AFOSR

HIGH TEMPERATURE
AEROSPACE MATERIALS
17 March 2011
Dr. Ali Sayir
Program Manager
AFOSR/RSA
Air Force Office of Scientific Research
Distribution A: Approved for public release; distribution is unlimited. 88ABW-2011-0790
 2306 PORTFOLIO OVERVIEW
NAME: HIGH TEMPERATURE AEROSPACE MATERIALS
BRIEF DESCRIPTION OF PORTFOLIO:
Scientific leadership to enable revolutionary advances for the high temperature materials:
• Ceramics
• Metals
• Hybrids (including composites)

LIST SUB-AREAS IN PORTFOLIO: TREND

• Mathematics to quantify microstructure.
• Theoretical and/or computational tools that aid in the discovery of new materials
• Nontraditional synthesis of materials and nanostructures by external electric field, lasers, etc.
• Transparent ceramics (interface science).
• Radiation reflection, catalytic response (surface science ) and acoustic Mitigation.

• Experimental and computational tools to address the complexity of combined external fields.
• Multi-modal diagnostics that validates the fidelity of simulations.
• In-situ characterization methods for at extreme environment.
• 3-D Structure Description – Tomography

• Conventional Materials Processing

• Bulk Metallic Glasses
• High Temperature Actuators
• Wear Resistant Materials 2
• Geopolymers
 Scientific Challenges
Create new foundations for new technology and solve formerly unsolveable Challenges

- Understand physical, chemical and structural challenges:

• Design and understand hierarchical structure
• Discovering new materials that exploits C-rich amorphous oxides
- Predict responses of materials under thermomechanical extremes:
• Understanding of materials under static, quasistatic, and dynamic thermomechanical extremes
• Property gradient measurements
• Electronic information of atomic species
• Fully exploit 3-D structure information
• Simulated damage evaluation and validation
- Deformation characteristic of bulk metallic glasses:
• Spatial electron density
- High temperature or high pressure phase transformation:
• Study materials in situ as the defects originate and evolve; T> 1900 C.
• Extending understanding of plastic deformation from mano to macroscale
- Eye-Safe Polycrystalline Lasers: Sesquioxides - Sc2O3
• Solving supersaturation problem and design interface structure to achieve superior lasing

Mathematics of microstructure :
• Quantification of heterogeneous structures
• Identifying sample distributions of shape descriptors
3
 Transformational Opportunities

PI – Dr. J. Ballato / Clemson University:

High Energy Laser Multi-disciplinary Research Initiative (JTO HEL MRI / AFOR).
Transitioning to ARMY.

PI – Dr. M. Pascucci / CeraNova Corp – STTR:

Aerodynamic Hypersonic Dome: Transparent, polycrystalline alumina
Transitioning to Eglin AFB.

PI – Dr. W. Kriven / UIUC:

Geopolymer has 3-D structure analogous to zeolite but 1500 C capability.
Transitioned to Tyndall AFB – 6.2 Funding

PI – M. Uchic / AFRL – RXLM – LRIR:

Microtesting: Meso-scale‘ size effects and spatial property mapping.
Transitioned to Academia

PI – Dr. Alp Sehirlioglu / CWRU:

High Temperature Piezoelectric Ceramics.
Transitioned to NASA – High temperature Actuator for Fuel Modulation.

4
 Materials and Structures for Propulsion
Flowpath
Cowl Leading Edge
Sustained hypersonic flight at high Mach No.
Blunt LE, - High heat flux & heat loads
- High T, oxidation, shear, erosive conditions
- Active cooling -> very high thermal gradients
- Conditions vary with location
Free-Stream Mach 8
~2000
CSharp leading edges
-Very high heat flux, small area
-Active cooling/heat pipes possible,
not preferred
UHTCs
- very high T, high conductivity
- very poor oxidation resistance

Flowpath surfaces
Large area: weight critical
Active cooling in some regions
CMCs:
x3 weight reduction c.f. metals
Reduced heat flux absorbed
5
 National Hypersonic Science Center for
Materials and Structures
AFOSR: A. Sayir Teledyne Scientific
NASA: A. Calomino D. Marshall (materials & structures)
B. Cox (mechanics of materials)

Missouri University UC Santa Barbara

new materials &
W. Fahrenholtz processing routes
F. Zok (structural materials)
G. Hilmas, (UHTCs) new experimental methods R. McMeeking (mechanics)
M. Begley (mechanics)
U. Virginia multi-scale models
B. Opila Combine experiments
U. of Colorado and multi-scale models UC Berkeley/ALS
R. Raj into a virtual test system R. Ritchie (mechanics, imaging)
(high temp. materials & properties)

U. of Texas U. of Miami Educational outreach

P. Kroll Q. Yang summer schools
(atomistics) (mechanics) co-location of students
web-based outreach
Collaborations, test and advisory
support (iMechanica)
AFRL/WPAFB (M. Cinibulk) web-based tools (nanoHUB) 6
NASA, Boeing, ATK, Lockheed-Martin
 Multiscale Nature of High-T CMCs
D. Marshall / Teledyne Scientific

interfacial degradation

stress-corrosion cracking

gas diffusion
e.g., brick
& mortar
gas flow O-barrier
through nano- material
micro crack loss
7
 Geometric Model  FEM Converter
R. Ritchie/ UC Berkeley Q. Yang / University of Miami

x-ray CT image & discrete data (UC-B) Constituent

microstructural features
of two woven fiber textile
composites investigated
in 3-D through the use of Validation
x-ray micro-tomography
(micro-CT) . (UC-SB)
Loci colored lines segmenting tomography
indicate the yaw of the data permits structural
tows along the weave information to be derived
in a 3-D heterogeneous
material.

Geometric model with explicit boundaries Meshing & A-FEM Analyzsis (UM)
after statistic analysis + discrete data or
analytical expressions (UCSB/TSC)
G1 CAE create solid G1
G2 with assigned
material types & G2
G3 properties (UM/TSC)
G3
G4 G4
G5 G5
G6 8
G6
 Simulated Damage Evolution
Q. Yang / University of Miami

Validation :
 Appreciable nonlinearity in s-
e at ~ 0.2% due to matrix
cracking
 Cracks tend to initiate near
locations of warp-weft tow
interlacing
 Matrix cracks facilitate
debonding
 Delaminatin crack wake
friction critical
 Failure s and e too low – lack
120 of 3D tow reinforcement in 2D
weft
UCSB test
models
Nominal stress (MPa)

100

80
F. Zok / UC Santa Barbra
warp

60

40 G2
G1 G5
20 A-FEM with
matrix cracking
0
0 0.002 0.004 0.006 0.008 0.01 9
Nominal strain
 Oxidation Mitigation
R. Speyer / Georgia Inst. Tech.

ZrB2-29.74 m % SiC after oxidation Developed UHT Coating that protects

SiC for 1h at 1600oC in air

SiC/PDC/HfO2 after
Top
surface
1h at 1600oC
HfO2 coating

SiC/PDC/HfO2
(as coated) R. Raj / Uni. Colorado
10
 18O diffusion studies confirm diffusion-barrier properties of C-
rich amorphous films. An abrupt amorphous-microcrystalline
Chemical Bonding
by XPS transition on removal of carbon D. Pejakovic/ SRI

Hf 4f Raman spectra  films contain nano-graphitic carbon

Annealed
D G
HfO2 D
G
D
G

Annealed

Intensity

Intensity
Intensity
Intensity

Si Annealed

Annealed
As-deposited As-deposited
HfO2

As-deposited
As-deposited

HfCxOy HfC 800 1000 1200 1400 1600 1800 2000

800 1000 1200 1400 1600 1800 2000 800 1000 1200 1400 1600 1800 2000
1
1 Raman Shift, cm
1 Raman Shift, cm
Raman Shift, cm
22 20 18 16 14

Binding Energy, eV 16
O Si

O, O, Si relative concentration, at%

100 100
O 1s

Hf, C signal intensity, a.u.

HfO2 Annealed

Hf C
10 10
Intensity

18
O
1 1
As-deposited
16

Organic
18
Natural O abundance (0.2%)
18

0.1 0.111
0 100 200 300 400
536 534 532 530 528 526
Binding Energy, eV Depth, a.u.
 Surface Temperature Histories
J. Marschall / SRI

The von Karman ZrB2-30vol%SiC-4mol%WC

Institute 1.2 MW 2600
Plasmatron 2800 3.3 Spontaneous
3.5 Temperature 2400
2600 Jump

SURFACE TEMPERATURE, °C
3.9
SURFACE TEMPERATURE, K
3.4 ~470 K 2200
2400 3.2
2000
2200 Plasmatron Power Increase
2
qcw= 40-80 W/cm
1800
2000
1600
1800
2
qcw=75-85 W/cm 1400
1600
1200
1400 Mass flow: 16 g/s
Pchamber: 10 kPa
1000
1200
0 60 120 180 240 300 360 420 480 540 600 660
Induct. heat: 1.2 MW (max)
Enthalpy: 10 – 50 MJ kg-1 (for air) TEST TIME, s
Ma range: < 0.3
qstag: 10 – 300 W cm-2
Pstag : 0.05 – 0.15 atm 12
 Atomic Emission Lines During Temperature Jump
J. Marschall / SRI
ZrB2-30vol%SiC-4mol%WC: Sample 3.3
2700
16000 Boundary Layer Emission (424 s) ZrB2-30vol%SiC-4mol%WC 2400
Air Plasma Background Emission 2650
Sample 3.3 2350
EMISSION INTENSITY, arb.

14000
B

SURFACE TEMPERATURE, °C
SURFACE TEMPERATURE, K
2600
2300
12000 Si 2550
2250
10000 2500
2200
8000 2450
2150
2400
6000 2100
2350
4000 W 2050
2300
2000 2000
2250
1950
0 2200
200 250 300 350 400 450 500 403 409 415 421 427 433 439
WAVELENGTH, nm Transient Atomic TEST TIME, s
ZrB2-30vol%SiC-4mol%WC: Sample 3.3
Emission Signatures 2800 15000
Spontaneous
2600 Temperature Plasmatron

SURFACE TEMPERATURE, K
Jump Off 12000

EMISSION INTENSITY, arb.

2400 Plasmatron
Power
2200 Increase
9000
2000

1800
6000
B 249.92 nm
1600
Si 288.16 nm
W 400.99 nm
1400 3000
1200

1000 0
350 400 450 500
13
TEST TIME, s
 Laser Diagnostics: Property Gradients
D. Fletscher / Uni. Vermont
•Collection optics are f/4 - f/6 and
aperture is ~ 1mm for 30 kW ICP
•Pulse energy ≤ 0.25 mJ with a 0.5
mm beam diameter to avoid
complications such as multi-photon
ionization
Translate collection optics and beam to
measure T and species distributions
T(x)
• Measurement with 207 nm ni(x)
transition (f/15 optics) normalized for
pulse energy
• Temperature determined from line
widths with Treact known
x
• Absolute number density from
Flow
spectrally integrated signals, with
additional measurements: Raman Sample
calibration, temporal profile, spatial
profile, lifetime
• From measured T and p: n = p/kT
• For nitrogen plasma and measured nN: nN2 = n - nN
14
 In-Situ Synchrotron Studies up to 2000 C
W. Kriven / UIUC

Phase Transformation of Hafnia

HTXRD Experimental Setup

An efficient, all-encompassing methodology, to investigate high temperature

properties and behavior of materials based on fundamental crystallographic 15

measurements performed in-situ at high temperatures.

 Plasticity in High Temperature Materials:
Tantalum and Monazite
J. W. Kysar / Uni. Columbia

Lower bound on GND density of Dislocation Tilt Walls with

Status Quo
one effective in-plane slip system Characteristic Spacing
• Traditional mechanical characterization
measures response of a material system
– e.g. tensile test or nanoindentation
• Physics-based predictive models require
information about the internal state of the
material
Objective
• Spatially resolved measurement of state of
material at the mesoscale
– Between 50 nm and 500 mm
• Physics-based variables
– Lattice rotation
– Nye tensor components
– Geometrically Necessary Dislocation Distribution of Characteristic GND Density Distribution
(GND) Density Length Scale along Slip Direction
Outcome of Experiments
• Measure the ―length scale‖ of plastic
deformation
• Distribution of characteristic spacing of
dislocation structures (tilt walls)
Significance
• These experiments provide an
unprecendented multiscale experimental
perspective on plastic deformation

16
 BMGs as Structural Materials

Amorphous metals, and new hybrid materials exhibit superior behavior at high pressures,
temperatures, and strain rates offering the promise of revolutionary capabilities.

Fracture Toughness, KIC (MPam)

104 103
ceramicsBMGs
fiber- (compression) steels
reinforced
103 polymers 102 fiber-
Strength, sf (MPa)

Specific Ti
strength reinforced
Ti polymers
= constant steels Al
102 10
polymers Al polymers
metals metals

10 1
ceramics BMGs
Mg-BMG
Zr-BMG Mg-BMG
1 0.1
Zr-BMG
Fe-BMG
Ti-BMG Fe-BMG
0.1 10-2
0.1 0.3 1 3 10 30 0.1 0.3 1 3 10 30
Density, r (Mg/m3) Density, r (Mg/m3)
• Pros: Properties: High strength (tension and compression); Large elastic range
Processing: Net shape casting; Excellent formability above Tg
• Cons: Fracture toughness ranges from reasonably tough to very brittle; 17

Limited tensile ductility below T

 Ductile, Fracture Resistant Bulk Metallic Glass –
Crystalline Composites
K. Flores / Ohio State University & W. L. Johnson / CALTECH

New Glass Stronger
and Tougher Than Steel
(Jan. 11, 2011) —
Metallic Glass Yields
Secrets Under Pressure
(Mar. 17, 2010) —
Metallic Glass For
Bone Surgery
(Sep. 29, 2009) —
Nanoscale Structures With
Superior Mechanical
PropertiesDeveloped
(Feb. 13, 2010) — • A cantilever beam is
A Plane With Wings Of
Glass?
(June 24, 2008) — • SEM images of
Fast-Tracking the
Manufacture of Glasses
(June 29, 2010) —
Nanostructured Material
Offers Environmentally Safe •
Armor-Piercing Capability,
May Replace Depleted
Uranium
(Feb. 1, 2007) —
Chemists Look Through
Glass To Find Secrets That
Are Less Clear
(June 6, 2006) —
Status Quo: Metallic glasses exhibit negligible tensile ductility due to highly localized
deformation in shear bands.
New Insight: Ductile crystalline dendrites formed in situ via thermal treatments can increase
ductility to > 10%.
Project Goal: * Understand structure and resulting properties through combination of
experiment and modeling
* Optimize performance of glass/crystalline composites
Highlight:
3D Microstructural
Characterization
FIB milled and
serial sectioned.
each slice face are
stacked and post-
processed to
produce detailed 3D
reconstructions.
Results show, for
the first time, that
the glassy phase is
completely
continuous, even at
crystalline dendrite
volume fractions
exceeding 70%!
18
 Deformation and free volume: What is the flow defect?
K. Flores / Ohio State University

tsoften
Spaepen, 1977
t tss Steif et al, 1982

Free volume
Falk and Langer, Phys. Rev. E 57, 7192 (1998).

―Free volume‖ is defined as the volume in excess of the ideal

glass structure. Steady state increase in free volume
• Defined over the entire structure, not locally. associated with softening, flow.
v0
Zr atom g
• Definition of ―free volume‖ is volume in
Cu atom excess of the ideal glass structure.
• How is the ideal defined?
• Typically perform voronoi tesselation, define
Unoccupied volume
―free‖ volume as voronoi cell less volume of
neglected by the
hard sphere atom core.
hard sphere model
• What is atomic radius?
Unoccupied volume • Neither of these approaches address
19
captured by the hard connectivity of ―free volume‖
sphere model
 LEDs as flow defects
K. Flores / Ohio State University

Kathy Flores
Identify Low Electron Density regions
Ohio State University(LEDs) in the glass structure

Crystal (0 K) Cores
Glass (0 K) (capped)

2nd, 3rd nearest

neighbors

1st nearest
neighbors

LEDs:
• regions with electron density < minimum in crystal 20

• ~2% glass volume at 0 K

 Enable New Research Opportunities for Microtesting
‗Meso-scale’ size effects, spatial property mapping, high-throughput testing
M. Uchic / AFRL

Explore Deformation More comprehensive

Measurement of size and
Mechanisms data for model input
microstructure dependent
properties and validation

Current Limitations:
-Expensive, slow, and serial sample fabrication method
21
-Limited High Temperature Capability
 Eye-Safe Polycrystalline Lasers: Sc2O3
J. Ballato / Clamson University

Critically need on-shore academic and industrial R&D

capabilities for highly transparent polycrystalline laser
hosts operating at eye-safe wavelengths for a series of
directed energy applications.

T1 = 1550°C T1 = 1500°C T1 = 1450°C

T2 = 1400°C T2 = 1350°C T2 = 1300°C

A B C

Two-Step Sintering of Sc2O3: Effect

of T1 on transparency

A B C  T1 has strongly influence on

the microstructures and the
transparency of transparent
Grain size 0.53m Grain size 0.42m Grain size 0.33m
22
ceramics.
 TWO STTR SUCCESSES
M. Pascucci / Cera Nova Corp X. Wu / Scientific Forming Corp.

Aerodynamic Hypersonic Domes Machining:

Microstructure-based
property modeling
90 (strength, creep):
80 Low g’ volume
70 fraction
% Transmission

60
50
High g’
40 volume
30 fraction
20 44-042M
10 44-050E
90
0 Location-specific
0 500 1000 1500 2000 80 2500
Location-specific grain Location-specific
microstructure variables
Wavelength (nm) 70 size, precipitate microstructure produces
are carried over from
60 distributions resulting location-specific material
process to process and
% Transmission

50 from processing properties

evolve during each step
40

30
Microstructure-based location specific properties (strength, creep)
20
44-042M influence overall part performance during simulated spin pit tests:
10
44-050E
0
2500 3500 4500 5500 6500
Wavelength (nm )

Little distortion
Low speed test
High speed test
Improved Centrifugal Force Calculations
Improve Spin Pit Test Predictions:
100

Max. Principal Stress (ksi)

With tangential force
80
Without
60 Tangential tangentia
acceleration l force
40 (X100)
20
23
0
0 0.1 0.2 0.3
Time (sec)
 SUMMARY AND PERSPECTIVE

• Fundamental and integrated science for the discovery of materials for AF aerospace concepts.

• Breakthrough research of materials response to combined loads.

• surface phenomena from the atomic scale up through the macro scale;
• physical and chemical processes by which such materials can be modified,
• predict response through multi-scale modeling efforts,
• multi-modal diagnostics that validates the fidelity of simulations.

• Quantification of microstructure that can revolutionize the design and performance.

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