Hurwitz, Frances I.

Palczer, Anna R.

Peysakhov, Feliks

Rogers, Richard B.

White, Scott P.

NASA Technical Reports Server

Development	  of	  Aluminosilicate	  Aerogel	  Impregnated	  	  
Oxide	  Foams	  for	  Structurally	  Integrated	  Thermal	  	  
Protec>on	  Systems	  
Frances	  I.	  Hurwitz	  
Anna	  R.	  Palczer	  
Richard	  B.	  Rogers	  
	  
NASA	  Glenn	  Research	  Center	  
Cleveland,	  OH	  	  44135	  
	  
Feliks	  Peysakhov,	  SUNY	  Stony	  Brook	  
ScoP	  P.	  White,	  U	  Iowa	  
	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
36th	  Annual	  Conference	  on	  Composites,	  Materials,	  and	  Structures	  
Cape	  Canaveral,	  FL,	  January	  23-­‐26,	  2012	  	  
https://ntrs.nasa.gov/search.jsp?R=20150010131 2019-08-31T07:54:55+00:00Z
– Light-­‐weight	  
– High	  volumetric	  heat	  capacity	  
– Low	  eﬀec>ve	  thermal	  conduc>vity	  
– Load	  bearing	  or	  non-­‐load	  bearing	  
– Non-­‐oxidizing	  
– Dimensional	  stability	  
Insula'ng	  Cores	  for	  Structurally	  Integrated	  TPS	  
(Integrated	  mechanical	  and	  thermal	  loads)	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
Can	  aerogel	  incorpora-on	  reduce	  
thermal	  conduc-vity	  while	  maintaining	  
dimensional	  stability,	  allowing	  for	  
lighter	  weight	  structural	  elements?	  
Susan	  White,	  Dan	  Rasky,	  “Fibrous-­‐Ceramic/Aerogel	  
Composite	  Insula>ng	  Tiles”,	  NASA	  Tech	  Briefs	  2004	  	  
Boehmite	  [γ-­‐AlO(OH)]+	  TEOS	   	  	  	  	  	  	  	  	  hydrogel	  	  	  	  	  	  	  	  	  	  	  	  	  aerogel	  
TEOS	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
S. Bruhne, Cryst. Growth Des., 2008, 8 (2), pp 489–493n 
S.	  Bruhne,	  Cryst.	  Growth	  Des.,	  2008,	  8	  
(2),	  pp	  489–493n	  
-0.2 
0.0 
0.2 
0.4 
0.6 
0.8 
1.0 
1.2 
1.4 
0 500 1000 1500 
µ
V/
m
g	

Temperature,	  ˚C	  
HG553	  P2	  3Al:1Si	  
KN570	  P2W	  3Al:1Si	  
HG626	  L4	  3Al:1Si	  
mullite	  forma>on	  
γ-Al2O3	
γ-AlΟΟΗ	

-0.2 
0.0 
0.2 
0.4 
0.6 
0.8 
1.0 
1.2 
1.4 
0 500 1000 1500 
µ
V/
m
g	

Temperature,	  ˚C	  
HG553	  P2	  3Al:1Si	  
KN570	  P2W	  3Al:1Si	  
HG626	  L4	  3Al:1Si	  
mullite	  forma>on	  
γ-Al2O3	
γ-AlΟΟΗ	

-0.2 
0.
0.2 
0.4 
0.6 
0.8 
1.0 
1.2 
1.4 
0 500 1000 1500 
µ
V/
m
g	

Temperature,	  ˚C	  
HG553	  P2	  3Al:1Si	  
KN570	  P2W	  3Al:1Si	  
HG626	  L4	  3Al:1Si	  
mullite	  forma>on	  
γ-Al2O3	
γ-AlΟΟΗ	

-0.2 
0.
0.2 
0.4 
0.6 
0.8 
1.0 
1.2 
1.4 
0 500 1000 1500 
µ
V/
m
g	

Temperature,	  ˚C	  
HG553	  P2	  3Al:1Si	  
KN570	  P2W	  3Al:1Si	  
HG626	  L4	  3Al:1Si	  
mullite	  forma>on	  
γ-Al2O3	
γ-AlΟΟΗ	

-­‐0.2	  
0.0	  
0.2	  
0.4	  
0.6	  
0.8	  
1.0	  
1.2	  
0	   500	   1000	   1500	  
µ
V/
m
g	  
Temperature,	  ˚C	  
γ-­‐Al2O3	  γ-­‐AlΟΟΗ	  
P2W	  3Al:1Si,	  412	  m2/g	  
Mullite	  forma>on	  
+	  
Boehmite	  
60	  
65	  
70	  
75	  
80	  
85	  
90	  
95	  
100	  
105	  
0	   500	   1000	   1500	  
M
as
s,
	  %
	  
Temperature,	  ˚C	  
γ-­‐Al2O3	  γ-­‐AlΟΟΗ	  
Oxide	  Foam	  Proper'es	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
Material Density (g/cc) 
Thermal 
Conductivity 
(W/m-K)
Specific 
Heat   
(J/kg-K)
Al2O3 SiO2 Binder Source
AETB-12 0.192 0.064 (predicted) 628 20% 68%
Glassy phase;  
Inclusion of silica 
and  
aluminoborosilicate 
fibers provides 
bonding
TPSX
 M15 0.240 0.16 1050 85% 15% High Purity Silica Zircar Zirconia
M2-35 0.624 - 1050 85% 15% Mullite Zircar Zirconia
ZAL-15 0.240 0.16 1047 85% 15% High Purity Silica Zircar Ceramics
M-­‐15	   M2-­‐35	  
Add	  AETB-­‐P	  250x	  
AETB-­‐12	   ZAL-­‐15	  
Microstructure:	  	  As-­‐received	  foams	  
AETB-­‐12	  
Microstructure:	  
As-­‐received	  foams	  
SiO2	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
ZAL-­‐15	  
Microstructure:	  
As-­‐received	  foams	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
M-­‐15	   M2-­‐35	  
Microstructure:	  	  As-­‐received	  foams	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
-8.0E-03 
-7.0E-03 
-6.0E-03 
-5.0E-03 
-4.0E-03 
-3.0E-03 
-2.0E-03 
-1.0E-03 
0.0E+00 
1.0E-03 
2.0E-03 
0 250 500 750 1000 1250 
L-
L 0
/L
0 
Temperature, ˚C 
Aerogel impregnated AETB-12 In-Plane 
-2.0E-03 
-1.5E-03 
-1.0E-03 
-5.0E-04 
0.0E+00 
5.0E-04 
1.0E-03 
1.5E-03 
2.0E-03 
2.5E-03 
3.0E-03 
0 250 500 750 1000 1250 
L-
L 0
/L
0 
Temperature, ˚C 
AETB-12 In-Plane 
-2.0E-02 
-1.8E-02 
-1.6E-02 
-1.4E-02 
-1.2E-02 
-1.0E-02 
-8.0E-03 
-6.0E-03 
-4.0E-03 
-2.0E-03 
0.0E+00 
2.0E-03 
0 250 500 750 1000 1250 
L-
L 0
/L
0 
Temperature, ˚C 
Aerogel impregnated AETB-12 through thickness 
-4.0E-03 
-3.0E-03 
-2.0E-03 
-1.0E-03 
0.0E+00 
1.0E-03 
2.0E-03 
0 250 500 750 1000 1250 
L-
L 0
/L
0 
Temperature, ˚C 
AETB-12 Through thickness 
Dilatometry:	  	  AETB-­‐12	  
-8.0E-03 
-6.0E-03 
-4.0E-03 
-2.0E-03 
0.0E+00 
2.0E-03 
4.0E-03 
6.0E-03 
0 250 500 750 1000 1250 
L-
L o
/L
o 
Temperature, ˚C 
Aerogel impregnated M-15, In-Plane 
0.0E+00 
2.0E-03 
4.0E-03 
6.0E-03 
8.0E-03 
1.0E-02 
1.2E-02 
0 250 500 750 1000 1250 
L-
L o
/L
o 
Temperature, ˚C 
M-15, In-Plane 
-6.0E-03 
-4.0E-03 
-2.0E-03 
0.0E+00 
2.0E-03 
4.0E-03 
6.0E-03 
8.0E-03 
1.0E-02 
0 250 500 750 1000 1250 
L-
L o
/L
o 
Temperature, ˚C 
M-15 Through thickness 
-3.5E-02 
-3.0E-02 
-2.5E-02 
-2.0E-02 
-1.5E-02 
-1.0E-02 
-5.0E-03 
0.0E+00 
5.0E-03 
1.0E-02 
0 250 500 750 1000 1250 
L-
L o
/L
o 
Temperature, ˚C 
Aerogel impregnated M-15 Through thickness 
Dilatometry:	  	  M-­‐15	  
0.0E+00 
1.0E-03 
2.0E-03 
3.0E-03 
4.0E-03 
5.0E-03 
6.0E-03 
7.0E-03 
8.0E-03 
9.0E-03 
1.0E-02 
0 250 500 750 1000 1250 
L-
L o
/L
o 
Temperature, ˚C 
ZAL-15 In-Plane 
-6.0E-03 
-4.0E-03 
-2.0E-03 
0.0E+00 
2.0E-03 
4.0E-03 
6.0E-03 
8.0E-03 
0 250 500 750 1000 1250 
L-
L o
/L
o 
Temperature, ˚C 
ZAL-15 Through thickness 
-1.0E-02 
-8.0E-03 
-6.0E-03 
-4.0E-03 
-2.0E-03 
0.0E+00 
2.0E-03 
4.0E-03 
0 250 500 750 1000 1250 
L-
L o
/L
o 
Temperature, ˚C 
Aerogel impregnated ZAL-15 In-Plane 
-3.0E-02 
-2.5E-02 
-2.0E-02 
-1.5E-02 
-1.0E-02 
-5.0E-03 
0.0E+00 
5.0E-03 
0 250 500 750 1000 1250 
L-
L o
/L
o 
Temperature, ˚C 
Aerogel impregnated ZAL-15 Through thickness 
Dilatometry:	  	  ZAL-­‐15	  
-2.0E-03 
-1.0E-03 
0.0E+00 
1.0E-03 
2.0E-03 
3.0E-03 
4.0E-03 
5.0E-03 
6.0E-03 
7.0E-03 
8.0E-03 
9.0E-03 
0 250 500 750 1000 1250 
L-
L 0
/L
0 
Temperature, ˚C 
M2-35 Through thickness 
0.0E+00 
1.0E-03 
2.0E-03 
3.0E-03 
4.0E-03 
5.0E-03 
6.0E-03 
7.0E-03 
8.0E-03 
0 250 500 750 1000 1250 
L-
L 0
/L
0 
Temperature, ˚C 
-1.0E-03 
0.0E+00 
1.0E-03 
2.0E-03 
3.0E-03 
4.0E-03 
5.0E-03 
6.0E-03 
7.0E-03 
8.0E-03 
9.0E-03 
0 250 500 750 1000 1250 
L-
L 0
/L
0 
Temperature, ˚C 
Aerogel-impregnated M2-35 In-plane 
-2.0E-03 
-1.0E-03 
0.0E+00 
1.0E-03 
2.0E-03 
3.0E-03 
4.0E-03 
5.0E-03 
6.0E-03 
7.0E-03 
8.0E-03 
9.0E-03 
0 250 500 750 1000 1250 
L-
L 0
/L
0 
Temperature, ˚C 
Aerogel-impregnated M2-35 through thickness 
M2-­‐35	  In-­‐plane	  
Dilatometry:	  	  M2-­‐35	  
-1.00E-03 
-5.00E-04 
0.00E+00 
5.00E-04 
1.00E-03 
1.50E-03 
2.00E-03 
2.50E-03 
3.00E-03 
3.50E-03 
0 250 500 750 1000 1250 
L-
L 0
/L
0 
Temperature, ˚C 
AETB-12 In-Plane 
-5.00E-04 
0.00E+00 
5.00E-04 
1.00E-03 
1.50E-03 
2.00E-03 
2.50E-03 
0 250 500 750 1000 1250 
L-
L 0
/L
0 
Temperature, ˚C 
AETB-12 Through thickness 
Dilatometry:	  	  AETB-­‐12	  
0.00	  
0.20	  
0.40	  
0.60	  
0.80	  
1.00	  
1.20	  
1.40	  
1.60	  
1.80	  
2.00	  
Sh
rin
ka
ge
,	  %
	  
*	   *	   *	   *	  
*	  	  No	  measurable	  shrinkage	  
As-­‐Received	  Foams	  
Aerogel-­‐Impregnated	  Foams	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
Dilatometry:	  	  Dimensional	  changes	  aSer	  5	  cycles	  to	  1200˚C	  
Aerogel-­‐inﬁltrated	  AETB-­‐12	  
Post	  5	  cycles	  to	  1200˚C	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
Aerogel-­‐inﬁltrated	  M-­‐15	  
Post	  5	  cycles	  to	  1200˚C	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
Aerogel-­‐inﬁltrated	  M2-­‐35	  
Post	  5	  cycles	  to	  1200˚C	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
 
Sample: FH_FP AETB-S1 
 
Chemical Formula Compound Name Crystal System Ref. Code SemiQuant [%] 
Al2 O3 Aluminum Oxide Rhombohedral 04-003-5819 53 
Al4.44 Si1.56 O9.78 Aluminum Silicate Orthorhombic 01-074-4143 35 
Si O2 Silicon Oxide Tetragonal 04-008-7636 1 
Al2.5 B0.5 O4.5 Aluminum Boron Oxide Orthorhombic 04-012-8917 11 
 
Sample: FH_FP Zal15-S1 
 
Chemical Formula Compound Name Crystal System Ref. Code SemiQuant [%] 
Al2 O3 Aluminum Oxide Rhombohedral 01-089-7717 61 
Al2 ( Al2.544 Si1.456 ) 
O9.728 
Aluminum Silicon Oxide Orthorhombic 01-074-8556 18 
Al2 O3 Aluminum Oxide Monoclinic 04-008-4095 12 
B6 O0.787 Boron Oxide Rhombohedral 01-087-2286 10 
 
Sample: FH_FP 07515 Bus M-15-S1 revisited 
 
Chemical Formula Compound Name Crystal Syste  Ref. Code SemiQuant [%] 
O3 Alpha alumina Rhombohedral 01-088-0826 71 
Al4.5  Si1.48 O9.74 mullite Orthorhombic 01-074-4144 21 
Theta alumina Monoclinic 01-086-1410 8 
 
 
Sample: FH_FP AETB-S1 
 
Chemical Formula Compound Name Crystal System Ref. Code SemiQuant [%] 
Al2 O3 Aluminum Oxide Rhombohedral 04-003-5819 53 
Al4.44 Si1.56 O9.78 Aluminum Silicate Orthorhombic 01-074-4143 35 
Si O2 Silicon Oxide Tetragonal 04-008-7636 1 
Al2.5 B0.5 O4.5 Aluminum Boron Oxide Orthorhombic 04-012-8917 11 
 
Sample: FH_FP Zal15-S1 
 
Chemical Formula Compound Name Crystal System Ref. Code SemiQuant [%] 
Al2 O3 Aluminum Oxide Rhombohedral 01-089-7717 61 
Al2 ( Al2.544 Si1.456 ) 
O9.728 
Aluminum Silicon Oxide Orthorhombic 01-074-8556 18 
Al2 O3 Aluminum Oxide Monoclinic 04-008-4095 12 
B6 O0.787 Boron Oxide Rhombohedral 01-087-2286 10 
 
Samples	  aoer	  5	  cycles	  to	  1000˚C	  are	  very	  similar,	  with	  possible	  very	  small	  SiC	  
phase	  present	  in	  AETB.	  	  	  
AETB,	  as	  received	  
M-­‐15,	  as	  received	  
ZAL-­‐15,	  as	  received	  
Signiﬁcant	  glassy	  phase	  
X-­‐ray	  Diﬀrac'on:	  	  As-­‐received	  foams	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
?	  
?	  
Sample: FP 855 A-TT-2 alt 
Chemical Formula Compound Name Crystal System Ref. Code SemiQuant [%] 
Al2 O3 alpha alumina Rhombohedral 01-089-7717 53 
Al4.44 Si1.56 O9.78 mullite Orthorhombic 01-074-4143 40 
Si C beta SiC Cubic 01-075-0254 2 
?Si O2 cristobalite Tetragonal 04-005-4875 4 
 Signiﬁcant	  glassy	  phase	  (SiO2)	  
Sample: FP 855 Z-TT-2 
 
Chemical Formula Compound Name Crystal System Ref. Code SemiQuant [%] 
Al2 O3 alpha alumina Rhombohedral 01-076-8056 64 
Al2 ( Al2.556 Si1.444 ) 
O9.722 
mullite Orthorhombic 01-074-8552 19 
Al2 O3 Theta alumina Monoclinic 01-086-1410 16 
?Si O2 cristobalite Tetragonal 04-008-7641 1 
Note1: there is a small glassy component to this sample. 
Sample: DM 783-TT1-2 
 
Chemical Formula Compound Name Crystal System Ref. Code SemiQuant [%] 
Al2 O3 alpha alumina Rhombohedral 01-088-0826 69 
Al4.52 Si1.48 O9.74 mullite Orthorhombic 01-074-4144 21 
Al2 O3 Theta alumina Monoclinic 01-086-1410 10 
 
Aerogel	  impregnated	  AETB,	  1200˚C	  x	  5	  
Aerogel	  impregnated	  M-­‐15,	  1200˚C	  x	  5	  
Aerogel	  impregnated	  ZAL-­‐15,	  1200˚C	  x	  5	  
X-­‐ray	  Diﬀrac'on:	  	  Thermally	  cycled	  composites	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
?	  
Sample: M2-35 as received (from XRD report 07610a) 
 
Chemical Formula Compound Name Crystal System Ref. Code SemiQuant [%] 
( Al2.34 Si0.66 ) O4.83 Aluminum Silicate Orthorhombic 01-076-2579 84 
Al2 O3 Aluminum Oxide Rhombohedral 01-073-6190 11 
?Ni ( P4 O11 ) Nickel Phosphorus Oxide Anorthic 01-073-5532 6 
 
 
M2-­‐35,	  5x	  to	  1200˚C	  
Aerogel	  inﬁltrated	  M2-­‐35,	  5x	  to	  1200˚C	  
M2-­‐35,	  as	  received	  
10	   20	   30	   40	   50	   60	   70	  
Degrees	  2θ	  
M2-­‐35	  As	  received	  
X-­‐ray	  Diﬀrac'on:	  	  M2-­‐35	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
M2-­‐35	  As	  received	  
Post	  CTE	  5	  cycles	  1200˚C	  
M2-­‐35	  microstructure	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
Thermal	  conduc'vity	  and	  heat	  capacity	  measurements	  	  
of	  as-­‐received	  and	  aerogel	  impregnated	  oxide	  foams	  	  
in	  progress.	  
• 	  Laser	  ﬂash	  method	  being	  evaluated	  
• 	  Samples	  being	  prepared	  compara>ve	  rod	  measurements	  	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
Ongoing	  work:	  
Addi'onal	  Oxide	  Foams	  
Glenn	  Research	  Center	  at	  Lewis	  Field	  
All	  Al2O3	  aerogels	  
Material Density (g/cc) 
Thermal 
Conductivity 
(W/m-K)
Specific 
Heat   
(J/kg-K)
Al2O3 SiO2 Binder Source
A-15 0.240 - 1050 97+% - Alumina Zircar Zirconia
M2-15 0.240 - 1050 85% 15% Mullite Zircar Zirconia
Glenn	  Research	  Center	  at	  Lewis	  Field	  
CONCLUSIONS:	  
• 	  Oxide	  foams	  (AETB-­‐12,	  ZAL-­‐15,	  M-­‐15)	  containing	  silica	  binders	  and	  glassy	  	  
phases	  undergo	  shrinkage	  on	  hea>ng	  above	  1100˚C.	  	  Foams	  con>nue	  to	  shrink	  	  
with	  repeated	  thermal	  cycling.	  
• 	  Incorpora>on	  of	  aluminosilicate	  aerogels	  exacerbates	  shrinkage	  in	  AETB-­‐12,	  	  
ZAL-­‐15,	  M-­‐15,	  par>cularly	  in	  through	  thickness	  dimension.	  
• 	  Mullite	  foams	  (M2-­‐35)	  oﬀer	  considerable	  improvement	  in	  dimensional	  stability,	  	  
including	  samples	  incorpora>ng	  aluminosilicate	  aerogels.	  	  Commercially	  available	  
M2-­‐35	  carries	  a	  weight	  penalty;	  however,	  trial	  fabrica>on	  of	  	  lower	  density	  M2-­‐15,	  	  
and	  a	  lower	  density	  all	  Al2O3	  foam,	  is	  in	  progress.	  
• 	  Thermal	  conduc>vity	  measurements	  of	  the	  foams,	  with	  and	  without	  aluminosilicate	  
incorpora>on,	  are	  underway.	  	  
• 	  A	  Boehmite-­‐derived,	  all	  Al2O3	  aerogel,	  will	  be	  compared	  with	  aluminosilicates.	  
	  
ACKNOWLEDGMENTS:	  
NASA	  ARMD	  Hypersonics	  Project	  
NASA	  Undergraduate	  Student	  Research	  Program	  
Derek	  R.	  Miller	  


Development of Aluminosilicate Aerogel Impregnated Oxide Foams for Structurally Integrated Thermal Protection Systems

Abstract

Similar works

Full text

Available Versions

NASA Technical Reports Server