Ultrahigh Temperature Composites for Thermal Protection Systems (TPS)

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Roadmap - Theme 2 Ops Safety, Payloads and Safety (November 3, 2014, Hosted by FCAAP) Ultrahigh Temperature Composites for Thermal Protection Systems (TPS) Donovan Lui, Fei Liang, Hongjiang Yang, Jay Kapat, Jan Gou Composite Materials and Structures Laboratory Department of Mechanical and Aerospace Engineering University of Central Florida

Team Members Principle Investigators Jan Gou - Composite materials and structures, nanocomposite materials, advanced composites manufacturing: PMCs, CMCs and C/C composites Jay Kapat - Heat transfer, film cooling, aerodynamics testing Graduate Students Hongjiang Yang: nanocomposite materials, design, manufacturing, characterization and testing of composite materials Donovan Lui: Ablation testing and CMC fabrication 2

Task Description Develop anisotropic thermal conductivity, ultrahigh temperature, light weight and cost effective carbon nanotube preform reinforced polymer derived ceramics (PDC) matrix composites for thermal protection systems. STATEMENT OF WORK Develop 3D fiber reinforced polymer derived ceramics (PDC) matrix structural ceramic composites. Develop carbon nanotube preforms (vertically aligned carbon nanotube (VACNT) arrays and buckypapers) for ceramic nanocomposites. Ground testing of CMC based thermal protection systems with Oxyacetylene Exposure Test, Shock Tube Test and Hot Jet Facilities. Multi-scale modeling of CMC based thermal protection systems. 3

Fiber Reinforced Structural Ceramic Composites Fiber Reinforced Polymer Derived Ceramics (PDC) Matrix Structural Ceramic Composites Prepreging Machine Autoclave Prepregging with Resin Impregnator Prepreg woven fiber fabrics (ceramic fiber, carbon fiber, glass fiber, etc.) with polymer derived ceramics (PDC) resin Autoclave Curing PDC resin curing in an autoclave with computer control over all process variables (max pressure 200 psi, max temperature 800ºF) to become a greenware Pyrolysis in Kiln Pyrolyze the greenware into a ceramic part (max temperature 1200 ºC) Kiln 4

High Temperature Ceramic Fibers Trade-Name Manufacturer Use Temperature Cost ($/Kg) Filament Diameter (µm) Density(g/cc) Tensile Strength (MPa) Tensile Modulus (GPa) Thermal Composition Expansion (Ppm/ C) T300 Toray 300~350 C 68 7 1.74 3100 230 C -0.7 Nextel 720 3M 1204 C 660 10~12 3.4 2930 260 Al 2 O 3 /SiO 2 6 SCS-Utra Specialty Material 1371 C ~9000 142 3.08 3900 380 SiC 4.1 SiC-1900X MATECH ~ 1482 C - 10~12 3.14 2500 367 β-sic - Nicalon NL-200 Hi-Nicalon Hi-Nicalon Type S Sylramic Tyranno SA 1-3 Nippon Carbon Nippon Carbon Nippon Carbon COI Ceramics Ube Industries 1100 C ~2000 14 2.55 3000 220 SiC 3.1-3.2 1230 C 8000 14 2.74 2800 270 SiC 3.3-3.5 1450 C 13000 12 3.1 2600 420 SiC 3.5 1420 C 10000 10 3.55 3200 380 SiC 5.4 1700 C 5000 10 3.02 2800 375 SiC - 5

Polymer Derived Ceramics (PDC) Matrix Property Starfire System Polysiloxane(PSO) Starfire System Polycarbosilane (PCS) Ceramic Precursor Denotation SPR-688/SPR-212 SMP-10 Operating temperature 1,100 C 1,800 C Density 1.11 g/cm 3 0.998 g/cm 3 Cure Cycle Catalyst Platinum CAT-776 Dicumyl Peroxide Advantages of PDC Matrix : Low cost Near net shape manufacturing Outstanding thermo-chemical stability Pyrolysis Cycle 6

Polymer to Ceramic Technology 7

Polymer to Ceramic Technology (Cont d) 8

High Temperature Ceramic Fibers (Cont d) BMC s Use of numerous short and randomly oriented fibers to reinforce the ceramic matrix. This method ensures a higher volume of PDC matrix within the composite, prioritizing the ceramic matrix characteristics. Continuous Fiber Use of continuous fiber fabric to reinforce the ceramic matrix. This method retains a higher mechanical tolerance within the composite, prioritizing the fiber characteristics while incorporating PDC properties to better transfer loads. 9

Carbon Nanotube Preform Control the direction of heat transfer pathway by arranging the orientation of carbon nanotubes: through-thickness direction and in-plane direction VACNT Array Buckypaper RELEVANCE TO COMMERCIAL SPACE INDUSTRY Ultra-high temperature, light weight, highly anisotropic thermal properties and cost effective thermal protection systems (TPS) are enabling technologies for viable commercial space transportation vehicles and their high-temperature systems. 10

Vertically Aligned Carbon Nanotube (VACNT) Arrays Grown by Chemical Vapor Deposition (CVD) Highly anisotropic properties Chemical Vapor Deposition (CVD) Mechanism Tube Furnace 11

Carbon Nanotube Paper (Buckypaper) Manufactured by using the pressureassisted infiltration process Release Film Clear Bag Carbon nanotubes are aligned in the plane Vacuum probe Buckypaper + PDC matrix Autoclave 12

Polymer Infiltration Process (PIP) Kiln Near net shape manufacturing Outstanding thermochemical stability Lower pyrolysis temperature, lower energy consuming VACNTs + PDC matrix 13

Anisotropic Conductivity Sample Conductivity Through-thickness σ (S/m) Conductivity In-plane σ (S/m) Buckypaper/PDC ~ 0 0.161 VACNT/PDC 80.1 ~ 0 14

Fracture Toughness Alignment in the nanocomposite VACNTs have a good bonding with PDCs 15

Summary Vertically aligned carbon nanotube (VACNT) forest was successfully grown with good quality. VACNT array/pdc and Buckypaper/PDC ceramic composites were fabricated through curing and pyrolysis procedures. Highly anisotropic conductivity was obtained. Scanning electronic microscopy images indicate that small cracks and pores have been developed after the PDC pyrolysis. The fracture toughness of the ceramic composite is expected to be improved. 16

On-going Work Resin transfer molding (RTM) process with carbon nanotube preforms will be designed to solve the shrinkage problem in PDC curing and pyrolysis cycles. Thermal conductivity in both in-plane and throughthickness directions will be characterized. Ground testing of ceramic composites will be conducted with Oxyacetylene Exposure Test, Shock Tube Test and Hot Jet Facilities 17

Lightning Strike Protection (LSP) of Composite Structures 18