Patent
Unsupported palladium alloy membranes and methods of making same
| العنوان: | Unsupported palladium alloy membranes and methods of making same |
|---|---|
| Patent Number: | 9,044,715 |
| تاريخ النشر: | June 02, 2015 |
| Appl. No: | 12/197218 |
| Application Filed: | August 22, 2008 |
| مستخلص: | The invention provides support-free palladium membranes and methods of making these membranes. Single-gas testing of the unsupported foils produced hydrogen permeabilities equivalent to thicker membranes produced by cold-rolling. Defect-free films as thin as 7.2 microns can be fabricated, with ideal H2/N2 selectivities as high as 40,000. Homogeneous membrane compositions may also be produced using these methods. |
| Inventors: | Way, J. Douglas (Boulder, CO, US); Thoen, Paul (Littleton, CO, US); Gade, Sabina K. (Westminster, CO, US) |
| Assignees: | Colorado School of Mines (Golden, CO, US) |
| Claim: | 1. A method of forming a free-standing hydrogen permeable palladium membrane comprising: electroless plating of a surface of a support to form a palladium membrane on the support; intentionally removing the palladium membrane from the support to produce the free-standing hydrogen permeable palladium membrane; and plating the free-standing hydrogen permeable palladium membrane with a second metal. |
| Claim: | 2. The method of claim 1 , wherein the support is seeded with metallic palladium crystallites prior to the electroless plating. |
| Claim: | 3. The method of claim 2 , wherein the seeding comprises contacting the support with a solution of palladium acetate in an organic solvent. |
| Claim: | 4. The method of claim 2 , further comprising decomposing the palladium acetate prior to the electroless plating. |
| Claim: | 5. The method of claim 4 , wherein the decomposing comprise immersing the seeded support in a 3 wt % solution of hydrogen peroxide. |
| Claim: | 6. The method of claim 5 , wherein the immersing is conducted for about 30 minutes. |
| Claim: | 7. The method of claim 2 , further comprising reducing the support. |
| Claim: | 8. The method of claim 7 , wherein the reducing comprises contacting the support with hydrazine after the seeding. |
| Claim: | 9. The method of claim 8 , wherein the contacting is conducted for about 20 minutes at about 50° C. |
| Claim: | 10. The method of claim 1 , wherein the support is a stainless steel support. |
| Claim: | 11. The method of claim 10 , wherein the support is a mirror-finished stainless steel support. |
| Claim: | 12. The method of claim 1 , wherein the electroless plating comprises immersing the support in a palladium plating bath. |
| Claim: | 13. The method of claim 12 , wherein the palladium plating bath contains no ethylenediaminetetraacetic (EDTA). |
| Claim: | 14. The method of claim 1 , wherein the electroless plating comprises immersing the support in a palladium plating bath at about 50° C.; and, adding hydrazine to the plating bath. |
| Claim: | 15. The method of claim 14 , wherein the hydrazine is a 3M solution of hydrazine added to the plating solution in a 100:1 ratio of plating bath to hydrazine. |
| Claim: | 16. The method of claim 1 , wherein the removing comprises scoring the edge of the palladium film and lifting the film away from the support. |
| Claim: | 17. The method of claim 1 , further comprising electroless plating of a second metal onto the palladium membrane to form a layered metal membrane before the removing. |
| Claim: | 18. The method of claim 17 , wherein the second metal is selected from the group consisting of copper, silver and gold. |
| Claim: | 19. The method of claim 17 , further comprising annealing the layered metal membrane prior to the removing. |
| Claim: | 20. The method of claim 1 , wherein the second metal is selected from the group consisting of copper, silver and gold. |
| Patent References Cited: | 2773561 December 1956 Hunter 3155467 November 1964 Yamamoto et al. 3350845 November 1967 McKinely 3439474 April 1969 McKinely 3556955 January 1971 Ancker et al. 3849076 November 1974 Gryaznov et al. 3881891 May 1975 Goltsov et al. 4179470 December 1979 Mischenko et al. 4313013 January 1982 Harris 4343013 August 1982 Bader et al. 4496373 January 1985 Behr et al. 4911803 March 1990 Kunz 5139541 August 1992 Edlund 5149420 September 1992 Buxbaum et al. 5215729 June 1993 Buxbaum 5451386 September 1995 Collins et al. 5498278 March 1996 Edlund 5518053 May 1996 Robison 5518530 May 1996 Sakai et al. 5645626 July 1997 Edlund et al. 5652020 July 1997 Collins et al. 5738708 April 1998 Peachey et al. 5888273 March 1999 Buxbaum 5904754 May 1999 Juda et al. 5931987 August 1999 Buxbaum 5980989 November 1999 Takahashi et al. 5997594 December 1999 Edlund et al. 6086729 July 2000 Bredesen et al. 6103028 August 2000 Juda et al. 6152984 November 2000 Drnevich 6152987 November 2000 Ma et al. 6152995 November 2000 Edlund 6168650 January 2001 Buxbaum 6171574 January 2001 Juda et al. 6183543 February 2001 Buxbuam 6214090 April 2001 Dye et al. 6221117 April 2001 Edlund et al. 6238465 May 2001 Juda et al. 6267801 July 2001 Baake et al. 6319306 November 2001 Edlund et al. 6372363 April 2002 Krueger 6375906 April 2002 Edlund et al. 6376113 April 2002 Edlund et al. 6383670 May 2002 Edlund et al. 6416729 July 2002 DeBerry et al. 6419728 July 2002 Edlund 6451464 September 2002 Edlund et al. 6458189 October 2002 Edlund et al. 6461408 October 2002 Buxbaum 6465118 October 2002 Dickman et al. 6494937 December 2002 Edlund et al. 6495227 December 2002 Cahuzac 6537352 March 2003 Edlund et al. 6540813 April 2003 Nelson et al. 6541676 April 2003 Franz et al. 6562111 May 2003 Edlund et al. 6569227 May 2003 Edlund et al. 6576350 June 2003 Buxbaum 6596057 July 2003 Edlund et al. 6649291 November 2003 Iijima et al. 6649559 November 2003 Drost et al. 6761929 July 2004 Damle 6916454 July 2005 Alvin 7108935 September 2006 Bauer et al. 7749305 July 2010 Bossard et al. 8163064 April 2012 Bredesen et al. 2003/0190486 October 2003 Roa 2004/0244583 December 2004 Ma et al. 2005/0109609 May 2005 Rei et al. 2005/0147859 July 2005 Kiefer et al. 2005/0249975 November 2005 Sandberg et al. 2006/0093848 May 2006 Senkevich et al. 2006/0188737 August 2006 Roa et al. 2008/0038567 February 2008 Way et al. 2008/0210088 September 2008 Pledger 2009/0000480 January 2009 Dardas et al. 2010/0092353 April 2010 Noda 2012/0012004 January 2012 Way et al. 0783919 July 1997 1096026 May 2001 63-295402 January 1988 63-294925 December 1988 8-266876 October 1996 9-029079 February 1997 10-203802 August 1998 WO 01/53005 July 2001 WO 2006/031080 March 2006 |
| Other References: | Zhao et al. (“Preparation of palladium composite membranes by modified electroless plating procedure”, Journal of Membrane Science 142 (1998) 147-157). cited by examiner Rodman et al. (“Studies of the oxidation of palladium complexes by the advanced oxidation process pretreatment of model catalysts for precious metal analysis”, Talanta 70 (2006) 426-431). cited by examiner Aggarwal, et al., “Spontaneous Ordering of Oxide Nanostructures”, Science, Mar. 24, 2000, Voil. 287, pp. 2235-2237. cited by applicant Alefeld, et al., (eds), Hydrogen in Metals I: Basic Properties, 1978, pp. 324-326, 342-348, Springer-Verlag, Berlin, Germany. cited by applicant Ali, et al. “Irreversible Poisoning of Pd—Ag Membranes”, International Journal of Hydrogen Energy, 1994, vol. 19, No. 11, pp. 877-880, Elsevier Science Ltd., London, UK. cited by applicant Amandusson, et al., “The effect of CO and O2 on hydrogen permeation through a palladium membrane”, Applied Surface Science, 2000, vol. 153, pp. 259-267. cited by applicant Armor “Applications of Catalytic Inorganic Membrane Reactors to Refinery Products”, Journal of Membrane Science, 1998, vol. 147, pp. 217-233, Elsevier Science B.V., Amsterdam, The Netherlands. cited by applicant Armor, “Membrane Catalysis: Where Is It Now, What Needs to Be Done?”, Catalysis Today, 1995, vol. 25, pp. 199-207, Elsevier Science B.V., Amsterdam, The Netherlands. cited by applicant Barbieri, et al. “Methane Steam Reforming Analysis in a Palladium-Based Catalytic Membrane Reactor”, Industrial & Engineering Chemistry Research, 1997, vol. 36, pp. 3396-3374, American Chemical Society, Washington, DC, USA. cited by applicant Benesi, et al. “Preparation of Highly Dispersed Catalytic Metals: Platinum Supported on Silica Gel”, Journal of Catalyis, 1968, vol. 10, pp. 328-335, Academic Press, London, UK. cited by applicant Berseneva, et al., “Alloys of Palladium With Metals of the Platinum Group as Hydrogen-Permeable Membrane components at High Temperature of Gas Separation”, International Journal of Hydrogen Energy, 1993, vol. 18, No. 1, pp. 15-18, Pergamon Press Ltd., Great Britian. cited by applicant Brey, et al., “Hydrogen as an energy carrier and its production by nuclear power”, International Atomic Energy Agency, 1999, IAEA-TECDOC-1085, Vienna Austria, pp. 1-348. cited by applicant Buxbaum, et al., “Hydrogen Transport Through Tubular Membranes of Palladium-Coated Tantalum and Niobium”, Industrial & Engineering Chemistry Research, 1996, vol. 35, pp. 530-537, American Chemical Society, Washington, DC, USA. cited by applicant Collins, et al., “Catalytic Dehydrogenation of Propane in Hydrogen Permselective Membrane Reactors”, Industrial & Engineering Chemistry Research, 1996, vol. 35,pp. 4398-4405, American Chemical Society, Washington, DC, USA. cited by applicant Collins, et al., “Preparation of Characterization of a Composite Palladium-Ceramic Membrane”, Industrial & Engineering Chemistry Research, 1993, vol. 32, pp. 3006-3013, American Chemical Society, Washington, DC, USA. cited by applicant Criscuoli, et al., “An Economic Feasibility Study for Water Gas Shift Membrane Reactor”, Journal of Membrane Science, 2001, vol. 181, pp. 21-27, Elsevier Science B.V., Amsterdam, The Netherlands. cited by applicant Dolan, et al., Composition and operation of hydrogen-selective amorphous alloy membranes, Journal of Membrane Science, 2006, vol. 285, pp. 30-55. cited by applicant Dorling, et al., “The Structure and Activity of Supported Metal Catalysts”, Journal of Catalysis, 1971, vol. 20, pp. 190-201, Academic Press, London, UK. cited by applicant Doyle, et al., “The Influence of intercystalline defects on hydrogen activity and transport in nickel”, Acta Metallurgica et Materialia, 1995, vol. 43, No. 8, pp. 3027-3033. cited by applicant Edlund, “A Membrane Reactor for H2S Decomposition”, FETC 1996 Conference Proceedings: Advanced Coal-Fired Power Systems '96 Review Meeting, Morgantown, West Virginia, Jul. 16-18, 1996, pp. 1-9, U.S. Department of Energy, Office of Fossil Energy, USA. cited by applicant Fisher, et al. “Psolution of Hydrogen in Palladium/Copper Alloys”, Journal of Solid State Chemistry, 1977, vol. 20, pp. 149-158, Academic Press Inc., Great Britain. cited by applicant Flanagan, et al., “Solubility of Hydrogen (1 atm, 298 K) in Some Copper/Palladium Alloys”, Solid State Communications, 1975, vol. 16, pp. 529-532, Pergamon Press, Great Britain. cited by applicant Foley, et al.“Effect of a Model Hydrogenation on a Catalytic Palladium Membrane”, Selectivity in Catalysis, 1993, pp. 168-184, American Chemical Society—published by Oxford University Press, UK. cited by applicant Foo “Chapter 4: Preparation and Characterization of a Composite Palladium—Gold Ceramic Membrane” and “Chapter 5: Conclusions and Recommendations”, Hydrogen Separation in Palladium Ceramic Membranes and Palladium—Gold Ceramic Membranes, 1995, pp. 71-90, Colorado School of Mines, Golden, USA. cited by applicant Gade, et al., “Fabrication of Unsupported Palladium-Alloy Dfilms by Electroless Plating”, Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2007, vol. 52, No. 2, pp. 661-662. cited by applicant Gade, et al., “Unsupported palladium allow foil membranes fabricated by electroless plating”, Journal of Membrane Science, 2008, vol. 316, pp. 112-118. cited by applicant Grashoff, et al. “The Purification of Hydrogen—a Review of the Technology Emphasising the Current Status of Palladium Membrane Diffusion”, Platinum Metals Review, 1982, pp. 157-169, Johnson Matthey PLC, London, UK. cited by applicant Gryaznov et al., “Hydrogen Permeability of Some Metallopolymer Membranes”, Polymer Science, 1993, vol. 35, No. 3, pp. 365-368, Russian Academy of Sciences, Moscow, Russia. cited by applicant Gryaznov, et al. “Palladium—Ruthenium Alloys as Membrane Catalysts”, Dokl. Akad. Nauk SSSR, Jul. 1973, pp. 604-606, Russian Academy of Sciences, Moscow, Russia. cited by applicant Gryaznov, “Membrane Catalysis”, Catalysis Today, 1999, vol. 51, pp. 391-395, Elsevier Science B.V., Amsterdam, The Netherlands. cited by applicant Hollein, et al., “Preparation and characterization of palladium composite membranes for hydrogen removal in hydrocarbon dehydrogenation membranes reactors”, Catalysis Today, 2001, vol. 67, pp. 33-42. cited by applicant Hughes, et al., “A Comparative Study of Hydrogen Permeabilities and Solubilities in Some Palladium Solid Solution Alloys”, Journal of Less-Common Metals, 1978, vol. 61, pp. P9-P21, Elsevier Sequois A.A., Lausanne, The Netherlands. cited by applicant Hunter, “A New Hydrogen Purification Process”, Platinum Metals Review, 1960, vol. 4, pp. 130-131, Johnson Matthey PLC, London, UK. cited by applicant Jayaraman, et al., “Fabrication of Ultrathin Mettalic Membranes on Ceramic Supports by Sputter Deposition”, Journal of Membrane Science, 1995, vol. 99, pp. 89-100, Elsevier Science B.V., Amsterdam, The Netherlands. cited by applicant Kajiwara, et al., “Hydrogen Permeation Properties Through Composite Membranes of Platinum Supported on Porous Alumina”, Catalysis Today, 2000, vol. 56, pp. 65-73, Elsevier Science B.V., Amsterdam, The Netherlands. cited by applicant Karavanov, et al.,“Hydrogenation of Acetylenic and Ethylenic Alcohols in the Liquid Phase on Membrane Catalysts Consisting of Binary Alloys of Palladium With Nickel and Ruthenium”, Kinet. Catal., 1984, vol. 25, pp. 56-60, Plenum Publishing Corporation, New York, USA. cited by applicant Karpova, et al., “Sorption of Hydrogen by Disperse Palladium—Copper Alloys”, Russ. J. Phys. Chem., 1959, vol. 33, No. 6, pp. 1393-1400, Leningrad (English summary at end of article). cited by applicant Kueler, et al., “Characterization of electroless plated palladium—silver alloy membranes”, Thin Solid Films, 1999, vol. 347, pp. 91-98. cited by applicant Keuler, et al., “Characterising Palladium—Silver and Palladium—Nickel Alloy Membranes Using SEM, XRD and PIXE”, Nuclear Instruments and Methods in Physics Research, 1999, B 158, pp. 378-382, Elsevier Science B.V., Amsterdam, The Netherlands. cited by applicant Keuler, et al., “Developing a heating procedure to optimise hydrogen permeance through Pd—Ag membranes of thickness less than 2.2μm”, Journal of Membrane Science, 2002, vol. 195, pp. 203-213. cited by applicant Kikuchi, et al., “Preparation of Supported Thin Palladium—Silver Alloy Membranes and Their Characteristics for Hydrogen Separation”, Gas Separation & Purification, 1991, vol. 5, pp. 261-266, Butterworth-Heineman Ltd., USA. cited by applicant Knapton, “Palladium Alloys for Hydrogen Diffusion Membranes”, Platinum Metals Review, 1977, vol. 21, pp. 44-50, Johnson Matthey PLC, London, UK. cited by applicant Koppel, et al., “A Fuel Cell Primer: The Promise and the Pitfalls”, Sep. 15, 2000, Rev. 4, pp. 1-31. cited by applicant Kajiwara, et al., “Stability and hydrogen permeation behavior of supported platinum membranes in presence of hydrogen sulfide”, International Journal of Hydrogen Energy, 1999, vol. 24, p. 839-844. cited by applicant Kulprathipanja, et al., Pd and Pd—Cu membranes: Inhibition of h2 permeation by H2S, Journal of Membrane Science, 2005, vol. 254, pp. 49-62. cited by applicant Lemier, et al., “Grain boundary segregation, stress and stretch: Effects on hydrogen absorption in nanocrystalline palladium”, Acta Materialia, 2007, vol. 55, pp. 1241-1254. cited by applicant Lewis, The Palladium Hydrogen System, 1967, pp. 70-71, 78-79, 82-85, 116-117, and 144-145, Academic Press, London, UK. cited by applicant Li, et al., “Preparation of Pd/Ceramic Composite Membrane 1. Improvement of the Conventional Preparation Technique”, Journal of Membrane Science, 1996, vol. 110, pp. 257-260, Elsevier Science B.V., Amsterdam, The Netherlands. cited by applicant Li, et al, The effect of carbon monoxide and steam on the hydrogen permeability of a Pd/stainless steel membrane, Journal of Membrane Science, 2000, vol. 165, pp. 135-141. cited by applicant McCool, et al., “Composition Control and Hydrogen Permeation Characteristics of Suptter Deposited Palladium—Silver Membranes”, Journal of Membrane Science, 1999, vol. 161, pp. 67-76, Elsevier Science B.B., The Netherlands. cited by applicant Morreale, et al., “Effect of hydrogen—sulfide on the hydrogen permeance of palladium—copper alloys at elevated temperatures”, Journal of Membrane Science, 2004, vol. 241, pp. 219-224. cited by applicant Morreale, et al., “The Permeability of Hydrogen in Bulk Palladium at Elevated Temperatures and Pressures”, Journal of Membrane Science, 2003, vol. 212, pp. 87-97. cited by applicant Nam, et al., “Hydrogen Separation by Pd Alloy Composite Membranes: Introduction of Diffusion Barrier”, Journal of Membrane Science, 2001, vol. 192, pp. 177-185, Elsevier Science B.V., Amsterdam, The Netherlands. cited by applicant Nam, et al.,“Preparation of a Palladium Alloy Composite Membrane Supported in a Porous Stainless Steel by Vacuum Electrodeposition,” Journal of Membrane Science, Jan. 10, 1999, vol. 153, No. 2, pp. 163-173, Elsevier Science, B.V., United Kingdom. cited by applicant Paglieri, et al.,“A New Preparation Technique for Pd/Alumina Membranes with Enhanced High-Temperature Stability”, Industrial & Engineering Chemistry Research, 1999, vol. 38, No. 5, pp. 1925-1936, American Chemical Society, Washington, DC, USA. cited by applicant Paglieri, “Chapter 6: Preparation of Palladiium—Copper Alloy Membranes for Hydrogen Separation” and “Chapter 7: Conclusions” and “Chapter 8: Recommendations for Future Work”, Palladium and Palladium—Copper Composite Membranes for Hydrogen Separation, 1999, pp. 119-146, Colorado School of Mines, Golden, USA. cited by applicant Paglieri, et al., “Innovations in palladium membrane research”, Separations and Purification Methods, 2002, vol. 31, No. 1, pp. 1-169. cited by applicant Di Pascasio, et al., “H2 plasma for hydrogen loading in Pd”, Intermetallics, 2003, vol. 11, pp. 1345-1354. cited by applicant Peachey, et al., “Composite Pd/Ta Metal Membranes for Hydrogen Separation”, Journal of Membrane Science, 1996, vol. 111, pp. 123-133, Elsevier Science B.V., Amsterdam, The Netherlands. cited by applicant Piper, “Diffusion of Hydrogen in Copper—Palladium Alloys”, Journal of Applied Physics, 1966, vol. 37, No. 2, pp. 715-721, American Institute of Physics, New York, USA. cited by applicant Roa, et al., “The Influence of Alloy Composition on the H2 Flux of Composite Pd—Cu Membranes”, Desalination, 2002, vol. 147, pp. 411-416, Elsevier Science B.V., Amsterdam, The Netherlands. cited by applicant Rodina, et al., “The Interaction of Hydrogen with Certain Palladium—Gold and Palladium—Silver—Gold Alloys”, Russian Journal of Physical Chemistry, 1971, vol. 45, No. 5, pp. 621-623. cited by applicant Roy, et al., “Economics and Simulation of Fluidized Bed Membrane Reforming”, International Journal of Hydrogen Energy, 1998, vol. 23, No. 9, pp. 745-752, Elsevier Science Ltd., Great Britain. cited by applicant Saracco, et al., “High-Temperature Membrane Reactors: Potential and Problems”, Chemical Engineering Science, 1999, vol. 54, pp. 1997-2017, Elsevier Science Ltd., Oxford, UK. cited by applicant Shu, et al., “Simultaneous Deposition of Pd and Ag on Porous Stainless Steel by Electroless Plating”, Journal of Membrane Science, 1993, vol. 77, pp. 181-195, Elsevier Science Publishers B.V., Amsterdam, The Netherlands. cited by applicant Subramanian, et al., “Cu—Pd (Copper—Palladium)”, Binary Alloy Phase Diagrams, 1990, vol.s 1-3, pp. 947-948, ASM International, USA. cited by applicant Thomas, et al., “Fuel Cells—Green Power”, 1999, pp. 1-33, Los Alamos National Laboratory, Los Alamos, USA. cited by applicant Uemiya, et al., “Hydrogen Permable Palladium—Silver Alloy Membrane Supported on Porous Ceramics”, Journal of Membrane Science, 1991, vol. 56, pp. 315-325, Elsevier Science Publishers B.V, Amsterdam, The Netherlands. cited by applicant Uemiya, et al., “Separation of Hydrogen Through Palladium Thin Film Supported on a Porous Glass Tub”, Journal of Membrane Science, 1991, vol. 56, pp. 303-313, Elsevier Science Publishers B.V., Amsterdam, The Netherlands. cited by applicant Uemiya, “State-of-the-Art of Supported Metal Membranes for Gas Separation”, Separation and Purification Methods, 1999, vol. 28, No. 1, pp. 51-85, Marcel Dekker, Inc., New York, USA. cited by applicant Van Swaay, et al., “Permeability and Diffusion on Hydrogen Through Palladium”, Transactions of the Metallurgical Society of AIME, Apr. 1960, vol. 218, pp. 285-289, The Metallurgical Society of AIME, USA. cited by applicant Wu, et al., “Preparation of a Palladium Composite Membrane by an Inproved Electroless Plating Technique”, Industrial & Engineering Chemistry Research, 2000, vol. 39, pp. 342-348, American Chemical Society, Washington, DC, USA. cited by applicant Xomeritakis, et al., “Fabrication of Thin Metallic Membranes by MOCVD and Sputtering”, Journal of Membrane Science, 1997, vol. 133, pp. 217-230, Elsevier Science B.V., Amsterdam, The Netherlands. cited by applicant Yeung, et al., “Novel Preparation of Pd/Vycor Composite Membranes”, Catalysis Today, 1995, pp. 231-236, 25, Elsevier Science B.V., Amsterdam, The Netherlands. cited by applicant Yeung, et al., “Novel Preparation Techniques for Thin Metal-Ceramic Composite membranes”, AIChE Journal, Sep. 1995, vol. 41, No. 9, pp. 2131-2139, American Institute of Chemical Engineers, New York, USA. cited by applicant Zetkin, et al., “Diffusion and Penetrability of Deuterium in the Alloy Pd-53 at % Cu”, Sov. Phys. Solid State, 1992, vol. 34, No. 1, pp. 83-85, American Institute of Physics, New York, USA. cited by applicant Zetkin, et al., “Influence of Structural Transformations on the Diffusion Parameters of Deuterium in Palladium—Copper Alloys”, Phys. Met. Metall., 1987, vol. 64, No. 5, pp. 130-134, Pergamon Press PLC, Poland. cited by applicant Zhang, et al., “High Temperature PEM Fuel Cells”, Journal of Power Sources, 2006, vol. 160, pp. 872-891. cited by applicant Zhao, et al., “Preparation and characterization of palladium-based composite membranes by electroless plating and magnetron sputtering”, Catalysis Today, 2000, vol. 56, pp. 89-96. cited by applicant Cheng et al., “Effects of electroless plating chemistry on the synthesis of palladium membranes,” Journal of Membranes, 2001, vol. 182, pp. 195-203. cited by applicant U.S. Appl. No. 13/356,410, filed Jan. 23, 2012, Way et al. cited by applicant Gade et al. “Palladium—ruthenium membranes for hydrogen separation fabricated by electroless co-deposition,” International Journal of Hydrogen Energy, 2009, vol. 34, pp. 6484-6491. cited by applicant Nam et al., “Methane steam reforming in a Pd-Ru membrane reactor,” Korean Journal of Chemical Engineering, 2000, vol. 17, Iss. 3, pp. 288-291. (Abstract only). cited by applicant Uemiya et al., “Palladium—Rhodium Alloy Membrane Fabricated Using Electroless Plating Technique and Its Hydrogen Permeance,” Journal of the Japan Institute of Metals and Materials, 2007, vol. 71, No. 9, pp. 736-741. cited by applicant |
| Primary Examiner: | Zhu, Weiping |
| Attorney, Agent or Firm: | Sheridan Ross P.C. |
| رقم الانضمام: | edspgr.09044715 |
| قاعدة البيانات: | USPTO Patent Grants |
| الوصف غير متاح. |