Carbon Fiber Production
from Textile Acrylics
Cliff Eberle
Technology Development Manager
Carbon and Composites
Oak Ridge National Laboratory
Director, Materials and Processing
IACMI – The Composites Institute
Presented at
Carbon Fibre Futures Conference
Geelong, VIC, Australia
1 – 3 March 2017
ORNL is managed by UT-Battelle
for the US Department of Energy
ORNL Carbon Fiber R&D Drivers
Key Insight
CF is far too expensive &
volatile for cost-sensitive
industrialization
CF outperforms many high
volume application
requirements
CF will shift from specialty
material to industrial material
Consequence
Alternative feedstocks &
manufacturing processes
needed
Performance (but not
quality) can be traded for
cost reduction
Economies of scale & lean
manufacturing practices are
critical
We anticipate CF industry emphasis to shift from
Extreme performance, high cost, low volume
to
Extreme volume, low cost, moderate performance
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Classes of Commercial Carbon Fibers
1000
IM
PAN
CF
Tensile strength, ksi
YTS ≅ UTS
650
500
SM
PAN
CF
Industrial
DOE Spec
HM PAN CF
UHM Pitch CF
LCCF
SM & IM Pitch CF
150
Tensile Modulus, Msi
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150
85
45
30
35
15
Functional
Classes of Commercial Carbon Fibers
1000
IM
PAN
CF
650
500
Strength
Critical
Tensile strength, ksi
YTS ≅ UTS
SM
PAN
CF
Industrial
DOE Spec
HM PAN CF
UHM Pitch CF
LCCF
Stiffness
Critical
SM & IM Pitch CF
150
Tensile Modulus, Msi
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150
85
45
30
35
15
Functional
Automobiles may use a wide
Specific potential
range of fiber specs
automotive
applications
600
E-glass
fibers
Tensile strength, ksi
500
400
300
“Nonstructural”
• Fascias
• Liners
• Covers
• Load floor
Semi-structural
• Door panels
• Fenders
• Hood
• Roof
• Deck lid
DOE-VT Spec
Approximate
commercial PAN-based
CF property range
Structural
• Chassis
components
• Engine cradle
• Crush cones
• Roof
• BIW
1% strain
0.5% strain
200
Functional
• Electrodes
• Capacitors
• Sorbents
• Fireproof fabrics
100
0
0
10
Data courtesy Plasan
Carbon Composites
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20
Tensile modulus, Msi
30
40
Key Barriers to CF Industrialization
• Materials cost
– CF production cost
– Market volatility
– Supply chain not lean
• Scale
• Sunk capital
• Workforce
– Entrenched metals culture
– Inadequate composites
training
• High-rate composites
manufacturing
• Standards
• Design tools
• Resin compatibility
• Proven
crashworthiness
• Recycling
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• Repairability
• Innovative competition
ORNL is addressing the highest cost
components of carbon fiber production
• New precursors to
replace specialty
PAN, including PAN
variants, polyolefin,
pitch, and lignin
• Advances in heat
treatment, including
microwave and
plasma technologies
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• Acrylonitrile
• Fiber spinning
• Carbon yield
ORNL has produced textile based IMCF
with estimated cost reduction up to 50%
Composites database generation
underway for use in design,
modeling and application
development
The data generated will be applicable to high volume industries
with energy applications
Lower cost precursor and
higher heat treatment throughput
CF tensile properties ~ 40 Msi (270 Gpa)
modulus and 400 ksi (2700 Mpa) strength
Estimated textile CF production cost
per modulus up to 50% lower than for
conventional CF
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Test material is NCF C-PLY™ / Epoxy
Huntsman resins
Araldite® LY 1568
Aradur ® 3489 / Aradur ® 3492
Carbon fibers
ZoltekTM PX 35
ORNL SM and IM textile CF
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Composite Mechanicals
Properties to be published
in a future publication
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Current and Future Benchmarking
• Continuous and Discontinuous LCCF versus Zoltek
– Arkema Elium Thermoplastic Resin
• Compounded LCCF versus Zoltek / BASF PA6 –
Injection molded
• Recycled Carbon Mats vs SMC vs Chopped LCCF
(Virgin)
• Pultruded continuous LCCF with TP and TS
• Tape overmolding
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Contrasts between Specialty and
Textile Acrylic Fibers
Parameter
SAF
TAF
Plant production capacity
Order 10k tpy
Order 100k tpy
Typical filaments per tow
12k – 60k
100k – 1,000k
Typical filament denier
0.7 – 1.5
1.5 – 3.0
Typical filament shape
Round
Often not round
Spool, non-crimped
Bale, crimped
Methyl acrylate
Vinyl acetate (usually)
or methyl acrylate
2% - 5%
7% - 13%
>> 100k grams/mol
Order 100k grams/mol
Polydispersity index
<3
>3
Relative purity
10
1
Typical package
Co-monomer
Co-monomer content
Molecular weight
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Carbon Fiber Cross Sections
Primary ORNL
precursor to date
Specialty acrylic fiber
~ 7 micron CF dia
Textile acrylic fiber A
2.5-3.5 x 5-8 micron CF
Textile acrylic fiber B
2-4 x 8-11 micron CF
• How does fiber
cross section affect
performance?
• It may be possible to
tailor cross section
if it is useful
Textile acrylic fiber C
Textile acrylic fiber D
3.7 – 5.5 micron CF dia
3.5 – 5.5 micron CF dia
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ORNL is negotiating up to five licenses
for textlle CF production process
• Establish a low cost carbon fiber
industrial base in the United States
• Licensees able and committed to
bring the technology to market
• Create jobs and economic
opportunity in the United States
• Provide a return on taxpayer
investment in this technology
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Three licenses signed to date
A third license has been
executed. A complete
public announcement is
planned within 90 days.
Licensees can collaborate with ORNL to opti-mize their
products, train staff and produce sample materials at ORNL
facilities until their factories are commissioned
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Other ORNL Carbon Composites R&D
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Carbon Fiber R&D: Low-Cost Precursors
•
•
•
•
•
PAN variants
Pitch
Lignin
Polyolefin
Scrap?
Photo courtesy of FISIPE
Photo courtesy of FISIPE
18-filament, melt-spun PAN tow
Courtesy MeadWestvaco
Lignin powder
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Melt spinning line
Spooled lignin fibers
Mesophase pitch (photo by Chris Levan)
Carbon Fiber R&D: Functional
Fibers from Low-Cost Precursors
• Thermal management
• Electrical energy storage
– Batteries
– Capacitors
• Adsorption / Filtration
• Flame resistance
18
18” diameter lignin CF insulation
prototypes
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Carbon Fiber R&D: Advanced Conversion
• Plasma oxidation
• Microwave-assisted plasma
carbonization
• Advanced surface treatment
• Novel sizings
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Precursor & Process Tradeoffs
Precursor/
Process
Standard PAN
precursor
Strength, elongation, knowledge
base, fiber architecture
Optimized PAN
precursor
Textile PAN
precursor
Melt stable PAN
precursor
Bio-PAN
Polyolefin
precursor
Pitch-based
precursor
Lignin-based
precursor
Recycled CF
Cost Δ
Energy Δ
Feedstock price and volatility, capital
cost, energy, yield, processing
0%
0%
Properties, knowledge base,
energy consumption and cost
Capital cost and yield comparable to
standard PAN precursor
-25%
-30%
Tensile modulus, knowledge
base, energy consumption, cost
Tensile strength, variability, product
form
-50%
-50%
Throughput and energy in
spinning, strength, elongation,
fiber architecture
Renewable; pricing decoupled
from oil
Feedstock price and stability,
spinning, yield, fiber architecture
Feedstock price and stability,
spinning, yield, knowledge base,
properties develop w/o stretching,
moderate capital
Feedstock price and stability,
renewable domestic feedstock
Same as standard PAN, but higher
energy productivity and lesser
knowledge base
- 30%
- 30%
TBD
TBD
Conversion process and equipment,
knowledge base, capital cost
- 20%
- 50%
Elongation and compression strength,
fiber architecture
- 70%
- 70%
- 50%
- 40%
-60%
-90%
Thermal process limits energy
reduction and process speed
-15%
-25%
Knowledge base, risk
- 25%
- 50%
Advantage
Cost, energy, capital cost, yield,
fiber architecture (future)
Optimized
Known technology and
conventional thermal
configuration, knowledge base
processing
Advanced conversion
Speed, energy, capital cost
processing
Disadvantage
Knowledge base, scale
Mechanical properties, yield,
processing, knowledge base
Feedstock availability, fiber
architecture (current), knowledge base,
risk
Sources: Das, S. and Warren J., “Cost Modeling of Alternative Carbon Fiber Manufacturing Technologies – Baseline Model Demonstration,”
presented DOE, Washington, DC, 5 April 2012; Unpublished analysis by Kline and Co, 2007; Suzuki and Takahashi, Japan Int’l SAMPE
Symposium, 2005; http://energy.gov/articles/energy-department-announces-new-investments-innovative-manufacturing-technologies-0 , and
ORNL internal estimates
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Other potential markets for low-cost
carbon fiber
Civil infrastructure
Rapid repair and installation, time and
cost savings
Nontraditional
energy
Geothermal, solar, and ocean
Non-aerospace
defense
Light weight, higher mobility
Aerospace
Secondary structures
Power transmission Less bulky structures, zero CTE
Oil and gas
Offshore structural components
Energy storage
Flywheels, batteries, capacitors
Electronics
Light weight, EMI shielding
Thermal
management
Thermal conductivity
Safety
Flameproof
Filamentary
sorbents
High specific surface area
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•
•
•
•
•
Common issues
Fiber cost
Fiber availability
Design methods
Manufacturing methods
Product forms
ORNL Carbon Fiber Mfg R&D Capabilities
Materials development, processing, and characterization from nanoscale to
semi-production scale
Spinning
Heat treatment
Lab
Pilot
Semi-production
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Composites
Manufacturing
• Key expertise
– Additive manufacturing
– Rapid preforming
– Chopped fiber composites
– Filament winding
– Fast, energy efficient
curing / processing
(includes out-of-autoclave)
– Design and analysis
– NDE
ORNL’s Research P4 Machine
Composite Hull Qualified
to 20,000-ft Depth
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Institute for Advanced Composites
Manufacturing
Innovation –
Shared RD&D
Assets
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Addressing Critical Challenges
Five/Ten Year Technical Goals
• 25/50% lower carbon fiber–reinforced
polymer (CFRP) cost
• 50/75% reduction in CFRP embodied energy
• 80/95% composite recyclability into useful
products
Impact Goals
•
•
•
•
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Enhanced energy productivity
Reduced life cycle energy consumption
Increased domestic production capacity
Job growth and economic development
Summary
• Emerging high volume, cost-sensitive markets
are driving the development of new carbon fiber
production technologies
• New developments in textile based CF may offer
cost-performance attributes matching the needs
of high volume industries, e.g., automotive
• Composites testing is underway with these new
textile based CF – further tests are planned to
evaluate applicability and/or tailorability to high
volume, cost sensitive industries
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Acknowledgements
• ORNL R&D Team
• IACMI – The Composites Institute
• Academic and industrial partners
• DOE-EERE Advanced Manufacturing
• DOE-EERE BioEnergy Technologies
• DOE-EERE Fuel Cell Technologies
• DOE-EERE Vehicle Technologies
• DOE-EERE Wind Program
• ORNL Laboratory Directed R&D Program
• ORNL Program Management
Oak Ridge National Laboratory is operated by UT-Battelle, LLC
for the U.S. Department of Energy under contract DE-AC05-00OR22725
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Questions?
ORNL Carbon Fiber
Technology Facility
Cliff Eberle
[email protected]
0011-1-865-661-4292
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