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
