111111 1111111111111111111111111111111111111111111111111111111111111 US007306828B2 c12) United States Patent (10) Patent No.: US 7,306,828 B2 Barrera et al. (45) Date of Patent: Dec. 11, 2007 (54) FABRICATION OF REINFORCED 6,976,532 B2 * 12/2005 Zhan eta!. ................. 165/185 COMPOSITE MATERIAL COMPRISING 2004/0150140 A1 8/2004 Zhan et a!. CARBON NANOTUBES, FULLERENES, AND 2004/0265489 A1 * 12/2004 Dubin ........................ 427/212 VAPOR-GROWN CARBON FIBERS FOR 2005/0181209 A1 * 8/2005 Karandikar ................. 428/408 THERMAL BARRIER MATERIALS, OTHER PUBLICATIONS STRUCTURAL CERAMICS, AND MULTIFUNCTIONAL NANOCOMPOSITE Nakano et al., "Fabrication and Characterization of Three-Dimen­ CERAMICS sional Carbon Fiber Reinforced Silicon Carbide and Silicon Nitride Composites," J. Am. Ceram. Soc., 78(10), 2811-2814 (1995). (75) Inventors: Enrique V. Barrera, Houston, TX Guo et a!., "Carbon fibre-reinforced silicon nitride composite," J. (US); Leonard Lee Yowell, Jr., Mater. 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(58) Field of Classification Search ............... 501/95.2, (Continued) 501/99, 100, 101; 427/427,249.3,249.4, 427/450, 453; 252/62; 977/1 Primary Examiner-Karl Group See application file for complete search history. (74) Attorney, Agent, or Firm-Robert C. Shaddok; Winstead P.C. (56) References Cited U.S. PATENT DOCUMENTS (57) ABSTRACT 5,420,081 A 5/1995 Mattes eta!. The present invention is directed towards a ceramic nano­ 5,965,470 A 10/1999 Bening eta!. composite comprising a nanostructured carbon component 6,027,326 A 212000 Cesarano et a!. 6,255,241 B1 * 7/2001 Miyazawa et a!. ............ 501/99 inside a ceramic host. The ceramic nanocomposite may 6,316,048 B1 * 1112001 Steibel et al ................ 427/180 further comprise vapor grown carbon fibers. Such nano­ 6,420,293 B1 7/2002 Chang eta!. structured carbon materials impart both structural and ther­ 6,492,014 B1 12/2002 Rolison et a!. mal barrier enhancements to the ceramic host. The present 6,495,483 B1 12/2002 Keller eta!. invention is also directed towards a method of making these 6,528,190 B1 * 3/2003 Campbell et al . ........... 428/701 ceramic nanocomposites and for methods of using them in 6,770,583 B2 8/2004 Keller various applications. 6,783,745 B1 8/2004 Voronov et a!. 6,875,374 B1 * 4/2005 Zhan et al . ................. 252/502 12 Claims, 20 Drawing Sheets US 7,306,828 B2 Page 2 OTHER PUBLICATIONS Cesarano et a!., "Processing of Highly Concentrated Aqueous alpha-Alumina Suspensions Stabilized with Polyelectrolytes," J. Rao eta!., "Zirconia nanotubes," Chern. Comm., 1581 (1997). Am. Ceram. Soc., 71 (12), 1062-1067 (1998). R. Taylor, The Chemistry of the Fullerenes, World Scientific Press, He eta!., "Robocasting and Mechanical Testing of Aqueous Silicon River Edge, NJ, 1995. O'Connell et a!., "Reversible water-solubilization of single-walled Nitride Slurries," Proceeding of the Materials Research Society, carbon nanotubes by polymer wrapping," Chern. Phys. Lett., 342, 627-635, (2000). 265-271 (2001). Sun et al., "Colloidal Processing of Carbon Nanotube/Alumina Liu eta!. "Fullerene Pipes," Science, 280, 1253-1256 (1998). Composites," 14 Chern. Mater. (2002), pp. 5169-5172. Bahr eta!., "Covalent chemistry of single-wall carbon nanotubes," J. Mater. Chern., 12, 1952-1958 (2002). * cited by examiner U.S. Patent Dec. 11, 2007 Sheet 1 of 20 US 7,306,828 B2 Heat Zr02 Zr02 Grain Grain FIG. 1 U.S. Patent Dec. 11, 2007 Sheet 2 of 20 US 7,306,828 B2 A B FIG. 2 U.S. Patent Dec. 11, 2007 Sheet 3 of 20 US 7,306,828 B2 z-motion stage nozzle . syrtnge x-y n1otion stage FIG. 3 U.S. Patent Dec. 11, 2007 Sheet 4 of 20 US 7,306,828 B2 Voluuw % Solids FlU 4 U.S. Patent Dec. 11, 2007 Sheet 5 of 20 US 7,306,828 B2 60.0 50.0 40.0 30.0 • Pure PSZ 20.0 • 1wt.%SWNT(AR) • •1wt.%SWNT(MR) '· "2wt.% SWNT(MR) " 10 0 < 1wt.%VGCF · j o2wt.%VGCF ·- 3wt.% VGCF '--'--'-"-'-'----"-"----' 0.0 -~----~------~------------------------~ I IOO"C II OWl' II OO"C 125U"C 14UO"l' I hour 12 hour 12 hour I hour I hour 300"C BB 400°C BB FIG. 5 U.S. Patent Dec. 11, 2007 Sheet 6 of 20 US 7,306,828 B2 Results - Co-deposited Films Hot Strip Method Yttria-Stabilized Zr02: 2.2 W 1 • O% Cso ...-~ e:. 5% cso ";"E • 30% Cso " 100% Cso ~ 0.1 - • • • --- Lambropoulos ~ .... , ~ ----~e:.~-M---~!~-~-'~~J~--~~------4::1. .e. 4c. • • (J • e:.e:. e. e:.c!> &> e. e. e. ..0. e. -::s ••• ~ e. "CCc 0 ••• •••• (J 0.01 ..................... ftl " ..... " " " " " ...E CD .s: 1- 0.001 -L-________.._ __________ '-- ______. ____ __._~..;_.,.--~ 300 350 400 450 500 550 Temperature (K) FIG. 6 U.S. Patent Dec. 11, 2007 Sheet 7 of 20 US 7,306,828 B2 0.55 400/1100/1 -...~ . E o.5 • Pure PSZ-50.8% • • 1wt.% SWNT(AR)-51.3% 4 1wt.% SWNT(AR)-52.7% ~....... 0.45 . x 1wt.% SWNT(MR)-50.5% z. .. "' 1wt.% SWNT(MR)-52.2% ·:;:: .. • • 2wt.% SWNT(MR)-55.9% ~ 0.4 • • 2wt.% SWNT(MR)-52.1% X - 1wt.% VGCF-54.3% ::l X " • " •& •+ + - 1wt.% VGCF-54.0% * :! "c 0.35 "' "' "' <> 2wt.% VGCF-54.2% 0 - o 1wt.% VGCF-54.4% 0 ,. 3wt.% VGCF-57.5% a D Iii i ~ 0.3 •,. ,. ,. A o 3wt.% VGCF-58.8% 1'1:1 0 •0 0 0 0 E ...cv 0.25 ..c: 1- 0.2 550 650 750 850 950 1050 Temperature (C) FIG. 7 U.S. Patent Dec. 11, 2007 Sheet 8 of 20 US 7,306,828 B2 0.8 400/1100/12 -~ 0.75 X X X E X Pure PSZ-46.8% ~ 0.7 ~ • - • • Pure PSZ-45.3% ;:: 0.65 • .. 1wt.% SWNT(AR)-45.9% • X ..... • • • 1wt.% SWNT(AR)-42.9% • • .. .. >: 1wt.% SWNT(MR)-48.4% :~ 0.6 I .. ..... & 0 1wt.% SWNT(MR)-46.4% (J 0 0 0 + 2wt.% SWNT(MR)-47.9% :J 0.55 e 0 <> 0 6 X 2wt% SWNT(MR)-49.5% "'C ! ;! - - 1wt.% VGCF-48.9% ~ "' g 0.5 0 1wt.% VGCF-48.0% (.) !;! + ~ 0 2wt.% VGCF-50.8% Gl "' Q - 0.45 - 3wt.% VGCF-53.0% ctJ -+-PS-PSZ" E 0.4 ~ G) " " " " "' .c 0.35 I- 0.3 550 650 750 850 950 1050 Temperature (C) FIG. 8 U.S. Patent Dec. 11,2007 Sheet 9 of 20 US 7,306,828 B2 ~ --IC 1.9 400/1250/1 E -::: 1.7 • • • • • ->. ~ 1.5 > .. • .. .. • Pure PSZ-19.3% ..... • • • • • • 1wt.% SWNT(AR)-24.7% X .. 1wt.% SWNT(MR)-19.4% u 1.3 x :0: )( 2wt.% SWNT(MR)-25.0% ::l )( "' " X )( )( "'C )( :0: 1wt.% VGCF-24.0% s 1.1 0 3wt.% VGCF-42. 1% -+-PS-PSZ (.) ca 0.9 0 E o Q; 0.7 ---..-----1-----l!'------.!,...._...------J?." J: 1- 0.5 -j----,----,----,------,.----l 550 650 750 850 950 1050 Temperature (C) FIG. 9 U.S. Patent Dec. 11, 2007 Sheet 10 of 20 US 7,306,828 B2 FIG. 10 U.S. Patent Dec. 11, 2007 Sheet 11 of 20 US 7,306,828 B2 r-·-····--------------·----------------------------------------------------··------------------------------------• i 1591 j ! -en :': c: :l ..0,_ -ltl 1450 1 500 1550 1600 1650 1700 Wavenumber (1/cm) FIG.