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Department of

Metallurgical and Materials Engineering


Indian Institute of Technology Patna

Low-density and high-modulus carbon fibres from polyacrylonitrile


with honeycomb structure

Presented By: Dr. Tamoghna Chakrabarti Presented By: Faique Shakil


1811MS02

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Contents:
1. Abstract
2. Introduction
3. Experimental
I. Materials and fibre processing
II. Characterization
4. Results & discussion
5. Conclusion
6. References

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1. Abstract
• Density of poly-acrylonitrile(PAN) - based Carbon fibre is around 1.75-1.93
g/cm3.
• The goal is to produce high-strength and high-modulus carbon fibres with
densities in the range of 0.9e1.3 g/cm3.
• The Honeycomb structure is being used in the PAN based Composite for
achieving desired properties.
• Dry-jet wet spinning and an islands-in-a-sea geometry bi-component
spinning method is used
• Honeycomb precursor fibres were manufactured that consisted of PAN as the
sea component and poly-methyl methacrylate(PMMA) as the islands
component.

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2. Introduction
• Hollow carbon fibres can be advantageous to solid carbon fibres in
applications where compressive properties are critical.
• Compressive properties and the failure mode of carbon fibres under
compression are influenced by its microstructure and also known to be due to
buckling behavior.
• Bending stiffness of the hollow carbon fiber reinforced composites is higher
than that of the composites made from solid carbon fibres.
• The hollow carbon fibers manufactured exhibited tensile strength and tensile
modulus of 0.5 GPa and 249 Gpa, tensile strength of 1.2 GPa and tensile
modulus of 60 GPa were obtained by this process.

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Experimental
• In this paper all fibres processed are sheath core type hollow structure.
• Islands-in-a-sea geometry by bi-component spinning technique has been
shown to be useful in the manufacture of polymeric precursor fibers to obtain
hollow carbon fibers.
• A bi-component precursor fiber is made in such a way that the sheath or sea
component is PAN and the islands component is made of a polymer that can
be degraded thermally.
• Thus, hollow carbon fibre can be made.
• PAN co-polymer and PMMA were used as sea and islands components,
respectively.

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Experimental - Materials and fiber processing
• Poly(acrylonitrile-co-methacrylic acid) (PAN-co-MAA) copolymer (4 wt%
methacrylic acid) with a viscosity average molecular weight of 250,000 g/mol.
• PMMA with a weight average molecular weight of 350,000 g/mol.
• Bi-component fiber-spinning system was used to make hollow fibres (Fig. 1).
• Fiber spinning equipment consisted of two solution reservoirs, one for the
PAN-co-MAA solution to be fed as the sea component.
• The spin pack used was such that the resulting bi-component fiber consisted
of 7 islands.
• During spinning, the flow rate of PAN-co-MAA solution was maintained at
1.275 cc/min and that of PMMA solution was maintained at 0.225 cc/min.
• Spinneret temperature was maintained at 80 C.

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Fig 1 : Schematic representing the bi-component fibre spinning system
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Experimental - Materials and fiber processing
• Combined flow rate of sea and islands components, the linear jet speed was
calculated to be 29.4 m/min, and take-up speed was set to be 88.2 m/min to
obtain a spin-draw ratio of 3.
• A single-hole spinneret with 200 mm diameter and L/D ratio of 5 was used.
• The collected as-spun fiber was kept immersed in a methanol bath at room
temperature for 3 days followed by multi-step drawing using a hot glycerol
bath at 100 C, 135 C, and 160 C.
• The drawn fiber was stabilized in air at a constant flow rate of 5 L/min.
• It is then carbonized in argon at a constant flow rate of 8 L/min using a batch
process in a tube furnace.

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Experimental - Materials and fiber processing
• In the stabilization stage, the PAN fibers are first stretched to align the febrile
networks within each fiber axis, and they are oxidized in air.
• In carbonization the stabilized PAN-based fibers are pyrolyzed (heated) until
they become transformed into carbon fibers by the elimination of O,H & N
from the precursor fiber.
• For stabilization, the fibers were heat-treated at two different temperatures
(60 min at 260 C and 20 min at 305 or 325 C).
• For carbonization, the furnace was heated up to 1300 C at a heating rate of 5
C/min followed by isothermal carbonization at 1300 C.

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Experimental - Characterization
Tensile testing of the precursor fibers was done with strain rate was 1 %/s for the
precursor fiber and the average of 20 tests is reported (Table 1).
Cross-sectional micrographs of as-spun fibers were obtained using a Leica optical
microscope (Fig 2).
Effective diameter of the carbon fiber was measured from SEM micrographs
using image-analysis software, ImageJ (Fig 3) (Table 2).
Wide-angle X-ray diffraction (WAXD) patterns were obtained on a multifilament
bundle of precursor fibers - Operated at 45 kV, 0.65 mA, λ = 0.1542 nm.

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Fig 2: Optical micrograph of the as-spun honeycomb precursor fiber. Sea component is PAN-co-MAA
co-polymer and islands component (7 islands) is PMMA.
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Experimental - Characterization
• Orientation of the precursor fiber (fc) was determined from the azimuthal scan
of diffractions (200, 110) corresponding to 2θ ~16.7.
• The crystallite size was determined from the equatorial scan of the same peak
using the Scherrer equation with K = 0.9.

• Scherrer Equation

• Raman Spectroscopy was performed on a cross-section of the carbonized fiber


using a confocal Raman microscope (Alpha-Witek) with a 514-nm laser
operated at 3 mW and a 100X objective lens.

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Results & discussion
• Tensile properties of the drawn precursor fiber are listed in Table 1, showing
that the precursor tensile properties are not as high as for the typical solid
PAN precursor fiber.
• For comparison, the tensile modulus and strength of the solid gel spun PAN
precursor fiber are >18 GPa and >0.9 GPa, respectively
• The highest average tensile modulus of the hollow carbon fiber is 368 GPa,
which
• Based on the overall outer diameter of the hollow carbon fiber, the modulus
value is 244 GPa, which is similar to that of T300 (230 GPa).is 60% higher than
that of T300 and 33% higher than that of IM7.
• This structural orientation information suggests that the overall orientation of
crystallites in the hollow carbon fiber is higher than that in T300 but lower
than that in IM7.

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Results & discussion
• The tensile modulus of the hollow carbon fiber is significantly higher than that
of both T300 and IM7, suggesting that the structure of the hollow carbon fiber
is different from that of the solid carbon fiber.
• Raman spectroscopy was carried out on a honeycomb carbon fiber cross
section.
• Raman line mapping was conducted using the G-band peak position (~1590
cm1), which corresponds to the graphitic structure in the carbon fiber.
• The intensity of the graphitic G-band peak is higher at the outer wall edges as
well as in the regions surrounding the removed islands than elsewhere in the
fiber, suggesting higher graphitic order in these regions.
• The IG/ID ratio is 1.26 at point E and 0.626 at mid-point between points E and
F.
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Fig 3: (a) Optical micrograph of the honeycomb carbon fiber cross-section prepared by FIB milling,
(b) SEM micrograph and (c) schematic of the honeycomb carbon fiber cross-section,

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Fig 3: (d) Raman G-band (1590 cm1) intensity variation across the honeycomb carbon fiber cross-
section along the line shown in Fig. 3 a. The alphabetical notes (AeH) in Fig. 3 d correspond to those
in Fig. 3 a, and represent the position of the fiber cross-section. (e) Raman spectra, (i) at mid-point
between E and F and (ii) at point E.

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Conclusion
• PAN-based precursor fibers with islands-in-a-sea geometry consisting of a
good distribution of seven islands in the sea were successfully manufactured.
• The best hollow carbon fiber manufactured possessed a tensile modulus of
209 N/tex, which is 60% higher than that of the commercial solid carbon fiber
T300 (130 N/ tex).
• The high tensile modulus of the hollow carbon fibers was attributed to the
highly ordered turbostratic structure at the wall edges as evidenced from G-
band mapping of the honeycomb carbon fiber cross-section using Raman
spectroscopy.
• Carbon fiber with specific tensile modulus of up to 209 N/tex is by far the best
modulus fiber reported for a material with density of less than 1.2 g/cm3.

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THANK YOU
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