Carbon Fiber

Composites
Presentation to the
Bridging the Gap
Conference at ORNL
Amit K Naskar

Materials Science and Technology Division

March 5, 2013

Carbon Fiber is Finding Many Application

Lightweight
portable ground
and sea system
for defense
industries

Secondary
aircraft
structures

Low-weight high
pressure gas storage
tank
Retrofit and
new
construction
in days
rather than
months Moldable conducting
composite (EMI shielding)

Low, stable price

Assured supply
Design methods
Product forms
Product consistency
Recovery and reuse

Composite
cored
conductor
(Low CTE)
10% mass savings = 6-7% fuel savings
In deep water strength or
stiffness/mass is critical

Greater energy capture by longer blade

Carbon Fibers The Gold Standard for LightWeight High-Performance

PBO Zylon
PBO

E-Glass
Kevlar

PAN

M5

TM SiC
Nicalon
Low
cost

MESOPHASE PITCH
RAYON
Alumina

Nylon
ISOTROPIC PITCH

Carbon fibers are widely used for high performance cars, aircraft, sports goods, but
the conventional PAN-based fibers are expensive.

Carbon Fiber Manufacturing Technology

OXIDATION

PRE-TREATMENT

LOW temp.

SURFACE TREATMENT

Oxidation Stage:
Four identical furnaces operated at
different temperature zones

HIGH Temp.

SIZING

Chemistry of carbon precursors

dictates processing protocol

CARBONIZATIONS

SPOOLING

Precursor has the Greatest Impact on Cost

Diagram from Harper International

Spooling &
Packaging

Surface
Treatment

$0.61
$0.41

$0.37
$0.33

Carbonization/
Graphitization

Stabilization
& Oxidation

$2.32
$1.48

$1.54
$0.99

Precursors

Baseline Today - $9.88

High Volume - $7.85

$5.04
$4.64

12
9

51

10

18
Precursor
Labor
Depreciation

Lignin and polyolefin will be an

attractive precursor candidate
compared to PAN if we can solve the
problems associated with those.

Data from Kline and Company

Utilities*
Other fixed

New Processing Required for Alternative

Precursor Conversion
ORNL invented advanced plasma
and microwave processing
technology
Filaments undergo
atmospheric pressure plasma
oxida7on and microwave
assisted plasma carboniza7on,
New technology requires about
one-third of the residence 7me
and one-half of the energy per unit
mass output of conven7onal
oxida7on and carboniza7on
processes.
Recent ORNLs discovery of
successful technology for
conversion of polyolen gives 25%
higher carbon yield.

Carbon ber tow exits high temperature

carboniza4on furnace

Microwave assisted plasma carboniza4on

Successful Processing of Polyolefin Teaching

Us General Approaches to Other Carbon
Precursors
Sulfonation renders PE
into an infusible material.
5 nm

Kinetic data for the

degree of sulfonation
versus reaction time and
the structure of carbon
fiber derived from
sulfonated polyethylene.
ORNL built a collaborative
program and the team
successfully secured
manufacturing
demonstration project of
$9 M.

5 nm

2 nm

Can we use these

materials for
separation, filtration
techniques?

Hunt, Saito, Brown, Kumbhar, Naskar, Advanced Materials, 24, 2386-2389 (2012)

20 nm

Lignin is the Byproduct of Biofuel Industries

Lignin Represents Grand Challenge with

Great Potential
How to make structural carbon fibers from Lignin?
Lignin tends to yield disordered carbon. How can we induce ordered
structure in lignin during pyrolysis?

TEM 002 lattice fringe image (a) and

selected area diffraction pattern (b)
of lignin carbon fibers

PAN-based carbon fibers show better

graphitic structure than the lignin-derived
carbon. Inset: SEM image of a single
filament of lignin derived carbon fiber.

Lignin Molecules are not Linear

Hardwood Lignin
H. H. Nimz, Angew. Chem. Int. Ed., 13, 313 (1974)

Softwood Lignin
E. Adler, Wood Science & Technology, 11, 169 (1977)

HO

HO

HO
coniferyl alcohol
(> 90%)

CH3O

HO

p-coumaryl alcohol

CH3O

HO

CH3O

HO

coniferyl alcohol

synapyl alcohol

(various ratios)

PAN-based conventional carbon

precursors

OCH3
HO

HO

Three Pathways Identified on Lignin

Precursor R&D

Artificially increased lignin molecular weight through chemical modification helps to enhance
performance of synthesized precursor. We are currently investigating how to translate that to
carbonized fibers by:

Use of varied lignin composition (Chemical Science and MST Division)

Use of solvent fractionated lignin with different chemistries (MST & CNMS Division)
Discovery new lignin compositions (Noble Foundation and BioEenergy
Science Center)

Functional use of lignin-derived carbon fibers:

CO2 capture, high temperature insulation materials, battery electrode, use in arc
furnace electrode, controlled adsorption and release of macromolecules.

Novel Deposition Methods are Being

Developed for Large Volume Manufacture to
Exploit Low-cost Carbon Fibers
Carbon ber
composite
material

Spools of carbon fibers

Improved tools to facilitate composites implementaPon:

Integrated process/structural models
Resin formulated for specic applica7ons
High rate processes at lower cost
Composite material Prin4ng
Fiber forms tailored to process requirements
Performance verica7on from thorough materials characteriza7on and structural tes7ng

ORNL is Developing New Surface Treatment and

Sizing Technologies
Thermochemical

Atmospheric plasma

Highly efficient and flexible ORNL Thermo-chemical and Atmospheric Plasma surface treatments

ORNL Thermo-chemical and Atmospheric Plasma surface treatments coupled

with ORNL sizings (coatings) are capable of delivering custom solutions for
high volume, rapid composite processes

Carbon Fiber Technology:

From Lab Discovery to Commercialization.
Basic Science
(Office of Science)

Applied R&D

(EERE Vehicle Technologies and

Precursor Materials and

Fiber Formation

Industrial Technologies Programs)

Precursor Chemistry
and Microstructure

Fiber Processing

Process Science

Gas phase reaction and

internal heating through
material dipole vibrations

Melt spinning increases

throughput with less
energy and no solvent

Manufacturing &
Commercialization
25 ton/yr carbon fiber pilot
line facility start up in 2013

Microwave/plasma-based
conversion processes
reduce residence time
and energy demand
Large IP portfolio available for
licensing
Developing key partnerships
in multiple industries

Lets Bridge the Gap Together and Develop

Low-Cost CF Composites Manufacturing
Technologies
PAN
Textile,
HMW, SAF

PRECURSOR
FIBERS

Solution
Spinning

PAN
Melt-spun

Polyolefin

Melt
Spinning

Lignin

CONVERSION

Advanced Conversion Processes

RAW
MATERIALS

Highly Flexible
Thermal
Process
Atmospheric
Pressure
Plasma
Microwave
Assisted
Plasma
Plasma
Surface
Treatment

CFTF in dashed area

15

COMPOSITE
FORMULATION

TESTING &
PROTOTYPING

Resin Design
Matrix
Formulation
Pre-pregging
Weaving

Testing

Pre-forming

And

Molding

Prototyping

Filament
Winding
Curing
Etc.

APPLICATIONS

STRUCTURAL
Vehicles
Wind
Defense
Aerospace
Oil & Gas
Infrastructure
NON STRUCTURAL
Flame Retardant
Energy Storage
Filtration
Thermal Mgmt.
Electrodes

End Users provide ORNL with cost & performance specs

. & move beyond that to grow the supply base

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for the U.S. Department of Energy