to approximately 30 %. Using a continuous one step
carbonization process (temperature profile: 300 – 340 – 380 – 570 – 900 °C, residence time per
heating zone: 4 min), the carbon yield was only 12.4 % for the untreated viscose yarn, but 36.1 %
for the impregnated one. Despite the extremely high carbon yield, the mechanical performance of
the CFs was poor. Therefore, the carbonization parameters were further optimized. As can be seen
in TGA curves in Figure 2., the pyrolysis mechanism of cellulose is changed, when DAHP is added.
Degradation starts at lower temperature, therefore, the carbonization process has to be changed for
the impregnated yarns. By addition of a stabilization step at 230 °C, the carbon yield could be
further increased to 39.3 %. But most importantly, the tensile strength could be increased by 300 %
compared to the one step carbonization process.

100%

90%

80%

70%
cellulose
mass loss [g/g]

60%
cellulose+DAHP
50%

40%

30%

20%

10%

0%
0 200 400 600 800 1000
temperature [ C]

Figure 1. FTIR spectra of oxidized non-viscose yarns Figure 2. TGA of viscose yarns

Conclusions
Among the two pre-treatment methods investigated, impregnation with DAHP seems to be more
promising, as carbon yields up to 39.3 % could be reached. However, it has to be mentioned that
this type of pre-treatment requires a change of the carbonization process as the pyrolysis mechanism
of cellulose is altered.

Acknowledgment
The work was supported by the European Regional Development Fund (EFRE) and the province of Upper Austria
through the program IWB 2014-2020 (project BioCarb-K).

References
1. Frank E., Steudle L.M., Ingildeev D., Spörl J.M., Buchmeiser M.R. (2014). Carbon fibers: precursor systems,
processing, structure, and properties. Angew. Chem. Int. Ed. 53, 5262-5298
2. Lewandowska A.E., Soutis C., Savage L., Eichhorn, S.J. (2015). Carbon fibres with ordered graphitic-like aggregate
structures from a regenerated cellulose fibre precursor. Composites Science and Technology 116, 50-57
3. Spörl J.M., Beyer R., Abels F., Cwik T., Müller A., Hermanutz F., Buchmeiser M.R. (2017). Cellulose-Derived
Carbon Fibers with Improved Carbon Yield and Mechanical Properties. Macromol. Mater. Eng. 302, 1700195

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