IP Library Granted Patent US 12,654,885
Granted Patent B2
US 12,654,885 · App. 18/461,209 · Granted Jun 16, 2026

Method of producing an aluminosilicate reinforced silicone syntactic thermal protection system

Inventor: Adam Kopysc (Renton, WA)
Assignee: Blue Origin Manufacturing, LLC
B64G1/58C08J9/0071C08J9/32C08K3/34C08K3/346C08K7/26C08K9/06C08L83/04C08J2203/22C08J2383/04C08K2201/011
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Quick Facts
Patent No.
US 12,654,885
App. No.
18/461,209
Granted
Jun 16, 2026
Kind
B2
Abstract

Techniques and systems are used to fabricate a thermal protection systems (TPS) for placement on various parts of a structure, such as a spacecraft. The TPS may comprise syntactic foam as a spray-on foam insulation (SOFI), which may be sprayed onto a surface. Alternatively, the TPS may comprise syntactic foam that is applied as preformed panels that are adhered or mechanically attached to a surface. Performance of a syntactic foam may be improved by including an aluminosilicate nanotube material, such as halloysite nanotubes, in a matrix material. The halloysite nanotubes may be hydrated and treated with a silane couplant before being mixed into the matrix material, which may be a two-part silicone based syntactic insulator material, for example. The halloysite nanotubes, in addition to acting as a filler and reinforcement for the syntactic insulator material, release water during oblation, thus contributing to the effectiveness of a TPS.

Claims (27)

1 . A method of producing a thermal protection system, the method comprising:

hydrating halloysite nanotubes to form hydrated halloysite nanotubes that contain water molecules trapped within scroll-like sheets, wherein the water molecules are between concentric layers of the scroll-like sheets and wherein hydrating the halloysite nanotubes comprises at least one of (i) soaking the halloysite nanotubes in water and subsequently drying to remove excess water, or (ii) exposing the halloysite nanotubes to non-condensing water vapor;

treating the hydrated halloysite nanotubes with a silane coupling agent to increase surface energy and to enable formation of strong chemical bonds between the hydrated halloysite nanotubes and a silicone-based matrix material; and

combining the silicone-based matrix material and the treated hydrated halloysite nanotubes to form a syntactic foam, wherein the hydrated halloysite nanotubes release water upon ablation to provide evaporative cooling, and wherein the syntactic foam is adapted for use in a thermal protection system to withstand high-temperature thermal cycling and ablation.

2 . The method of claim 1 , wherein treating the hydrated halloysite nanotubes to increase the adherability comprises increasing surface energy of the hydrated halloysite nanotubes.

3 . The method of claim 1 , wherein treating the hydrated halloysite nanotubes to increase the adherability comprises applying silane to the hydrated halloysite nanotubes.

4 . The method of claim 3 , wherein the silane comprises, at least in part, 3-aminopropyltrimethoxysilane.

5 . The method of claim 1 , wherein treating the hydrated halloysite nanotubes to increase the adherability comprises silanizing the hydrated halloysite nanotubes to allow formation of chemical bonds between the hydrated halloysite nanotubes and the syntactic foam.

6 . The method of claim 1 , further comprising adding microspheres to the syntactic foam.

7 . The method of claim 1 , further comprising forming the syntactic foam into panels or sheets.

8 . The method of claim 1 , further comprising spraying the syntactic foam onto a surface.

9 . The method of claim 1 , further comprising packing the syntactic foam into a honeycomb or grid core that is attached to a surface.

10 . The method of claim 1 , wherein a concentration of the hydrated halloysite nanotubes in the syntactic foam is in a range from about 5% to 40% by mass.

11 . A method of producing a thermal protection system, the method comprising:

hydrating halloysite nanotubes to form hydrated halloysite nanotubes that contain water molecules trapped within scroll-like sheets, wherein the water molecules are between concentric layers of the scroll-like sheets and wherein hydrating the halloysite nanotubes comprises at least one of (i) soaking the halloysite nanotubes in water and subsequently drying to remove excess water, or (ii) exposing the halloysite nanotubes to non-condensing water vapor;

applying a silane coupling agent to the hydrated halloysite nanotubes to produce silanated hydrated halloysite nanotubes that are configured to chemically bond to a silicone-based matrix material;

combining the silanated hydrated halloysite nanotubes with the silicone-based matrix material to form a syntactic foam; and

arranging the syntactic foam into the thermal protection system, wherein the syntactic foam resists degradation by thermal cycling and ablation and provides cooling by release of water from the hydrated halloysite nanotubes.

12 . The method of claim 11 , wherein applying the silane to the hydrated halloysite nanotubes increases surface energy of the hydrated halloysite nanotubes.

13 . The method of claim 11 , wherein the silane comprises, at least in part, 3-aminopropyltrimethoxysilane.

14 . The method of claim 11 , wherein combining the silanated hydrated halloysite nanotubes with the silicone-based matrix material further comprises forming chemical bonds between the silanated hydrated halloysite nanotubes and the syntactic foam.

15 . The method of claim 11 , further comprising adding microspheres to the syntactic foam.

16 . The method of claim 11 , wherein arranging the syntactic foam into the thermal protection system further comprises forming the syntactic foam into panels or sheets.

17 . The method of claim 11 , wherein arranging the syntactic foam into the thermal protection system further comprises spraying the syntactic foam onto a surface.

18 . The method of claim 17 , wherein the surface includes a honeycomb or grid core that is attached to the surface.

19 . The method of claim 11 , wherein arranging the syntactic foam into the thermal protection system further comprises packing the syntactic foam into a honeycomb or grid core that is attached to a surface.

20 . The method of claim 11 , wherein a concentration of the hydrated halloysite nanotubes in the syntactic foam is in a range from about 5% to 40% by mass.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 20, 2025
From: BLUE ORIGIN, LLC
To: BLUE ORIGIN MANUFACTURING, LLC
Reel/Frame 070585/0358 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 5, 2023
From: KOPYSC, ADAM
To: BLUE ORIGIN, LLC
Reel/Frame 064799/0349 →
Continuity (1)
Related Publication 20250074628A1 · Mar 6, 2025
References Cited (36)
US 4456208A · Macconochie et al. · 1984 [cited by applicant]
US 4713275A · Riccitiello et al. · 1987 [cited by applicant]
US 6293496B1 · Moe · 2001 [cited by applicant]
US 7888419B2 · Cooper · 2011 [cited by examiner]
US 8147943B1 · Byrd et al. · 2012 [cited by applicant]
US 8648132B2 · Fleischer · 2014 [cited by examiner]
US 10259972B2 · Fish · 2019 [cited by examiner]
US 11459247B2 · Almasri · 2022 [cited by examiner]
US 11505684B2 · Dai · 2022 [cited by examiner]
US 11667408B2 · Brendel · 2023 [cited by examiner]
US 11708517B1 · Onaizi · 2023 [cited by examiner]
US 11746278B1 · Onaizi · 2023 [cited by examiner]
US 12144823B2 · Jermy · 2024 [cited by examiner]
US 12269934B2 · Prevoir · 2025 [cited by examiner]
US 20080248201A1 · Corkery · 2008 [cited by examiner]
US 20080249221A1 · Corkery · 2008 [cited by examiner]
US 20090326133A1 · Daly · 2009 [cited by examiner]
US 20110183146A1 · Wendell, Jr. · 2011 [cited by examiner]
US 20120189808A1 · Wendell · 2012 [cited by examiner]
US 20170072604A1 · Sjong · 2017 [cited by examiner]
US 20180277811A1 · Liu · 2018 [cited by examiner]
US 20180345247A1 · Akbari · 2018 [cited by examiner]
US 20200002030A1 · Brendel et al. · 2020 [cited by applicant]
US 20230358741A1 · Xu · 2023 [cited by examiner]
US 20240117180A1 · Benfatti · 2024 [cited by examiner]
Yuan, Peng, et al. “Functionalization of halloysite clay nanotubes by grafting with Î [cited by examiner]
Pasbakhsh, Pooria, et al. “EPDM/modified halloysite nanocomposites.” Applied Clay Science 48.3 (Feb. 1, 2010): 405-413. (Year: 2010). [cited by examiner]
Yuan, Peng, Daoyong Tan, and Faà [cited by examiner]
Berahman, Reyhaneh, et al. “Preparation and characterization of vulcanized silicone rubber/halloysite nanotube nanocomposites: Effect of matrix hardness and HNT content.” Materials & Design 104 (May 6, 2016): 333-345. (… [cited by examiner]
Karami, Zohre, et al. “Well-cured silicone/halloysite nanotubes nanocomposite coatings.” Progress in Organic Coatings 129 (Feb. 1, 2019): 357-365. (Year: 2019). [cited by examiner]
Hayeemasae, Nabil, et al. “Viable properties of natural rubber/halloysite nanotubes composites affected by various silanes.” Polymers 15.1 (Dec. 21, 2022): 29. (Year: 2022). [cited by examiner]
Uner, Gizem, Gulderen Karakus, and Hatice Kaplan Can. “Design, fabrication and characterization of silane tailored surface of halloysite based polymer nanocomposites.” Polymer Composites 44.2 (Nov. 28, 2022): 1305-1330.… [cited by examiner]
Hu, Yongwei, et al. “Progress in application of silane coupling agent for clay modification to flame retardant polymer.” Molecules 29.17 (Aug. 31, 2024): 4143. (Year: 2024). [cited by examiner]
Zielecka, Maria, and Anna Rabajczyk. “Silicone Nanocomposites with Enhanced Thermal Resistance: A Short Review.” Materials 17.9 (Apr. 25, 2024): 2016. (Year: 2024). [cited by examiner]
Christian Gogu, Satish K. Bapanapalli, Raphael T. Haftka, and Bhavani V. Sankar, “Comparison of Materials for an Integrated Thermal Protection System for Spacecraft Reentry” Journal of Spacecraft and Rockets, vol. 46, N… [cited by applicant]
Greene, Effie E., “Thermal Protection and Control” Flight Structures & Thermal Protection Systems Branch, Kennedy Space Center, University of Nebraska-Lincoln, Summer 2013. [cited by applicant]