Ceramic Structural Composites

The Most Advanced Structural Material

 Composite -v- Monolithic Ceramics
Interphase
LOAD

matrix

fiber
crack
crack
arrest

Fiber Composite materials, whether platelet, chopped

Matrix fiber, or continuous fiber reinforced are superior
engineeringmaterials to monolithics:

generally higher strength, especially in tension

higher Weibull modulus (more uniform failure)
much higher damage tolerance (fracture toughness)
 Composite -v- Monolithic Ceramics
200
Carbon
Fiber
150 Composite

Strength (MPa)
100
Graphite

50

Toughness 0
MPa/m-1/2 0 0.2 0.4 0.6 0.8 1
Displacement (mm)
Steel >50

Monolithic Ceramic 3 Monolithic Composite

Platelet Reinforced Ceramic 6 Strength (MPa) Strength (MPa)
SiC 100 50 220 20
Chopped Fiber Reinforced 10

Continuous Fiber Reinforced 25-30 Graphite 107 20 176 20

Ceramic
 Ceramic Structural Composites
The Most Advanced Structural Material

Composite Examples
 Structural Composites in Aerospace Applications

Thermal protection system for a re-entry space vehicle:

Nose corn, leading edge,
Rocket engine: Extendable nozzle, aerospike engine,
Scram-jet engine for a future space vehicle.
C/C with TBC/EBC is in commercial.
SiC/SiC will be more attractive (e.g. Tyrannohex).
 Exhaust Tail-cone

Weaving / 2D Cloth + Stitching

Successfully engine demonstrated at gas temperature 1573K (1998)
 SiC/SiC Thrust chamber

Weaving / 3-Axial Braiding

Successfully hot firing tested at gas temperature 2073K (1998)
 Carbon Fiber Reinforced Composites
TREK Madone 5.9
Carbon Fiber Composite
Glass Fiber Reinforced Composites

Ferrari 308 GT4

Glass Fiber Composite
Reinforced Concrete Composite

Steel reinforced rebar

Carbon Fiber/epoxy rod

Reinforced Fired Adobe Composite
 Reinforced Fired Adobe Composite

Inca city ~ 1500 AD Present Day

 Reinforced Fired Adobe Composite

Inca city ~ 1500 AD Present Day

1.5

Compressive Strength (Kg/cm2)

Andes Straw

LOAD Ichu grass

matrix
fiber

crack 0.5

crack J. Vargas Data

0
arrest
-0.5 0 0.5 1 1.5 2 2.5 3 3.5
% Straw or Grass
Puye Cliff Dwelling
Anasaze Indians
1100-1580 AD
Fort Paramonga Chimu civilization ~1300 AD
Tel-Dan Arch
~1600 BC
 Short History of Materials
10000 bc 5000 bc 0 1000 1500 1600 1900 1940 1960 1980 1990 2000

GOLD COPPER
BRONZE
IRON METALS
CAST IRON
POLYMERS/ STEELS ODS STEELS
ELASTOMER
WOOD
LIGHT ALLOYS NEW SUPERALLOYS
SKIN
FIBERS
GLUES SUPER ALLOYS GLASSY METALS

RUBBER TITANIUM,
COMPOSITES ZIRCONIUM
etc. ALLOYS HIGH TEMPERATURE
STRAW-BRICK HORSEHAIR
POLYMERS
PLASTER
STONE HIGH MODULUS
FLINT BAKELITE POLYMERS
POTTERY NYLON POLYESTERS CERAMIC
GLASS P.E. EPOXIES MATRIX
METAL
CEMENT PMMA ACRYLICS MATRIX
REFRACTORIES
CERAMICS/ PORTLAND C/C
GLASSES GFRE
CEMENT FUSED
SILICA PYROLITIC TOUGHENED
CERMETS CERAMICS CERAMICS

10000 bc 5000 bc 0 1000 1500 1600 1900 1940 1960 1980 1990 2000

Date
 Ceramic Structural Composites
The Most Advanced Structural Material

Fusion Structural Composites

 Yield Strength of Various Materials
Yield Strength of Various Structural Materials
600

500
Superalloy
C/C Composite
400
Yield Strength (MPa)

300 SiC/SiC
Carbon Steel
Zircaloy
200

Stainless Steel
100
Graphite
0

0.0 400.0 800.0 1200.0 1600.0

Temperature (C)
Operating Range, Highly Irradiated Structural Materials

C/C

SiC/SiC

Tungsten

Molybdenum

ODS Ferritic

F/M Steel Questionable

316 Stainless
Reasonable
Alloy 718

0 200 400 600 800 1000 1200 1400 1600

Operating Temperature (C)
 Ceramic Structural Composites
The Most Advanced Structural Material

Carbon/Carbon Composites

- In widespread structural use

- Manufacturing and design methods understood
- Expensive
 Divertor Designs Using C/C Composites

Full-scale vertical target

armored mock-up uses
a pure Cu clad DS-Cu
tube armored with
saddle-block C/C and
W CVD-W armors.
(Hitachi Ltd., Japan)

Pure Cu clad DS-Cu

tube armored with
C/C monoblocks.
C/C
C/C (Kawasaki Heavy
Industries, Japan)
 Ceramic Structural Composites
The Most Advanced Structural Material

Irradiation Performance of Carbon Fiber Composites

- Lifetime is limited
- Tritium Retention Unavoidable
Graphite Under Irradiation

H451 Graphite

0.4

Normalized Thermal Conductivity

0.35

0.3
1150 C

Kirr / Kunirr
0.25
600 C
0.2
450 C 920 C
0.15

0.1
300 C
250 C
0.05 200 C
150 C
0
0.1 1 22 2
10
Dose, 10 n/cm
 1
1-D Fiber Composite (UFC)
CFCs Under Irradiation 0

Dimensional Change (%)

(HFIR , 600C)
-1

-2

Fiber Axis
-3 Fiber Axis

axis parallel to
-4 fiber axes

0 1 2 3 4 5
Dose (dpa)
0
3D Balanced Weave

Dimensional Change (%)

-0.5
-1 Pitch Fibers
-1.5
-2
-2.5 PAN Fibers
-3
-3.5 axis parallel to
a set of fiber axes

-4
0 1 2 3 4 5
Dose (dpa)
 CFCs Under Irradiation
fiber
Composite allows engineering of
properties such as dimensional change

gap
500C ~ 10 dpa 800C
sample
surface
bundle
swelling

bundle
shrinkage
 gap

bundle
swelling

bundle
 CFCs Under Irradiation : Tritium Retention
T-3 attaches to basal plane edges and highly defected structure. More perfect
material and/or high temperature allows less retention.

Intermediate Quality Irradiated Graphite

(Causey, Snead)
1000
T-3 Retention (appm)

High Quality Irradiated CFC

100 (Causey, Snead)

Non-irradiated, infinite charge time

10
Non-Irradiated
1 hr Charge Time

1
200 400 600 800 1000 1200 1400
Irradiation / T-3 Loading Temperature (C)

NRL IFE 2/2001

 Ceramic Structural Composites
The Most Advanced Structural Material

SiC/SiC Composites

- Essentially no current structural application

- Manufacturing and design methods immature
 ARIES-I First Blanket Design Using SiC/SiC

Excellent safety & environmental

characteristics (very low activation
and very low afterheat).
High performance due to high
strength at high temperatures
(>1000C).
ARIES-AT Liquid Wall Blanket Concept (USA)

Simple, low pressure design with SiC structure and self-cooled Pb-17Li breeder.
High Pb-17Li outlet temperature (~1100C) and high thermal efficiency of 58.5%.
- Max SiC/SiC temp.: 996C.
- Max SiC/SiC-coolant (Pb-17Li) interface temp.: 900-940C.
Simple manufacturing technique.
Very low afterheat.
Class C waste by a wide margin.
 TAURO SiC/SiC Blanket Design in EU

Self-cooled Pb-17Li
breeder and n multiplier.
Pb-17Li inlet/outlet
temperature (650/860C).
- Max SiC/SiC temp.:
995C.
- Max SiC/SiC-coolant
(Pb-17Li) interface
temp.: 915C.
Simple manufacturing
technique (based on
joining of panels/tubes
by brazing).
The maximum shear in
the joints is 60MPa.
6mm thickness as first
wall to deal with thermo-
mechanical loads.
Brayton cycle thermal
efficiency: >47%.
 Ceramic Structural Composites
The Most Advanced Structural Material

SiC/SiC Composites Under Irradiation

- May survive for life of machine

- Thermal conductivity is likely less than assumed
- Electrical conductivity appears not to be a problem
 SiC
Under Irradiation

Irradiation-induced
thermo-physical
QuickTime and a
property changes Photo decompressor
are needed to see this picture.
(swelling, thermal
conductivity, strength)
saturate by a few dpa
for T< 1000C. Driven
by simple defect
clusters.

Irradiation
performance for
T>1000C is not well
understood.
Silicon Carbide Under Irradiation
amorphization point-defect swelling void swelling regime

10
Irradiation-induced
thermo-physical
property changes
(swelling, thermal
conductivity, strength) Linear Swelling (%) 1
saturate by a few dpa for
T< 1000C. Driven by
simple defect clusters.

Irradiation
performance for 0.1
T>1000C is not well
understood.

0.01
0 200 400 600 800 1000 1200 1400 1600
Irradiation Temperature (C)
 SiC/SiC Composites : Strength and Stability
Until recently, SiC/SiC composites exhibited significant degradation in
mechanical properties due to non-SiC impurities in fibers causing interfacial debonding.
Bulk SiC FCVI SiC Matrix, C-interphase, Plain Weave Composite
~ 1 dpa, HFIR irradiation
1.4 Unirradiated
Fiber type Stress (MPA), S
ave

Regular Nicalon 292 (3 tests)

1.2 Hi-Nicalon 359 (7 tests) Type-S Nicalon

) ave
Type-S Nicalon 416 (2 tests)
SiC-interlayer Composite

/S
Thin C-interlayer

irr
1
SiC-interlayer

Normalized Stress (S
0.8
High Nicalon
Ceramic fiber 0.5 m Composite
0.6

SiC multilayers 0.4

Ceramic Grade
10 mm Nicalon Composite
0.2
2.3 x 6 x 30 mm
20 mm ORNL / Kyoto U.
0
SiC fiber 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Cross Head Displacement (mm)

300 nm Upon irradiation, if fibers

densify, fiber/matrix
interfaces debonds
-->strength degrades
SiC/SiC Composites : Strength and Stability

Bend strength of irradiated

advanced composites show
no degradation up to 10 dpa

1st- and 2nd generation

irradiated SiC/SiC
composites show
large strength loss after
doses >1 dpa
SiC/SiC Composites : Thermal Conductivity

Thermal Conductivity (W/m-K)

400
350 CVD SiC
300
250
200
150
100
CVD SiC Irradiated
50
0
0 200 400 600 800
Temperature (C)
 SiC/SiC Composites : Thermal Conductivity

Specific Heat

Grain Umklapp
Boundary
1 1 1 1
K (T )
1

K u (T ) K gb(T ) K d 0 K rd
Irradiation Defects

Grain Boundaries radiation

defects

intrinsic
defects

0 200 400 600 800 1000 boundaries

Temperature (C) umklapp
 SiC/SiC Composites : Thermal Conductivity
1000
Rohm Haas CVD SiC

Room Temperature Thermal Conductivity (W/m-K)

200C Irradiation
Temperature
800C
Data for an ideal SiC 100

600C 10

Swelling (%)
Thermal conductivity
reduction is due to simple 400C 500C
10
vacancies and vacancy 300C
clusters. This is a strict
material property which 300C 500C
1
can not be improved upon.
400C

600C

200C
800C
0.1
0.001 0.01 0.1 1 10
Neutron Damage (dpa)
 SiC/SiC Composites : Thermal Conductivity

Room Temperature Thermal Conductivity (W/m-K)

200 0.14

Thermal Defect Resistance, (1/K ) (m-K/W)

0.12

150
0.1

1 1 1 1
200C
1
K (T) K (T) K (T) K K 100
300C 0.08
400C
u gb d0 rd 500C 0.06
600C
Umklapp 700C
(phonon boundaries
800C 0.04

rd
Scattering) intrinsic 50
defects
radiation 0.02
defects

0 0
0 0.5 1 1.5 2 2.5
Irradiation-Induced Swelling (%)
 SiC/SiC Composites : Thermal Conductivity
0.30 35

Maximum K
Defect Resistance
Pres ent (340 W/m-K)
30

Thermal Defect Resistance (m-K/W)

Youngblood (185 W/m-K)
0.25 Senor (170 W/m-K)
Price (72 W/m-K) K 25
Price (50 W/m-K) th
0.20 20
x=goal 15

th
0.15

1 1 1 1
10

(W/m-K)
1
K (T) K (T) K (T) K K 0.10 5
u gb d0 rd
0
0.05
Umklapp
(phonon boundaries

Density Change(%)
Scattering) intrinsic 0.00 1.5
defects
radiation 1.0
defects
Density
Pres ent (3.21 g/cc) 0.5
Price (3.20 g/cc)
0

200 400 600 800 1000 1200

Irradiation Temperature (C)
 SiC/SiC Composites : Thermal Conductivity

Thermal Conductivity @ 20C (W/m-K)

100
Rohm Haaas CVD SiC
ORNL Data
Tirr 800
Due to interfaces and
cracks in SiC composite,
thermal conductiivity will
necessarily be less than
ideal SiC. Tirr 500

10 Tirr 300
Present materials are
significanlty lower than
~15 W/m-K reactor study
CVI SiC/Type-S (thru thickness)
goal.
Tirr 800
Tirr 500
Tirr 300
1
0 1 2 3 4 5
Dose dpa
 Composite Comparison for FISSION (at 1000C)

Irradiation-Indu ced Property Ch ange @ 1000C

Material Cost Life Volume Strength Modulus Thermal
$/Kg (dpa) (MPa) Conductivity
W/m-K
Superalloy 25 ~5 - - - -
CFC* ~200 10-15 -5% 150250 +20% 250180
SiC/SiC* ~400 >50? +1% 7575 -10% 5010

* does not include prototyping or NDE evaluation.

 Ceramic Structural Composites
The Most Advanced Structural Material

SiC Matrix / Graphite Fiber Composites

- Now being used in NASA application

- Manufacturing and design methods immature
- May solve the dual problems of low thermal
conductivity of SiC/SiC and high T-3 retention of C/C
Argument #1: Strength (& toughness) as good or superior to SiC/SiC

Tensile
Strength
(MPa)

SiC/SiC Composite (2-D lay-up) SiC/graphite Composite (2-D lay-up)

 Argument #2: Reduced tritium retention over best C/Cs

10 4 Tirr=600C
Tload=1000C

Tritium retention, non-

Hydrogen Solubility (appm)

irradiated and
1000 irradiated, is highly
dependent on graphite
perfection.

K-1100 type fibers are

100
nearly perfect.

Unirradiated SiC has very low

Neutron Irradiated tritium retention.
10
0 20 40 60 80 100
Graphitic Perfection (%)
 Argument #2: Reduced tritium retention over best CFCs

10 4
N3M graphite
FMI-222 CFC Intermediate Quality
MKC-1PH CFC
Graphite
1000
By replacing the
Tritium Retention (appm)

lower perfection
matrix of CFCs with
100 SiC, SiC/graphite will
have lower retention.
High Quality
Graphite Fiber Composite
10
Tirr=200C
Tload=1000C

1
0.001 0.01 0.1 1 10
Radiation Damage (dpa)
Argument #3: Significant thermal conductivity enhancement

1 Defect
1 1 1
K (T)
1

Resistance
Ku (T) Kgb (T ) Kd 0 Krd
1 1/Krd Comp S iC-g
Thermal Defect Restistance (m-K/W)

CVD SiC
Irradiated at 60 and 30 0C
0.1

0.01

Graphite Composite
Irradiated at 60 C Graphite Composite
Irradiated at 30 0C
0.001
0.001 0.01 0.1 1 10
dpa
 Engineered High Thermal Conductivity SiC/G Composite
Matrix : CVI SiC , no interphase
Fibers : Z-direction either Amoco P55
or Thornel K-1100 fiber
X-Y direction Amoco P-55 fiber.
Total Volume Fraction 44%.
Architecture: Unbalanced 1-1-6 weave.

High TC

K1100 fiber
SiC Matrix / Graphite Fiber Composites
At fusion-relevant temp., SiC/g:
--> conductivity exceeds present SiC/SiC
--> conductivity exceeds SiC theoretical max.
--> Low TC direction on order of SiC/SiC thermal conductivity (for this composite).

400 IC FRM10 SiC /G

350
Thermal Conductivity (W/m-K)

Morton CVD SiC

300

250
200 K1100 Graphite/
CVI SiC (high TC)

150
100
P55 Graphite/CVI SiC (high TC)
50
Type-S Compos ite (trans verse)
0
0 200 400 600 800
Temperature (C)
 SiC Matrix / Graphite Fiber Composites

At fusion-relevant temperature, SiC/g exceeds theoretical maximum of SiC/SiC

400
Thermal Conductivity (W/m-K)

350 CVD SiC

Non-Irradiated
300

250

200
CVD SiC/K1100
150 Non-Irradiated

CVD SiC/K1100
100 Irradiated

50
CVD SiC Irradiated
0
0 200 400 600 800 1000 1200
Temperature (C)
 Summary

Fiber reinforced composites are arguably the oldest man-made structural

material. However, because predictive design tool (codes) have been based
on metallic design over the past century structural design with composites is
currently impractical. Design is based on prototyping, not modeling.

Carbon fiber composite manufacturing and application is fairly mature,

however lifetime of composite structures is strictly defined to ~ 15 dpa, or a
year in a fusion reactor. Tritium retention in CFCs can be reduced, but never
eliminated.

SiC/SiC composite offer the possibility of lifetime components, but as-

irradiated thermal conductivity will almost certainly be less than the 15 W/m-K
assumed in present studies.
 Questions ???

Questions ?
 Fabrication of C/C Composites
Carbon Fiber:
PAN (polyacrylonitrile) based carbon fiber
- Commercial use for general purpose.
- Varieties: high strength, high modulus, long elongation,
Pitch based carbon fiber
- High performance carbon fiber: Anisotropic, high graphitization.
Tensile strength: 2.3~4.0GPa, Tensile modulus: 400~900GPa
- General purpose (low cost) carbon fiber: Isotropic microstructure.
Tensile strength: 0.6~1.0GPa, Tensile modulus: 30~60GPa
Carbon Matrix:
carbon
Chemical vapor deposition (CVD)
Impregnation and pyrolysis Temperature
using resin or pitch.
Environmental Barrier Coating: graphite
Concern about high reactivity to
oxidative products.
Boron based glasses (<1000C)
Silicon carbide (<1500C)
Graphitization
Key Characteristics of SiC(-based) Fibers
C/Si Oxygen Tensile Tensile
Elongation Density Diameter
SiC Fiber Atomic Content Strength Modulus
(%) (g/cm3) (m)
Ratio (wt%) (GPa) (GPa)

Tyranno SA Gr.3 1.07 <0.5 2.6 400 0.6 3 7

Hi-Nicalon Type-S 1.05 0.2 2.6 420 0.6 3.1 11

Hi-Nicalon 1.39 0.5 2.8 270 1.0 2.74 14