Development of Ultra High Temperature Ceramics for Aerospace Applications

Dr. V Jayaram SSCU Department Indian Institute of Science Bangalore - 560012

Outline
Fundamental Aeronautics Program UHTC background Current experimental approaches
Morphology and composition Grain boundary phases

Summaries and conclusion

Fundamental Aeronautics Program

Long-term, multidisciplinary investment in critical research of core areas in aeronautics technology Evaluate new concepts and technology Accelerate new technology applications Not tied to specific vehicle/mission, but to tool development Hypersonics element covers all hypersonic regimes Planetary missions (crewed and probes) LEO (including commercial access to space) Ames materials effort addresses wide range of vehicle types

MER

Orion

SHARP

Shuttle

Materials Development Approaches

Comprehensive readiness versus specific application Families of materials trade space for rapid tailoring to mission needs:
Consistently desired properties:
Strength Thermal conductivity

Properties defined by mission

Goal for all TPS materials is efficient and reliable performance during entry

Sharp Leading Edge Technology

For enhanced aerodynamic performance
Improvements in safety
Increased vehicle cross range Expanded launch window with safe abort to ground

Applicable to out-of-Earth-orbit missions

Aerogravity assist missions (solar exploration at Venus) Accurate placement of probes where rapid deployment is necessary

Require materials with significantly higher temperature capabilities

Current shuttle RCC leading edge materials: T~1650C Materials for vehicles with sharp leading edges: T>2000C

UHTC compositions are candidate materials

Sharp Leading Edge Energy Balance

Sharp Nose

UHTC

High Thermal Conductivity

qconv qrad qcond

Insulators and UHTCs manage energy in different ways:

Insulators store energy until it can be eliminated in the same way it entered UHTCs conduct energy through the material and re-radiate it through cooler surfaces

UHTCs for Sharp Leading Edges

Properties required High thermal conductivity (directional) Fracture toughness/mechanical strength/hardness Oxidation resistance

Current approach Combining our experimental process with computational methods to achieve desired property improvements Exploring the design space (processing/ properties)

Previous Work on UHTCs

Optimization tied to particular vehicle development Required early selection of baseline material hot pressed HfB2/ 20v%SiC Focused on improving homogeneity and characterization of properties SiC Required for processing dense material Promotes refinement of microstructure Decreases thermal conductivity of HfB2 >20v% may not be optimal for oxidation behavior

Current Experimental Approaches

Approach 1: Morphology and composition High-aspect-ratio grains Growing SiC acicular grains Processing approaches Hot-pressing Spark Plasma Sintering (SPS) Approach 2: Grain boundary phases Third-phase additions Powder-coating Processing approaches Hot-pressing Spark Plasma Sintering (SPS)

Morphology and Composition

Acicular grains for mechanical improvements

Conventional source for SiC is powder

Preceramic polymer route Preceramic polymer will affect densification and morphology May achieve better distribution of SiC source through HfB2 Previously added Si3N4 preceramic polymer to Si3N4 powder to promote formation of acicular Si3N4 grains*

Effects of SiC Precursor Amounts on Final Microstructure

Samples processed with 5 to >20 volume % SiC Can adjust volume of SiC in the UHTC without losing the high l/d architecture Amount of SiC affects number and thickness (but not length) of rods length constant (~2030m)

Microstructures at Higher SiC Loadings

Coalesced high aspect ratio SiC High aspect ratio SiC phase

3D interconnected network of SiC observed at > 20% SiC volume fractions Evidence of HfB2 grains trapped in SiC high-aspect ratio grain Majority of SiC coalesced and formed larger grains some finer acicular SiC grains still evident High aspect ratio architecture of the SiC phase is preserved

Effect of Heating Schedule on Formation of Acicular Grains

Heating schedule 1 results in limited high aspect ratio phase

Heating schedule 2 yields larger volume fraction of high aspect ratio phase

Investigating the range of possible microstructures

Comparison of Processing Methods: SPS and Hot Pressing

10% SiC

10% SiC

Materials processed by SPS

Materials processed by hot-pressing

Spark Plasma Sintering (SPS) results in a very refined microstructure no evidence of acicular grains

Large Grain Growth

Poorly processed HfB220v%SiC

100 m

Large HfB2 agglomerate

Large SiC-rich agglomerate

Areas deficient or rich in SiC result in large grains of HfB2 or SiC. This behavior is echoed in the preceramic polymer work.

SiC derived from polymer

5% SiC

>20% SiC

Arc Jet Testing

Provides sustained conditions that simulate aerothermal environment of reentry for understanding thermal performance of materials and systems under controlled heating conditions

SiC Depleted During Arc Jet Testing

SiC Depletion Layer

Post-test arc jet model

Oxide Layer

In baseline material, SiC depleted during arc jet testing amount of SiC near percolation threshold Preceramic polymer route possible way to achieve good mechanical properties and lower amounts of SiC
qCW = 350 W/cm2, Pstag = 0.07 atm

SiC Depletion Layer

ZrB2-SiC System

Nominally 15% SiC high aspect ratio phase in a ZrB2 matrix

Preliminary work on the ZrB2-SiC system indicates possibility of obtaining high aspect ratio SiC phase.

Third-Phase Additions Explore effect of additional refractory phases on oxidation resistance / fracture toughness (ductile-phase toughening)* Investigate additions of refractory metals Focus on
Effect of additives on microstructure Evaluation of thermal conductivity Evaluation of mechanical properties

Third-Phase Additions
Processing and compositions Two different hot pressing schedules SPS an alternative consolidation approach short processing times Two variants of baseline material (HfB2-20 v% SiC): Ir Ir with TaSi2
Sample Consolidation Process SPS

HfB2

HfB2-SiC (baseline material)

SPS & Hot Press

HfB2-SiC-Ir

Hot Press

HfB2-SiC-TaSi2Ir

Hot Press

Effect of Processing Parameters on Microstructure

HfB2/20v%SiC Hot Pressed (Schedule 1) HfB2/20v%SiC Hot Pressed (Schedule 2) HfB2/20v%SiC Spark Plasma Sintered

Schedule 2 results in finer grain structure than Schedule 1.

SPS results in finer grain structure than hot pressing.

Effect of Additives on Microstructure

HfB2-SiC (hot press)

Addition of Ir

Addition of Ir and TaSi2

Samples processed with additional phases show less grain growth

HfB2-SiC-Ir (hot press) HfB2-SiC-TaSi2-Ir (hot press)

Similar microstructure
HfB2-SiC (SPS)

Similar microstructure

Density and Hardness

Sample Process
HPschedule 1

Density (g/cm3)

Density
(% Theoretical)

Vickers Hardness
(GPa)

HfB2-SiC
HfB2-SiC HfB2-SiC HfB2-SiC-Ir

9.6
9.6 9.6 9.9

100
100 100 100

16.5
20.3 17.8 18.3

SPS
HPschedule 2 HPschedule 2

HfB2-SiC-TaSi2-Ir HPschedule 2

9.7

100

18.8

Hardness increases with: Processing route SPS processing and hot pressing schedule 2 are beneficial. Additional phases

Thermal Conductivity
140

Pure HfB2
120

SPS

Conductivity (W/(m*K))

100

SHARP-B2
80

HfB2-SiC
Hot Press Method 2

HfB2-SiC
60

SPS

HfB2-SiC-TaSi -Ir 2
Hot Press - Method 2

40

HfB2-SiC
Hot Press Method 1

HfB2-SiC-Ir
Hot Press Method 2

20

0 0 100 200 300 400

o

500

600

700

Temperature ( C )

Schedule 1 hot pressing lowest thermal conductivity

Schedule 2 hot pressing significant increase in thermal conductivity SPS similar increase in thermal conductivity Addition of Ir or Ir and TaSi2 to HfB2/SiC (modified HP) lowers thermal conductivity

Powder-Coating Approach
Advantages of coatings over particles to introduce additives:
Uniformly distribute and control coating composition Bypass traditional sources of processing contamination Improve oxidation and creep resistance (less O2 contamination) Control thickness (amount of additive) Reduce hot-press temperature, pressure, and time

Use of fluidized bed reactors to deposit controlled, thin, adherent, uniformly dispersed coatings (HfB2, ZrB2, SiC).

Fluidized Bed Reactor Chemical Vapor Deposition Technique (FBR-CVD)

Vent

Quartz Reactor

450 kHz Copper Induction Coil UHTC Fluidized Powder Bed

Quartz Frit
Reactant Gases
Examples: HCL + CH4 or TiCl4 or SiCl4

Fluidizing Gas (Ar)

Summary: Morphology
Forming acicular SiC grains in both HfB2 and ZrB2 by adding preceramic polymer Adjusting volume of SiC in UHTC without losing high aspect ratio grains Processing samples with 5 to >20 volume % SiC from polymer:
Amount affects diameter of acicular grains, but not length At >20% groups of interconnected acicular grains form

Processing method affects formation of acicular grains Modified microstructure does not have significant effect on hardness Mechanical properties in preliminary results:
Comparable fracture toughness in reinforced systems with lower SiC volume fractions Implications for oxidation behavior arc jet testing for verification Indications that acicular SiC phase is improving toughness

Summary: Grain Boundaries

Addition of Ir and of Ir with TaSi2 to baseline material appears to:
Further improve the microstructures of hotpressed materials (SPS more refined and more marked effect on hardness) Reduce thermal conductivity

The FBR-CVD technique:

Can be used to deposit controlled uniformlydispersed phase additions Avoids grain boundary contaminants introduced during mixing and milling operations

Conclusion
Exploring large design space has yielded potential for tailoring material for both:
Comparable or improved mechanical properties Good oxidation behavior in entry conditions

Future directions:
Continue modification of morphology, composition, and grain boundaries to understand influence on properties Modeling/computation for efficiency in experiment Arc jet testing to evaluate performance in relevant environment