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Carbon Fiber:

Alternative Approaches
and Recycling Methods
MAE298: Sustainable Manufacturing
Matthew Gabel
Curtis Yau
What is Carbon Fiber?

● Carbon fiber: the thin strand of crystallized carbon atoms whose structure is parallel to
the length in which the fiber is formed.
○ Thousands of strands can be weaved into yarn, which can then be woven into
fabric.
● Carbon Fiber Reinforced Polymers (CFRP): Common composite form of carbon fiber that
we are familiar with; bonded with thermosetting polymers
● Benefits:
○ High Tensile Strength
○ Low Weight to Strength Ratio
○ Thermally Resistant
○ Low Chemical Reactivity
○ Shaped Easily
How’s It Made?
● Types of Precursors
○ PAN → Product of the polymerization of acrylonitrile
(highly flammable and toxic in low doses)
○ Pitch → Produced through distillation of carbon-
based materials
● Spinning: Precursor material turns into fiber form
● Stabilizing: Mildly heated in an oxygen-rich environment so
that the carbon absorbs the oxygen to rearrange atomic
bonding pattern
● Carbonizing: Heated at extremely high temperatures
without oxygen to dispel all non-carbon atoms
● Treating the Surface: Oxidized to create better bonding
surface for epoxies, etc.
● Sizing: Fiber is coated, then twisted to form yarns of various
sizes.
Carbonization Furnaces
How Carbonization Changes the Fibers
Polyacrylonitrile (PAN) Method
● Acrylonitrile is comes from propene, a byproduct of
petroleum refinement
● Reaction occurs in a fluidized bed reactor
2CH3-CH=CH2 + 2NH3 + 3O2 → 2CH2=CH-C≡N + 6H2O
● Free radical polymerization
● Polymerization usually occurs with Sulfuric Acid
Polyacrylonitrile (PAN) vs Pitch

● Pitch refers to viscoelastic polymers like


tar or plant resin
● Acrylonitrile base is more expensive than
pitch
● Pitch has more waste and clean up and is
ultimately more expensive
● PAN carbon filaments are generally
superior
● PAN is more reliant on the oil industry

Nine Drops
Since 1930
End of Life Procedures

● Typically, CFRPs are simply thrown away after


failure.
● The recycling processes introduced had a high
possibility of damaging the carbon fiber and
cutting fiber to short lengths
● Two Major Problems:
○ 1) Carbon fiber and thermosetting polymers
do not decompose in the landfills
○ 2) Many people ignore the embodied energy
required to make the carbon fiber
Taxing the Environment
● The embodied energy required to create carbon fiber: 183 - 286 [MJ/kg]
● Comparison to other composite materials and metals:

Material Embodied Energy [MJ/kg]

Polyester Resin 63-78

Epoxy Resin 76-80

Aluminum Alloys 196-257

Steels 110-210

● During carbonization process, significant levels of hydrogen cyanide (HCN), carbon


monoxide (CO), and ammonia (NH3) are released.
● Carbon fiber dust is carcinogenic and essentially like needles that stay in the lung once
inhaled.
How Can We Improve the Carbon Fiber
Manufacturing Process?

1. Emission Control Strategies:


● To control the toxic fumes that are created
during the heating process, companies have
produced Regenerative Thermal Oxidizers
capable of 98% destruction removal efficiency
and 95% thermal heat recovery.
1. Switching Precursor Materials
2. Optimizing a Recycling Method
Switching to Plant-Based Carbon Fiber Raw
Materials

● The vanilla bean orchid produces


the lignin poly-(caffeyl alcohol)
● PCFA can be used as a pitch base
for carbon filaments
● PCFA carbon fiber offers superior
mechanical properties to other
pitch methods
● The PCFA carbon does not need
to be cooked as much as PAN
based carbon fiber
● Lignins come from renewable
sources
Recycling Carbon Fiber Reinforced Polymers
(CFRP)
● Most waste from shaping parts; broken parts also
form waste.
● Involves extracting the carbon fiber from the
polymer.
○ Difficult because thermosetting polymer
○ i.e. epoxy, polyester, nylon, urethane, etc.
● Three main methods of recycling:
○ 1) Mechanical Method
○ 2) Thermal Method
○ 3) Chemical Method
● Boeing estimates that carbon fiber can be recycled at
approximately 70% of the cost to produce virgin fiber ($8/lb
to $12/lb vs. $15/lb to $30/lb), using less than 5 percent of
the electricity required (1.3 to 4.5 kWH/lb vs. 25 to 75
kWH/lb).
Mechanical Method of Recycling CFRP

● Using mills, shredders, or breakers.


● Does not separate the polymers from the carbon fiber strands!
● Many of the carbon fiber strands are crushed into short, discontinuous
pieces.
● Example: https://www.youtube.com/watch?v=wFkFChchwS4
Results from Mechanical Method of
Recycling CFRP
● Comparison between the embodied energy of
virgin carbon fiber filaments vs. embodied
energy of carbon fiber from milling recycling
process.
● LCA of a cradle-to-grave process →
○ Virgin Carbon Fiber: Measure embodied
energy for creating the filaments.
■ 183 - 286 [MJ/kg]
○ Recycled Carbon Fiber: Measure
embodied energy for recycling process.
■ 0.27 - 2.03 [MJ/kg]
● Manipulated mechanics of milling to predict
energy usage.
● ~ 99% less energy used!
Thermal Method for Recycling CFRP

● This method is preferred because the


carbon fiber isn’t cut into small pieces
● Occurs in a low oxygen environment
● Heating temperatures range from
400°C to 700°C
● Polymers begin a phase change from
solid to gaseous, evaporating it from
the CFRP
● Resulting fibers not as damaged
compared to mechanical recycling.

An oven heating the CFRP to retrieve carbon fibers


Results from Thermal Method for Recycling
CFRP

● During pyrolysis, residue from the


other materials that make up the
composite may stay.
● Pyrolysis can be paired with
subsequent oxidation to oxidize the
residue while revealing a new carbon
fiber surface.
● Recycled Carbon Fibers from pyrolysis
Oxidation Time:
are longer than from mechanical
5 [min] 20 [min] 40 [min] recycling, but still slightly damaged
and will never be as long as virgin
material.
Chemical Process for Recycling CFRP

● Also known as solvolysis.


● Process involves using chemicals to
break down the thermosetting polymers,
while maintaining the strength existing in
the carbon fibers.
○ Typically, solvents used to break
down thermoset polymers are
unsafe and ecologically damaging.
● Researchers at Washington State
Dr. Zhang and his research team at WSU
University looking for a chemical process
involving mild acids and ethanol.
Structural Integrity of Recycled Carbon Fiber

● There is <4% loss in tensile strength for recycled carbon fibers from pyrolysis; Young’s
Modulus stays the same, according to ELG Carbon Fibre Ltd.
○ Keep in mind this is using their proprietary processes.
● Researchers’ work shows varying results when keeping processes constant and using
different manufacturers’ CFRPS.
○ Generally, there is a slight strength decrease when pyrolysis is implemented.
○ There is the same strength decrease through chemical methods.
Conclusion

● Boeing estimates that recycled carbon fiber costs ~70% less than virgin carbon fiber
($8/lb-$12/lb vs. $15/lb-$30/lb), while using 5% of the energy used to make it.
● Orchid-based Pitch Carbon Fiber is comparable to PAN-based Carbon Fiber material
properties
○ The Orchid-based Pitch Carbon Fiber produces less ecological footprint than
PAN, although none of the carbon fiber breaks down naturally.
● Recycled carbon fiber has a length much shorter than virgin carbon fiber, which can be
spun into lengths however long the manufacturers want.
References

[1] “What is Carbon Fiber?” Internet: http://www.innovativecomposite.com/what-is-carbon-fiber/, 2015 [Dec. 10, 2017].
[2] “Thermoset vs. Thermoplastics.” Internet: http://www.modorplastics.com/plastics-learning-center/thermoset-vs-thermoplastics/, 2017 [Dec. 10, 2017].
[3] “How Products are Made: Carbon Fiber.” Internet: http://www.madehow.com/Volume-4/Carbon-Fiber.html, 2017 [Dec. 10, 2017].
[4] McConnel, Vicki. “The making of carbon fiber.” Internet: https://www.compositesworld.com/articles/the-making-of-carbon-fiber, Dec. 19, 2008 [Dec.
10, 2017].
[5] Maxineasa, Sebastian. (2015 July). “Environmental impact of carbon fibre-reinforced polymer flexural strengthening solutions of reinforced concrete
beams.” The International Journal of Lice Cycle Assessment. [Electronic]. Vol. 20. (10), 1343-1358. Available:
https://link.springer.com/article/10.1007/s11367-015-0940-5 [Dec 10. 2017]
[6] “Carbon Fiber: Oven Emission Control Strategies.” Internet: https://www.anguil.com/case-studies/composites-fiberglass-carbon-fiber/carbon-fiber-
oven-emission-control-strategies/, 2017 [Dec. 10, 2017].
[7] Wood, Karen. “Carbon fiber reclamation: Going commercial.” Internet: https://www.compositesworld.com/articles/carbon-fiber-reclamation-going-
commercial, Feb. 4, 2010 [Dec. 10, 2017].
[8] Limburg, Marco and Peter Quicker. “Disposal of Carbon Fiber Reinforced Polymers: Problems During Recycling and Impacts on Waste Incineration”
[Electronic]. Available: http://www.vivis.de/phocadownload/Download/2016_wm/2016_WM_221-236_Quicker.pdf [Dec 10. 2017]
[9] WSU News Posts. “Researchers develop recycling for carbon fiber composites.” Internet: https://news.wsu.edu/2017/05/01/wsu-recycling-carbon-
fiber-composites/, May 1, 2017 [Dec. 10, 2017].
[10] ELG Carbon Fibre Ltd. “Recycled Carbon FIbre: A New Approach to Cost Effective Lightweighting” Internet:
https://www.igcv.fraunhofer.de/content/dam/igcv/de/docs/Travelling_Conference_Unterlagen/03_Recycled%20Carbon%20Fibre_Gehr_ELGCF.pdf, [Dec.
10, 2017].
[11] Pimenta ,Soraia. (2011 Feb.) “Recycling carbon fibre reinforced polymers for structural applications: Technology review and market outlook”
[Electronic]. Vol. 31 (2), 378-392. Available: http://www.sciencedirect.com/science/article/pii/S0956053X10004976#tblfn29, [Dec 10, 2017].

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