IP Library › Granted Patent US 12,359,316
Granted Patent B2
US 12,359,316 · App. 16/925,782 · Granted Jul 15, 2025

Hydrogen permeation barrier coatings and methods of making the same

Inventors: Abdellatif M. Yacout (Naperville, IL); Sumit Bhattacharya (Darien, IL); Yinbin Miao (Naperville, IL); Nicolas E. Stauff (Oak Park, IL)
Assignee: UCHICAGO ARGONNE, LLC
C23C16/45529C23C16/06C23C16/403C23C28/32C23C28/345C23C28/42C23C28/44B32B15/01Y10T428/12535Y10T428/12542Y10T428/12549Y10T428/12576Y10T428/12583Y10T428/1259Y10T428/12597Y10T428/12604Y10T428/12611Y10T428/12618Y10T428/12625
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,359,316
App. No.
16/925,782
Granted
Jul 15, 2025
Kind
B2
Abstract

Provided herein is a hydrogen permeation barrier coating, a coated substrate, and methods of coating a substrate.

Claims (25)

1. A hydrogen permeation barrier coating, comprising:

a plurality of alternating layers, wherein the plurality of alternating layers comprises alternating metal layers and ceramics layers, wherein each alternating layer, independently, comprises a microstructure comprising nanocrystalline and/or equiaxed grains, and wherein the hydrogen permeation barrier coating has a total thickness of about 200 nm to about 2 microns.

2. The hydrogen permeation barrier coating of claim 1 , wherein the metal layers comprise one or more of refractory metals, high-temperature metals, high-temperature metal alloys, and intermetallic compounds.

3. The hydrogen permeation barrier coating of claim 1 , wherein the ceramics layers comprise one or more of oxides, nitrides, carbides, aluminides, silicides, elemental ceramics, complex oxides, and max phases, wherein the max phases are represented by the formula M n+1 AX n where n is an integer 1 to 4, M is a transition metal, and A is one or more of Al, Si, P, S, Ga, Ge, As, Cd, In, Sn, Ti, and Pb, and X is carbon and/or nitrogen.

4. The hydrogen permeation barrier coating of claim 3 , wherein the ceramic layers comprise Al 2 O 3 .

5. The hydrogen permeation barrier coating of claim 1 , wherein the metal layers comprise W.

6. The hydrogen permeation barrier coating of claim 1 , wherein the plurality of alternating layers comprises 4 to 50 layers.

7. The hydrogen permeation barrier coating of claim 1 , wherein each ceramics layer has a thickness of about 5 nm to about 25 nm.

8. The hydrogen permeation barrier coating of claim 1 , wherein each metal layer has a thickness of about 25 nm to about 75 nm.

9. The hydrogen permeation barrier coating of claim 1 , wherein the hydrogen permeation barrier coating is monolithic and substantially pinhole free.

10. The hydrogen permeation barrier coating of claim 1 , wherein the hydrogen permeation barrier coating can withstand temperatures of greater than 600° C. in the presence of hydrogen, without substantial degradation.

11. The hydrogen permeation barrier coating of claim 1 having a hydrogen permeation of 1×10 −10 m/s/Torr (0.5) or less over a 24-hour time period at a temperature of 500° C. or more.

12. The hydrogen permeation barrier coating of claim 1 having less than 1% pinhole density after deposition.

13. The hydrogen barrier coating of claim 1 , wherein the metal layers are deposited by physical vapor deposition.

14. A method of forming the hydrogen permeation barrier coating of claim 1 on a substrate comprising: depositing a hydrogen permeation barrier coating onto a substrate via atomic layer deposition (ALD), wherein the depositing comprises two or more deposition cycles of at least a first precursor and separately two or more deposition cycles of at least a second precursor such that the plurality of alternating layers comprising the alternating metal layers and ceramic layers are formed on the substrate resulting from the first precursor deposition and the second precursor deposition, and each cycle of the first and second precursors comprises a pulse time of about 0.1 seconds to 20 seconds, a purge time of about 5 seconds to about 60 seconds, and a deposition temperature in a range of about 150° C. to about 400° C.

15. The method of claim 14 , wherein the substrate comprises one or more of a metal or alloy thereof, a metal with a ceramic composite structure, and a carbon fiber or composites thereof.

16. The method of claim 14 , wherein each depositing step is repeated 5 or more times.

17. The method of claim 14 , wherein the metal layers comprise one or more of refractory metals, high-temperature metals, high-temperature metal alloys, and intermetallic compounds.

18. The method of claim 14 , wherein the ceramic layers comprise one or more of oxides, nitrides, carbides, aluminides, silicides, elemental ceramics, complex oxides, and max phases, wherein the max phases are represented by the formula M n+1 AX n where n is an integer 1 to 4, M is a transition metal, and A is one or more of Al, Si, P, S, Ga, Ge, As, Cd, In, Sn, Ti, and Pb, and X is carbon and/or nitrogen.

19. A method of forming the hydrogen permeation barrier coating of claim 1 comprising:

depositing a ceramic layer onto the substrate;

depositing a metal layer onto the ceramic layer,

repeating alternatingly the depositing of the ceramic layer and the metal layer, wherein each depositing is performed under conditions sufficient to form a respective one of the ceramic or metal layers having a microstructure comprising nanocrystalline and/or equiaxed grains.

20. The method of claim 19 , comprising depositing by one or more of physical vapor deposition, chemical vapor deposition, electrochemical deposition, and atomic layer deposition.

21. The method of claim 19 , comprising depositing the metal layer by physical vapor deposition and the ceramic layer by atomic layer deposition.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 17, 2023
From: YACOUT, ABDELLATIF; BHATTACHARYA, SUMIT; MIAO, YINBIN; STAUFF, NICOLAS E.
To: UCHICAGO ARGONNE, LLC
Reel/Frame 063013/0051 →
CONFIRMATORY LICENSE Recorded Feb 9, 2021
From: UCHICAGO ARGONNE, LLC
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 055195/0832 →
Continuity (1)
Related Publication 20220010429A1 · Jan 13, 2022
References Cited (76)
US 3277565A · Bohlander · 1966 [cited by applicant]
US 3784384A · Webb · 1974 [cited by applicant]
US 4071587A · Eggers · 1978 [cited by applicant]
US 5747830A · Okita · 1998 [cited by examiner]
US 6541371B1 · Ashtiani · 2003 [cited by examiner]
US 8652589B2 · Ramm · 2014 [cited by applicant]
US 20100123993A1 · Laor · 2010 [cited by examiner]
US 20150063523A1 · Yacout et al. · 2015 [cited by applicant]
US 20170226633A1 · Cabral, Jr. · 2017 [cited by examiner]
US 20200411758A1 · Lin · 2020 [cited by examiner]
CN 101265603A · 2008 [cited by applicant]
CN 101629028A · 2010 [cited by applicant]
CN 103557612A · 2014 [cited by applicant]
CN 110670040A · 2020 [cited by examiner]
JP 2008296434A · 2008 [cited by examiner]
KR 20000027925A · 2000 [cited by examiner]
WO WO9426604A1 · 1994 [cited by examiner]
Metal Supermarkets What are Refractory Metals; https://www.metalsupermarkets.com/what-are-refractory-metals/ ;Feb. 18, 2022 (Year: 2022). [cited by examiner]
Translation—CN-110670040-A; Ding J; Jan. 10, 2020 (Year: 2020). [cited by examiner]
Translation—JP-2008296434-A; Igari M ; Dec. 11, 2008 (Year: 2008). [cited by examiner]
Anderson et al., Reactivity control of fast-spectrum reactors by reversible hydriding of yttrium zones, NASA TN D-4615 (1968). [cited by applicant]
Appel et al., Gamma Titanium Aluminide Alloys: Science and Technology, John Wiley & Sons (2011). [cited by applicant]
Bejaoui et al., ECRIX-H experiment: Synthesis of post-irradiation examinations and simulations, J. Nuclear Materials, 415(2):158-66 (2011). [cited by applicant]
Brimahll et al., Database on Permeation, Diffusion, and Concentration of Hydrogen Isotopes in Fusion Reactor Materials, Fusion Reactor Materials Semiannual Progress Report, DOE/ER-0313/16 (1994). [cited by applicant]
Chaffron et al., Innovative SiC/SiC Composite for Nuclear Applications, EPJ Web of Conferences (2013). [cited by applicant]
Chai et al., Ultra-thin Al2-O3 films grown by atomic layer deposition for corrosion protection of copper, RSC Advances, 4(92):50503-9 (2014). [cited by applicant]
Comeli et al., Effects of tempering temperature on the microstructure and creep resistance of X22C4MoV12-1 steel used on steam turbine blades, Am J Materials Sci., 8(4):65-72 (2018). [cited by applicant]
Dever et al., Research on high-termperature aerospace materials at NASA Glenn Research Center, J. Aerospace Engineering, 26(2):500-514 (2013). [cited by applicant]
El-Genk et al., A review of refractory metal alloys and mechanically alloyed-ixude dispersion strengthened steels for space nuclear power systems, J Nuclear Materials, 340(1):93-112 (2005). [cited by applicant]
Elen et al., Voids in vanadium, niobium and molybdenum by fast neutron irradiation at high temperatures, J. Nuclear Materials, 39(2):194-202 (1971). [cited by applicant]
Forcey et al., Formation of hydrogen permeation barriers on steels by aluminising, J. Nuclear Materials, 182:36 (1991). [cited by applicant]
Forcey et al., Hydrogen transport and solubility in 316L and 1.4914 steels for fusion reactor applications, J. Nucleaer Materials, 160:117-24 (1988). [cited by applicant]
Gibala et al., Hydrogen embrittlement and stress corrosion cracking, ASM International, 324 (1984). [cited by applicant]
Hishinuma et al., Void swelling in electron irradiated Hastelloy-X. J. Nuclear Science and Technology, 15(4): 288-295 (1978). [cited by applicant]
Hollenberg et al., Tritium/hydrogen barrier development, Fusion Engineering and Design, 28:190-208 (1995). [cited by applicant]
Honeycombe et al., Steels: Microstructure and Properties. Metallurgy and Materials Science, American Society for Metals (Jan. 1982). [cited by applicant]
Horak et al., Creep properties of Nb—1Zr and Nb—1Zr-0.1 C, No. ORNL-6809, Oak Ridge National Laboratory (1994). [cited by applicant]
Investigation of the Environment Fate of Tritium in the Atmosphere, Canadian Nuclear Safety Commission (CNSC), INFO-0792 (2009). [cited by applicant]
James et al., 700 Bar type IV H2 pressure vessel cost projections. In: Department of Energy Physical-Based Hydrogen Storage Workshop: Identifying Potential Pathways for Lower Cost 700 Bar Storage Vessels (2016). [cited by applicant]
Johnson et al., A brief review of atomic layer deposition: from fundamentals to applications, Materials Today, 16(5):236-46 (2014). [cited by applicant]
Katoh et al., Observation and possible mechanism of irradiation induced creep in ceramics, J. Nuclear Materials, 434(1-3):141-151 (2013). [cited by applicant]
Kellner, Space Age Ceramics Are Aviation's New Cup of Tea, General Electric Reports, downloaded from the Internet at: <https://www.ge.com/reports/space-age-cmcs-aviations-new-cup-of-tea/> (published Jul. 13, 2016). [cited by applicant]
Koyanagi et al., SiC/SiC Cladding Materials Properties Handbook, Technical Report ORNL/TM-2017/385, Oak Ridge National Laboratory (2017). [cited by applicant]
Leonard et al., Nb-base FS-85 alloy as a candidate structural material for space reactor applications: Effects of thermal aging, Metallurgical and Materials Transactions A, 40(4):838-55 (2009). [cited by applicant]
Lundin et al., Pressure-temperature-composition relationships of the yttrium-hydrogen system, J. Electrochemical Soc., 109(9):838-42 (1962). [cited by applicant]
Management of Tritium at Nuclear Facilities, IAEA Vienna, Technical Report Series No. 234, 1984. [cited by applicant]
Matejicek et al., Characterization of less common nitrides as potential permeation barriers, Fusion Engineering and Design, 139:74-80 (2019). [cited by applicant]
Merrigan, Heat Pipe Technology Issues, 1st Symposium on Space Nuclear Power Systems, Albuquerque, New Mexico, Jan. 11-13, 1984, Los Alamos National Laboratory LA-UR-84-1238 (1984). [cited by applicant]
Miao et al., Advanced moderation module for thermal neutron reactors operating at elevated temperatures, United States. doi:10.2172/1656612 (published Aug. 31, 2020). [cited by applicant]
Mueller et al. (eds.), Metal Hydrides, Elsevier 2013. [cited by applicant]
Muroga, Refractory metals as core materials for Generation IV nuclear reactors, In: Structural Materials for Generation IV Nuclear Reactors, pp. 415-440. Woodhead Publishing, 2017. [cited by applicant]
Olander et al., Uranium-zirconium hydride fuel properties, Nuclear Engineering and Design, 239(9):1406-24 (Aug. 2009). [cited by applicant]
Osborne et al., Reducing Irradiation Damage in a Long-Life Fast Reactor with Spectral Softening, Energies, 11(6):1507 (2018). [cited by applicant]
Perujo et al., Tritium permeation barriers for fusion technology, Fusion Engineering and Design, 28:252 (1995). [cited by applicant]
Prasad et al. (eds.), Aerospace Materials and Material Technologies, vol. 3, Singapore: Springer (2017). [cited by applicant]
Ribeiro et al., Hydrogen gas permeation through amorphous and partially crystallized Fe40Ni38Mo4B18, Mat. Res. vol. 15 No. 5 Aug. 30, 2012. [cited by applicant]
Sauder, Ceramic matrix composites: nuclear applications, Ceramic Matrix Composites: Materials, Modeling and Technology: pp. 609-646 (2014). [cited by applicant]
Senor et al., Thermophysical property correlations for the niobium-1% zirconium alloy, J. Nuclear Materials, 173(3):261-73 (1990). [cited by applicant]
Senor et al., Transport property correlations for the niobium-1% zirconium alloy, J. Nuclear Materials, 173(3):274-83 (1990). [cited by applicant]
Serra et al., Hydrogen permeation measurements on alumina, J. Am. Ceramic Soc., 88:15 (2005). [cited by applicant]
Shivprasad et al., High temperature moderator material for microreactors, No. LA-UR-20-21710, Los Alamos National Lab, United States (Feb. 25, 2020). [cited by applicant]
Simnad, The U—ZrHx alloy: its properties and use in TRIGA fuel, Nuclear Engineering and Design, 64(3):403-22 (1981). [cited by applicant]
Singh et al., Interlaboratory round robin study on axial tensile properties of SiC—SiC CMC tubular test specimens, Int. J. Applied Ceramic Technology, 15(6):1334-49 (2018). [cited by applicant]
Snead et al., Handbook of SiC properties for fuel performance modeling (thermal conductibility), J. Nuclear Materials, 371:329-77 (2007). [cited by applicant]
Snyder, Aircraft Nuclear Propulsion: An Annotated Bibliography, prepared for the United States Air Force History and Museums Program, May 3, 1996. [cited by applicant]
Song, Hydrogen permeation resistance of plasma-sprayed Al2O3 and Al2O3-13wt.% TiO2 ceramic coatings on austenitic stainless steel, Surface and Coatings Technology, 168:191 (2003). [cited by applicant]
Stone et al., Stress analysis and probabilistic assessment of multi-layer SiC-based accident tolerant nuclear fuel cladding, J. Nuclear Materials, 466:682-97 (2015). [cited by applicant]
Summary Report of HTRE No. 3 Nuclear Excursion, United States: N. p., 1965. Web. doi: 10.2172/4643464. [cited by applicant]
Suzuoka, Lattice and Grain Boundary Diffusion in polycrystals, Transactions of the Japan Institute of Metals, 1961 vol. 2 Issue 1 pp. 25-32. [cited by applicant]
Tamura, Hydrogen Permeation Characteristics of TiN-Coated Stainless Steels, Journal of Materials Science and Engineering A, 5 (5-6) (2015) 204-208. [cited by applicant]
U.S. Appl. No. 16/925,781, “Hydrogren Permeation Barrier Coatings and Methods of Making the Same”, filed Jul. 10, 2020. [cited by applicant]
Vetrano, Hydrides as neutron moderator and reflector materials, Nuclear Engineering and Design, 14(3):390-412 (1971). [cited by applicant]
Ward et al., Technical challenges and future direction for high-efficiency metal hydride thermal energy storage systems, Appl. Physics A, 122(4):462 (2016). [cited by applicant]
Yokoyama et al. Proceedings of the International Conference on Nuclear Engineering (ICONE-9), pp. 8-12 (2001). [cited by applicant]
Yvon (ed.), Structural Materials for Generation IV Nuclear Reactors, Woodhead Publishing (2016). [cited by applicant]
Zhu, Aerospace ceramic materials: thermal, environmental barrier coatings and SiC/SiC ceramic matrix composites for turbine engine applications, NASA/TM-2018-219884 (2018). [cited by applicant]