(12) United States Patent Stewart et al. TOUGHENED UNI-PIECE, FIBROUS, REINFORCED, OXIDIZATION-RESISTANT COMPOSITE Inventors: David A. Stewart, Santa Cruz, CA (US); Daniel B. Leiser, San Jose, CA (US) Assignee: United States of America as represented by the Administrator of the National Aeronautics and Space Administration (NASA), Washington, DC (US) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 171 days. Appl. No.: 10/911,747 Filed: Jul. 27, 2004 Related U.S. Application Data Continuation-in-part of application No. 101779,504, filed on Feb. 12, 2004. Int. C1. B05D 7/00 (2006.01) U.S. C1. ....................... 427/299; 4281137; 4281138 Field of Classification Search ................ 4271299; 4281137, 138 See application file for complete search history. References Cited U.S. PATENT DOCUMENTS 4,083,771 A 4/1978 O'Hara 4,093,771 A * 6/1978 Fletcher et al. .......... 42W312.6 4,148,962 A 4/1979 Leiser et al. 4,713,275 A 12/1987 Riccitiello et al. 5,079,082 A * 1/1992 Leiser et al. ............. 42W307.7 (io) Patent No.: (45) Date of Patent: US 7,314,648 B1 Jan. 1,2008 5,985,433 A * 11/1999 Leiser et al. ............. 42W312.6 6,225,248 B1 5/2001 Leiser et al. 6,497,390 B1 * 12/2002 Fischer et al. ........... 244/171.7 OTHER PUBLICATIONS Curry, et al., Material Characteristics of Space Shuttle Rein . . . , Proc of the 24th National Symposium and Exhibition,Book 2, May 8-10, 1979, 1524-1539, San Francisco, CA, USA. Riccitello, et al., A Ceramic Matrix Composite Thermal Protection System for Hypersonic Vehicles, SAMPE Quarterly, May 1, 1993, 10-17,24-4, USA. Stewart, et al., Thermal Response of Integrated Multicomponent Com . . . , Ceramic Engineering and Science Proc, Jul. 1987, 613-625, vol. %No. 7-8, American Ceramic Society, Inc. First Office Action, dated Oct. 20, 2006, from patent application US. Appl. No. 10/779,504, parent to the above identified applica- tion. * cited by examiner Primary Examiner-Kirsten Jolley (74) Attorney, Agent, or Firm-John F. Schipper; Robert M. Padilla (57) ABS TRAC 'I A composite thermal protection structure, for applications such as atmospheric re-entry vehicles, that can withstand temperatures as high as 3600" F. The structure includes an exposed surface cap having a specially formulated coating, an insulator base adjacent to the cap with another specially formulated coating, and one or more pins that extend from the cap through the insulator base to tie the cap and base together, through ceramic bonding and mechanical attach- ment. The cap and insulator base have corresponding depressions and projections that mate and allow for differ- ences in thermal expansion of the cap and base. A thin coating of a reaction cured glass formulation is optionally provided on the structure to allow reduce oxidization and/or to reduce catalytic efficiency. 16 Claims, 9 Drawing Sheets 168 Y \w, U.S. Patent Jan. 1,2008 Sheet 1 of 9 US 7,314,648 B1 246 I 165 U.S. Patent Jan. 1,2008 Sheet 2 of 9 US 7,314,648 B1 TaSi , 6 %O 6 B202 SiO, MoSi2 %oo U.S. Patent Jan. 1,2008 Sheet 3 of 9 1 - 0.9 0.8 5 0.7 0.6 $= 0.5 E W 0.4 0.3 0.2 0.1 0 0 c m .- US 7,314,648 B1 - 220 225 - - - - - - - - ' " I ' ' " I I ' ' I I I ' 1 0.9 0.8 0.7 ci o 0.6 a" 0.5 .- E 0.4 E 0.3 0.2 0.1 0 W I I I 1 1 I 1 I 1 I 1 1 1 I 1 1 1 1 I I 1 I 1 1 1 I I I 1 I 1 1 1 1 1 I 1 1 I I 0 2 4 6 8 10 12 14 16 18 20 Wavelength, h , microns U.S. Patent Jan. 1,2008 Sheet 4 of 9 0 7 - - - - 0 0 0 0 0 0 0 9 8 8 8 0 11 .-.I I . . cu II cv 0 8 0 d 0 0 9 - id 0 0 z 0 8 US 7,314,648 B1 Y .r 7 7 T 7 0 0 0 0 0 0 0 9 0 9 0 8 z U.S. Patent Jan. 1,2008 Sheet 5 of 9 US 7,314,648 B1 0 z 0 8 x 0 2 - k 0 0 z 0 8 7 7 7 T 7 7 0 0 0 0 0 0 0 9 0 9 0 8 8 U.S. Patent Jan. 1,2008 Sheet 6 of 9 US 7,314,648 B1 0 7 7 - 7 - 7 0 0 0 0 0 0 8 8 8 8 0 0 0 0 F 1 Y 7 - 0 0 0 0 0 6 7 7 7 8 8 8 8 0 U.S. Patent Jan. 1,2008 Sheet 7 of 9 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 co co N N N z 2 0 00 (D M N F 7 US 7,314,648 B1 0 z 0 7 U.S. Patent Jan. 1,2008 Sheet 8 of 9 51 0 / US 7,314,648 B1 \ 505 510 507 505 U.S. Patent Temperature, O F Temperature, O F Jan. 1,2008 3500 3000 2500 2000 1500 1000 500 0 Sheet 9 of 9 US 7,314,648 B1 Time, Seconds Time, Seconds