Deformation Mechanisms in Cellulose Fibres, Paper and Wood
Deformation Mechanisms in Cellulose Fibres, Paper and Wood
Deformation Mechanisms in Cellulose Fibres, Paper and Wood
The use of Raman spectroscopy in probing the deformation mechanisms of cellulose fibres
(regenerated and natural), and two natural cellulose composite systems (wood and paper)
is described. It is shown that during tensile deformation the 1095 cm−1 Raman band,
corresponding to the stretching of the cellulose ring structure, shifts towards a lower
wavenumber due to molecular deformation. By analysing a number of fibres with different
microstructures this shift is shown to be invaluable in understanding the micromechanisms
of deformation in these materials. Moreover, the rate of Raman band shift is shown to be
invariant with stress for all fibre types, consistent with a fibre microstructure based on a
modified series aggregate model. In the composite systems, such as wood and paper, it is
shown that the stress-induced Raman band shift in the cellulose gives an important insight
into their local deformation micromechanics. C 2001 Kluwer Academic Publishers
0022–2461
C 2001 Kluwer Academic Publishers 3129
2. Experimental procedure 2.3. Raman spectroscopy
2.1. Materials A Renishaw 1000 Raman Imaging Microscope was
Six different regenerated cellulose fibres were investi- used to record the spectra of fibre monofilaments. A
gated. Fibres (CA-CD) were produced by the viscose low power 25 mW He-Ne laser (633 nm) was em-
process, CE by an alternative solution spinning process ployed with an intensity of 1 mW when focussed on the
and CF produced by the NMMO (N -methylmorpholine monofilament. An infra-red laser (780 nm) was used for
N -oxide) process. Fibres CA-CE were provided by the wood and paper samples to overcome fluorescence.
Akzo Nobel and CF by Courtaulds (now merged The low power laser spot diameter was about 2 µm.
with Akzo Nobel as ACORDIS). The trade names of A highly-sensitive Peltier-cooled charge couple device
CA, CB, CC, CD, CE, and CF are Cordenka-EHM, (linked to a PC with Renishaw software) was used to
Cordenka-1840, Enka Viscose, Cordenka-700, Alter- record spectra. The spectra were curve fitted using a
native Cellulose and Lyocell respectively. mixed Lorentzian-Gaussian distribution function to de-
Steam exploded flax and field retted hemp fibres were termine the peak positions based on a mathematical
also examined. The steam exploded flax was produced algorithm [13].
as hackling tow and processed by FH, Reutlingen,
Denmark and the hemp was provided by the British
Fibre Federation, UK. Single fibres (5 mm in length) of 2.4. Raman deformation studies
the natural cellulose fibres were extracted from larger Cellulose fibres with a gauge length of 50 mm for
bundles by placing in hydrogen peroxide for 48 hrs. CA-CF and 5 mm for flax and hemp were fixed us-
This had the effect of bleaching the fibre, which re- ing cyanoacrylate adhesive on a tensile deformation rig
duced fluorescence under the Raman laser, and also that fitted directly onto the stage of the microscope.
assisted in releasing the fibres from the stems. The fibre axis was aligned parallel to the incident po-
Sections of Pinus radiata wood were also investi- larised laser beam to within ±5◦ . For the Raman de-
gated. The Pinus radiata samples used had a microfibril formation analysis, each straining increment required
angle of 13◦ , measured using small angle x-ray scatter- 150 s, which included 120 s for exposure and 30 s for
ing (SAXS) as described elsewhere [12]. The cotton pa- the focussing. The fibre stress was recorded using a
per studied had been produced on a pilot plant machine purpose-built rig, housing a load cell with a full-scale
in the Department of Paper Science, UMIST. load of 2N and Raman spectra were obtained during
deformation.
The wood samples were sectioned into small sliv-
2.2. Single-fibre deformation ers, which were then secured onto PMMA beams with
Single fibres were tested using an Instron 1121 univer- adhesive. A strain gauge was attached to the beams
sal testing machine following recommendations given close to where Raman spectra were obtained. Samples
in ASTM D3379-75, at 23 ± 10 ◦ C and 50 ± 5% rela- were then deformed using a 4-point-bending rig, and the
tive humidity. The regenerated cellulose fibres (50 mm strain was recorded on a digital multi-meter. An expo-
gauge length) were tested at a strain rate of 0.166 %/s, sure time of 5 minutes, with 5 accumulations, was used
and the natural fibres at 0.333 %/s, and a full-scale load at each strain level. The paper samples were cut from a
of 1N was used. The diameters of the fibres were mea- sheet using a razor blade to dimensions of 15 × 5 mm
sured using a calibrated Phillips FEG-SEM with an ex- and glued to the straining rig. At each strain level the
citing voltage of 2 keV and these values are reported samples were exposed with the laser for 120 s.
in Table I. From these values, and assuming a circular
cross section, the cross-sectional areas were calculated
and thus the load could be converted to stress. Exam-
ples of SEM micrographs obtained for the fibres are 3. Results and discussion
shown in Fig. 1. For statistical reasons 30 natural fibres 3.1. Cellulose fibres deformation
were tested, whereas only 20 regenerated fibres were The stress-strain curves for Fibres CA-CF are shown in
required for the same significance. Fig. 2, along with those for flax and hemp fibres. The
regenerated cellulose fibres exhibit non-linear stress-
strain curves. Each regenerated fibre exhibits charac-
T A B L E I Mechanical properties of cellulose fibres, where df — teristic behaviour with an initially linear section, a
fibre diameter (30 measurements), E—Young’s Modulus, σf∗ —breaking knee at the yield point and an approximately linear
stress and εf∗ —breaking strain. Number of mechanical tests (CA-CF— increase after yielding. It is noted, however, that the
20, Flax and Hemp—30)
higher modulus fibres show more strain hardening. The
Fibre Sample df (µm) E (GPa) σf∗ (GPa) εf∗ (%) flax and hemp fibres, however, show near linear elastic
behaviour with some strain hardening apparent in the
CA Cordenka EHM 9.4 ± 0.2 32.2 ± 2.2 0.71 ± 0.12 3.9 ± 0.7 hemp fibre samples. The mechanical properties of the
CB Cordenka 1840 12.9 ± 0.3 16.9 ± 1.5 0.66 ± 0.08 12.7 ± 1.4
CC Enka Viscose 18.0 ± 0.7 9.4 ± 0.5 0.22 ± 0.05 17.2 ± 1.3
fibre samples are listed in Table I.
CD Cordenka 700 13.1 ± 1.3 20.0 ± 6.1 0.66 ± 0.01 10.7 ± 0.4 Typical Raman spectra for a regenerated and a natu-
CE Alternative ral cellulose fibre are shown in Fig. 3. For regenerated
cellulose 15.6 ± 1.1 30.6 ± 0.1 1.01 ± 0.07 4.9 ± 0.3 cellulose fibres there are peaks located at 1095 cm−1
CF Lyocell 12.3 ± 0.9 15.2 ± 2.9 0.54 ± 0.01 7.0 ± 0.3 and 895 cm−1 corresponding to the cellulose C−O ring
Flax Steam Exploded 17.1 ± 2.9 43.5 ± 4.2 0.27 ± 0.03 5.5 ± 0.4
Hemp Field Retted 31.2 ± 4.9 19.1 ± 4.3 0.27 ± 0.04 0.8 ± 0.1
stretching, and mixed modes (C−C−C, C−H−O) in-
cluding angle bending respectively [14]. However, in
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Figure 1 SEM micrographs of (a) CA fibres and (b) steam exploded flax fibres.
natural cellulose it was found that no peak occurred composite peak, and hence to locate its precise posi-
at the 895 cm−1 position. It has been reported that the tion, the region from 1080–1120 cm−1 was fitted using
Raman peak located at 895 cm−1 is more intense in 4 Lorentzian/Gaussian peaks to account for the shoul-
highly-crystalline cellulose II fibres, compared to Val- der peaks located at 1145 cm−1 and 1120 cm−1 .
onia ventricosa (cellulose I) [15]. For this reason, only Fig. 4 shows examples of shifts for the 1095 cm−1
the shift of the 1095 cm−1 peak was used for com- Raman peak for the high modulus CE fibre and for
parison between samples. This peak is also clearly a flax. This shift is thought to be due to deformation of
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Figure 2 Typical stress strain curves of CA (Cordenka EHM), CB
(Cordenka 1840), CC (Enka Viscose), CD (Cordenka 700), CE
(Alternative cellulose) and CF (Lyocell) regenerated cellulose fibres and
Steam Exploded Flax and Field Retted Hemp fibres. These curves are
examples of the typical form of the stress-strain curves, not averages.
Figure 4 Strain induced Raman band shifts in the smoothed spectra for
the 1095 cm−1 peaks of (a) CE and (b) flax fibres.
Figure 8 An SEM micrograph of a specimen of wood showing the region in which the laser was focussed (arrow).
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has shown that this effect is indicative of the stress in
the fibres. The invariance of the shift rate with stress,
no matter what supposed cellulose crystal structure or
specific mechanical property of the fibre confirms their
structures could be modelled using a modified series
aggregate model, as reported previously [1, 5]. This
technique has also been shown to be a useful tool in
analysing composite systems; namely paper and wood.
In particular it is found that the wood samples behave
like typical unidirectional composites, with the lignin
matrix bearing little load and the cellulose acting as the
reinforcement. In paper the deformation of single fibres
within the sheet can be followed and the processes of
fibre deformation and slippage identified.
Acknowledgements
This work was completed using funding via EPSRC
grant No. GR/M82219 and from the Thai government
(JS). The authors would also like to thank Dr. Bill
Sampson, Department of Paper Science, UMIST for
helpful discussions and the paper samples, Dr. Mau-
rits Northolt of ACORDIS for supplying regenerated
cellulose fibres (CA-CE) and to Emeritus Prof. K. M.
Entwistle for the wood samples.
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in the cellulose spectrum gives information on the direct Received 25 September
molecular deformation of the material, and this work and accepted 23 November 2000
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