R&D on Low-Cost Carbon Fiber Composites for Energy ... · PDF fileR&D on Low-Cost Carbon Fiber...
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R&D on Low-Cost Carbon
Fiber Composites for
Energy Applications
Cliff Eberle
Technology Development Leader
Carbon & Composites
Oak Ridge National Laboratory
Presented at
Carbon Fiber R&D Workshop
July 25 – 26, 2013
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ORNL is DOE’s Largest Science and
Energy Laboratory
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$1.65B budget
World’s most intense
neutron source
4,400 employees
World-class research reactor
3,000 research guests annually
$500M modernization
investment
Nation’s largest
materials research portfolio
Most powerful open
scientific computing
facility
Nation’s most diverse
energy portfolio
Managing billion-dollar U.S. ITER
project
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Discovering and Demonstrating
Advanced Materials for Energy
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Advanced Manufacturing
R&D Ecosystem for Technologies
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ORNL Develops Composite
Technologies across Applications
Gas Centrifuge Vehicle Technologies
Wind Turbines
• Motor/Generator
• Power Electronics
• Lightweight Materials (e.g., composites)
• Sensing and Measurement Science
• Modeling and Simulations
• Systems Engineering, etc. Figures from wikimedia, http://cardisplayreviews.blogspot.com/2012/11/gm-hy-wire.html, & http://exportcontrols.info/centrifuges.html
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Why DOE Cares About Composites
Source: Transportation Energy Data Book, 31st Edition (2012)
US Petroleum Production and Consumption
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Source: Transportation Energy Data Book, 31st Edition (2012)
US Cost of Oil Dependence
Why DOE Cares About Composites (2)
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Carbon fiber potential in 5 years at 50% of current price
Source: Lucintel, ACMA
Composites 2012
Potential automotive market is huge
for low-cost carbon fiber
Global automotive production by car type
Expected vehicle
production Expected use of CF in cars
Demand for CF at 50% of current price (pounds)
Market for CF at 50% of current
price ($M)
6,000 100% 1.3 million $7M
600,000
10% 101.2 million $506M
4 million
92 million 1% 202.4 million $1,012M
Total 97 million 305 million $1,525M
Super cars
Super luxury cars
Other/regular cars
3 current global CF demand for all applications; 10B lb potential automotive demand at full market penetration
Potential to reduce US petroleum demand by 2-3 Mbpd (~10-15%)
Luxury cars
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Enable deployment of low-cost technology in high-volume applications
– Low-cost raw materials
– Low-cost fiber manufacturing processes
– High-rate, robust composites manufacturing processes
Develop and transition to industry technology with significant impacts on U.S. and global energy security
Carbon Fiber and Composites
at ORNL
Maximize impact through industry
partnerships
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ORNL Carbon Fiber Mfg R&D Capabilities
Precursor evaluation system
Pilot CF conversion line
Materials development, processing, and characterization
from nanoscale to semi-production scale
Energy efficient processing - Unique facilities
Multi-scale characterization
Mesh Belt Furnace
Robotic preformer
Microwave-assisted plasma carbonization
Melt spinning Advanced oxidation
Carbon Fiber
Technology Facility
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Conventional PAN Conversion
Typical processing sequence for PAN –based carbon fibers
Major Cost Elements Precursor ~ 50% Conversion ~ 40% Other ~10%
• Automotive targets $5 - $7/lb, tensile 250 ksi, 25 Msi, 1% ultimate strain
• Hydrogen storage targets 25% cost reduction for tensile 700 ksi strength, 33 Msi modulus
• ORNL is developing technological breakthroughs for major cost elements
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Low-Cost PAN Precursor
Textile PAN and/or melt spun PAN
Estimated 20% - 30% cost reduction vs. conventional PAN
Textile PAN tensile mechanicals > 500 ksi strength and > 30 Msi modulus
Now developing higher strength version of textile PAN (> 600 ksi strength requirement)
Melt spun PAN requires ~ 650 ksi with ≥ 25% cost reduction; recently met 250 ksi / 25 Msi milestone
Textile PAN mechanicals
10-filament, melt-spun PAN tow
Textile PAN precursor
(courtesy FISIPE)
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Dow and Ford team up to bring low-cost, high-volume carbon fiber composites to next-generation vehicles
– Reducing weight of new cars and trucks by up to 750 lbs by the end of the decade
– Builds on foundational work at ORNL
– DOE, Dow, Ford, and state of Michigan fund $13.5M research agreement to develop lower cost carbon fiber production process using polyolefin in place of conventional polyacrylonitrile (PAN) as feedstock
– Novel process to reduce production cost
– High-volume commercial launch anticipated outcome
Dow and Ford partner with ORNL to
scale up polyolefin based carbon fiber
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Lignin-Based Fibers
Produced ~ 1,500 lb of precursor fibers in web form
Batch stabilized ~ 180 lb of fibers
Developed stretchable single filaments
Demonstrated that lab-scale properties meet requirements for selected “functional” applications
Estimated mill cost ~ $4-5/lb in web form
Melt-blowing lignin fiber web Stabilized lignin fiber mats
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PAN
68 wt% C
PAN-MA
64-67 wt% C
PE
86 wt% C
Softwood Lignin
E. Adler, Wood Science & Technology, 11, 169 (1977)
Precursor Chemistry
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Precursor Status Summary
Precursor Strength
ksi
Modulus
Msi Scale
DOE Requirement
Semi-structural 250 25 Semi-production
Structural (for
pressure vessels) ~650 ~33 Semi-production
Textile PAN > 500 > 30 Multiple continuous large tows
Melt spun PAN 250 25 Spun 10 filaments, 100 ft
Converted 100 filaments, 10 ft
Polyolefin > 200 > 20 Spun 3000 filaments continuous
Converted 3000 filaments, 1-10 ft
Lignin tow ~ 175 ~ 12 Spun 10 filaments, continuous
Converted 10 filaments, 1 ft
Lignin web* ~ 70 ~ 7 Spun 100 lb batches
Converted 10 lb batches
* Lignin web applications are primarily functional
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Plasma Stabilization/Oxidation
Atmospheric pressure, nonthermal plasma processing
– Short residence time
– Energy efficient
Updated cost estimate suggests that it reduces oxidation cost by about half vs. conventional oxidation
2X – 3X reduction of residence time for aerospace grade 3k tow
Tensile mechanicals 350 - 450 ksi strength, > 30 - 37 Msi modulus, > 1.0% - 1.4% strain (conventionally carbonized)
Reduced processing temperature
Multiple commodity grade tows have been processed, mechanicals TBD
Commenced processing of textile PAN and lignin chemistries – qualitatively good, too early to report quantified results
Installed 1 tpy scale reactor
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Microwave-Assisted Plasma Carbonization
Combined microwave and low-pressure plasma processing
– Short residence time
– Energy efficient
Residence time reduced by 2X – 3X vs. conventional carbonization, property requirements exceeded
Updated cost estimate suggests that it reduces carbonization cost by about one-fourth vs. conventional (potential reduction likely higher if coupled with plasma oxidation)
Modeling electromagnetic field distribution and coupling
Evaluated tow spatial configuration – need to resolve discrepancies between model and experiments
Achieved good energy balance
Currently developing next generation reactor for five large tows (nominal capacity ≥ 1 tpy)
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Advanced Post-Treatment
Includes both surface treatment and sizing
Improves short beam shear strength by ~ 40% in vinyl ester resin vs. standard practice
Emphasis on compatibility with commodity resins including both thermosets and thermoplastics
Dry surface treatment is preferred approach
Advanced post-treatment module fabricated for ORNL’s small (~1 tpy) pilot line
1 tpy dry surface treatment module
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Composites
Manufacturing
Key expertise / thrusts
– Rapid preforming
– Direct digital manufacturing
– Filament winding
– Fast, energy efficient curing, processing (includes out-of-autoclave)
– Design and analysis
– Testing, characterization, NDE
ORNL’s Research P4 Machine
Composite Hull Qualified
to 20,000-ft Depth
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Energy Efficient Processing
Oxidized tows
Plasma Oxidation
Microwave-Assisted Plasma Carbonization
E-Beam Curing
Microwave Processing
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Morphology
Properties
and
(Multi-)
Functionality
10 m 100 m
Source: Hunt et al. Adv. Mat. (2012)
Source: Hunt et al. Adv. Mat. (2012)
IM PAN Fiber HM PAN Fiber HM Pitch Fiber
New Technology Enables Fibers
Tailored with New Functionality
Lignin powder Polyolefin pellets
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Polyurethanes, nylons, polyesters
Nylons
Vinyl Esters
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Fused Deposition Modeling
Polymer Additive Manufacturing
6061 Aluminum = 102 Nm/g (275 MPa)
Injection Molding = 86 Nm/g (110 MPa)
FDM = 45 Nm/g (70 Mpa)
Specific Strength (Nm/g)
Research Impact Goal
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Nanocomposite Material for FDM
Carbon Fiber Composite
• Min Fiber Dia = 5μm
• FDM tip will clog
• L/D is too small
• Need nano-fiber
~10 μm
100-200 nm
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LBCF’s meet performance requirements
for high temperature thermal insulation
Figures courtesy
GrafTech
18” diameter lignin GRITM prototypes
GRI
GRITM insulation in a furnace
for polysilicon production Various GRITM products
machined into shapes.
LBCF is a “drop-in” replacement
for Chinese-sourced isotropic
pitch CF used in GrafTech’s
commercial GRITM product
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High Performance Battery Electrodes
Bio-PowderBio-Carbon
Fiber
High performance battery
electrodes made from
bio-derived carbon fibers
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CF Composites Can Function as Batteries
All alternative powertrain vehicles must be light weight to achieve range metrics
“Structural battery” that stores electrochemical energy in structural composites can significantly extend range
Volvo is funding structural battery development at Swerea Sicomp
Can new carbon fiber functionality enable this radical concept?
Source: Autoblog http://www.dailytech.com/Volvo+Plans+to+Insert+EV+Batteries+Into+Body+Panels/article19723.htm
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Courtesy Umeco
Potential low-cost carbon fiber markets
Vehicle technologies Necessary for >50% mass reduction
Wind energy Needed for longer blade designs
Oil and gas Offshore structural components
Pressurized gas storage High specific strength
Energy storage Flywheels, batteries, capacitors
Power transmission Less bulky structures, zero CLTE
Nontraditional energy Geothermal, solar, and ocean
Civil infrastructure Rapid repair and installation, time and cost savings
Non-aerospace defense Light weight, higher mobility
Aerospace Secondary structures
Electronics Light weight, EMI shielding
Thermal management Thermal conductivity
Safety Flameproof
Filamentary sorbents High specific surface area
Common issues
• Fiber cost
• Fiber availability
• Design methods
• Manufacturing methods
• Product forms
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PAN
Polyolefin
Lignin
Building a sustainable carbon fiber
commercialization strategy
Today
1 tpy conventional line
Bench-scale advanced line
25 tpy conventional line
Bench-scale advanced line
~2015
25 tpy advanced line
Resin design
Matrix formulation
Pre-pregging
Weaving
Pre-forming
Molding
Filament winding
Precursor development
Carbon fiber conversion
Composite formulation and manufacturing
processes
End users
Cost and performance specifications
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Summary
ORNL program driver is US energy security
New materials and manufacturing technologies can enable cost-effective use of carbon fiber composites to improve energy production, distribution, and use
Reinventing carbon fibers can lead to innovative new functionalities and applications
Transition/deployment strategies include key scaling capabilities, industrial partnerships, and workforce training
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Acknowledgements
ORNL R&D Team
Academic and industrial partners
DOE-EERE Vehicle Technologies Program
DOE-EERE Fuel Cell Technologies Program
DOE-EERE Advanced Manufacturing Office
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