Recent Developments on Carbon

Fibers from Rayon-Based Precursors

Gajanan Bhat, Sammy Akato, Nicholas Cross,

The University of Tennessee, Knoxville
West Hoffman, AFRL, Edwards, AFB, CA and
Farhad Mohammadi, Advanced Cerametrics, Lambertville, NJ
 Carbon Fiber Precursors

 Rayon (or regenerated cellulose)

 PAN (Polyacrylonitrile)
 Pitch (petroleum and coal tar based)
 Natural materials such as lignin, wool, cotton,
ramie, and jute
 High performance highly crystalline aramid
fibers such as Kevlar
 Polymeric materials like phenolic resins
 Rayon Fibers

 Rayon is produced from

naturally occurring cellulose
polymers

 Some properties of rayon

fibers
– Availability
– Low cost
– Non-melting character Repeat unit of cellulose
– Ease of production

 ~ 44% carbon content

Earlier Research on Rayon-Based CF

 Thomas Edison used CCF as filaments for

incandescent lamps (1880)
 Bacon et al. patented a process using viscose rayo
fibers to produce high strength, high modulus RCF
 Union Carbide used stress graphitization to produce
strong RCF (1959)
 RCF were the first to be qualified by NASA
 Later other precursors became more prominent
 Why This Study?

 Currently rayon fibers are not produced in

the US
 Rayon-based CF are still of interest to DoD
 Experimental rayon fibers (Advance
Cerametrics) are being evaluated as a
candidate for CF precursor
 Precursors

 Commercial rayon fibers from Lenzing, Austria

 Experimental rayon fibers from Advanced
Cerametrics, Lambertville, NJ USA

X-ray patterns of the commercial rayon and experimental rayon fibers

Physical and Mechanical Properties of Rayon
Fibers
 Production of Carbon Fibers

 Stabilization of the precursor at low

temperatures
– Oxidation in air at lower temperature (<400°C)
 Carbonization in an inert atmosphere up to
~1500°C
– Longitudinal orientation
– Development of the crystalline ordering
 Graphitization in an inert environment up to
3000°C
– Optional for high modulus
Set-up for Stabilization and Carbonization

1200

1000
Temperature (C)

800

600

400 130C
600C
200
1200C
0
Production of Rayon Carbon Fibers
(RCF)

 Pretreatment
– Impregnated in 1 normal solution of phosphoric acid
for 5 hours
– Dried at room temperature overnight
 Oxidation in air at lower temperature up to
380°C
 Carbonization in an inert atmosphere (Nitrogen)
up to 1200°C under tension
 HTT
 Effect of HPA Pretreatment

DSC TGA

 Catalyzed the dehydration reactions

 Lowered degradation temperature over a wider
range
 Suppressed the release of volatile organic
substances by reacting with hydroxyl groups
Stabilization Conditions
 Carbonization Conditions

 All samples were stabilized first from 110C to 380C in

air for a total time of 3 hours
 Applied load for sample 6003 is 10g and applied load for
sample 6005 is 50g
SEM of Untreated and Treated rayon
Fibers after Pyrolysis
TGA
TGA Scans of Fibers
Change in Crystalline Structure

380
350
300
250
200
150
Precursor

0 10 20 30 40 50 60 70
2 Theta

 The dehydration only changed the crystal structure partially

 Fibers become amorphous at 300°C
 Order develops after 380°C
SEM

SEM micrographs of the surface and cross-section of the carbonized sa

 The fiber diameter changes with temperature
 Smaller fibers
 Smoother surface
 The fibers appear to be of good quality
 Elemental Analysis

Carbon content
Hidrogen content

80

70

60

50
% Content

40

30

20

10

0
Precursor Stabilized 6002 6003
Sample ID
EDAX
EDXA results of the precursor, the stabilized fibers
and the carbonized fibers to 1200C respectively
Mechanical Properties
Effect of tension during carbonization
High temperature heat treatment

 HT to 1700 C at ORNL
Change in Thermal Behavior (TGA)
 Elemental Analysis
80

70

60
% content

50

40
Carbon content
30 Hidrogen content

20

10

0
Precursor 502 506
Sample ID
 SEM of CF

SEM micrographs at 2KX of the

carbonized sample
Comparison of the Produced CFs
SEM of HTT CF
 Initial Observations

 The use of phosphoric acid shifts the pyrolysis

reactions to lower temperatures
 As the pyrolysis progresses, the structure changes
 The mechanical properties of the obtained fibers
need to be improved
 To improve the mechanical properties of the
obtained fibers:
– Lower fiber diameter
– Control the shrinkage
– Higher HTT
 Studies with a Smaller Diameter
Precursor

 Precursor Diameter ~ 12 micron

Shrinkage and Fiber Diameter Change
 Shrinkage

Shrinkage Percentages with Varying Tension

20

18

16

14
Shrinkage (%)

nc-17 (10 grams)

12
nc-16 (20 grams)
10 nc-14 (50 grams)
nc-18 (75 grams)
8
nc-19 (100 grams)
6 nc-110 (120 grams)
nc-30 (50 grams)
4

0
100 150 200 250 300 350 400 450
Temperature (°C)
 Shrinkage
40

35
Amount of Shrinkage (%)

30

25

20
50 grams
120 grams
15

10

0
0 200 400 600 800 1000 1200

Temperature (Celsius)
SEM of Carbon Fibers
Elemental Analysis
 Future Work

 Smaller diameter fiber stabilization

optimization
 Tension is critical
 Tension during Carbonization & HTT is also
important
 Increase HTT to achieve higher ‘C’ content
 Continuous processing
 Acknowledgements

 AFRL
 Advanced Cerametrics
 Lenzing
 Harper International