History of Carbon and Graphite Foams


    Carbon foams were first developed by researchers in the late 60’s as a reticulated vitreous (glassy) carbon foam.  Ford (1) reported on carbon foams produced by carbonizing thermosetting organic polymer foams through a simple heat treatment.  Then, Googin et al. (2) at the Oak Ridge Atomic Energy Commission Laboratory reported the first process dedicated to controlling the structure and material properties of carbon and graphitic foams by varying the precursor material (partially cured urethane polymer).  In the several decades following these initial discoveries, many researchers explored a variety of applications for these materials (3-12)  ranging from electrodes to insulating liners for temperatures up to 2500°C.  In fact, reticulated carbon foams have been used as the template for many of the metal and ceramic foams currently used in industry.   In the 1970’s, research focused primarily on producing carbon foams from alternative precursors.  For example, Klett, R. (6) at the Sandia National Laboratories produced the first carbon foams from cork, a natural cellular precursor.  Others worked on various processing and precursor changes in an attempt to modify properties and reduce cost.  The majority of these carbon foams were used for thermal insulation, although some structural applications were found.  

    In the early 1990’s, researchers at the Wright Patterson Air Force Base Materials Lab pioneered mesophase-derived graphitic foams, specifically for replacing expensive 3-D woven fiber performs in polymer composites and as replacements for honeycomb materials (13-20).  Their work was centered on developing a highly structural material that was lightweight, and to date, exhibits the highest specific strength of carbon foams.  Concurrently, Ultramet Corp, performed research on RVC foam and used chemical vapor deposition (CVD) as a technique to place pyrolytic graphite on the glassy carbon ligaments of RVC, producing 3-D carbon structures with high-modulus ligaments.  

With the goal of producing very inexpensive carbon foams, researchers at West Virginia University developed a method that used coal as a precursor for high strength foams with excellent thermal insulation properties (21-24).   In 1997, Klett, J. (25-35) at the Oak Ridge National Laboratory (ORNL) reported the first graphitic foams with bulk thermal conductivities greater than 40 W/m·K (recently, conductivities up to 180 W/m·K have been measured (36)).   By combining an open cellular structure with a thermal conductivity to weight ratio of greater than 200 (compared to 45 for copper), this material presents a unique opportunity to radically change the approach to solving many heat transfer problems.  This graphite material has been examined for the core of heat transfer devices such as radiators and heat sinks, evaporative cooling and phase change devices.  Furthermore, the ability of the graphite foam to intercalate lithium and absorb acoustic energy makes them candidates for several applications beyond thermal management.


References
  1. W. Ford, Method of Making Cellular Refractory Thermal Insulating Material, US Patent 3,121,050, 1964.
  2. J. Googin, J. Napier, M. Scrivner, Method for Manufacturing Foam Carbon Products, US Patent 3,345,440, 1967.
  3. F. C. Cowlard, J. C. Lewis, Journal of Materials Science 2, 507-512 (1967).
  4. W. F. Knippenberg, B. Lersmacher, Phillips Technical Review 36, 93-103 (1976).
  5. T. Noda, M. Inagaki, S. Yamada, Journal of Non-Crystalline Solids 1, 285-302 (1969).
  6. R. D. Klett, High Temperature Insulating Carbonaceous Material, US Patent 3,914,392, 1975.
  7. A. Bonzom, A. P. Crepaux, A.-M. E. J. Montard, Process for Preparing Pitch Foams and Products so Produced, US Patent 4,276,246, 1981.
  8. B. Ettinger, S. Wolosin, Refractory Porous Bodies, US Patent 3,666,526, 1972.
  9. H. Luhleich, e. al., Method of Making Carbonaceous Bodies, US Patent 3,927,187, 1975.
  10. R. Marek, W. Udichak, Foam Carbonization and Resulting Structure, US Patent 3,922,334, 1975.
  11. H.-G. Franck et al., Process for Making a Foam from a Composition Comprising Bituminous Masses, a Novolac, and Hexamethylenetetramine, US Patent 3,784,487, 1974.
  12. C. Vinton, C. Franklin, Method for the Preparation of Carbon Structures, US Patent 3,927,186, 1975.
  13. J. W. Hager, Materials Research Society Symposium Proceedings 270, 41-46 (1992).
  14. J. W. Hager, D. P. Anderson, 21st Biennial Conference on Carbon Extended Abstracts 1993.
  15. J. W. Hager, D. P. Anderson, 40th International Sampe Symposium, Anaheim, California, May 8-11 1995.
  16. J. W. Hager, M. L. Lake, Materials Research Society Symposium Proceedings 270, 29-34 (1992).
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  18. S. S. Sandhu, J. W. Hager, Materials Research Society Symposium Proceedings 270, 35-40 (1992).
  19. K. Kearns, 21st Annual Conference on Composites, Materials, and Structures, Cocoa Beach, Florida, January 26-31 1997.
  20. K. M. Kearns, Process for Preparing Pitch Foams, US Patent 5,868,974, 1999.
  21. A. H. Stiller, P. G. Stansberry, J. W. Zondlo, Method of Making a Carbon Foam Material and Resultant Product, US Patent 5,888,469, 1999.
  22. A. H. Stiller, A. Yocum, J. Plucinski, Method of Making a Reinfoced Carbon Foam Material and Related Product, US Patent 6,183,854, 1999.
  23. A. H. Stiller, P. Stansbery, J. Zondlo, Method of Making a Carbon Foam Material and Resultant Product, US Patent 6,346,226, 2001.
  24. A. H. Stiller, P. Stansbery, J. Zondlo, Method of Making a Carbon Foam Material and Resultant Product, US Patent 6,241,957, 1999.
  25.  J. Klett, Proceedings of the 1998 43rd International SAMPE Symposium and Exhibition, Part 1 (of 2), Anaheim, California, U.S.A., May 31-June 4 1998.
  26. J. Klett, Journal of Composites in Manufacturing 15, 1-7 (1999).
  27. J. Klett, Process for Making Carbon Foam, US Patent 6,033,506, 2000.
  28. J. Klett, Pitch-Based Carbon Foam and Composites, US Patent 6,261,485, 2001.
  29. J. Klett, Pitch Based Foam with Particulate, US Patent 6,287,375, 2001.
  30. J. Klett, Method for Extruding Pitch Based Foam, US Patent 6,344,159, 2002.
  31. J. Klett, Pitch Based Carbon Foam and Composites, US Patent 6,387,343, 2002.
  32. J. Klett, Method of Casting Pitch Based Foam, US Patent 6,398,994, 2002.
  33. J. Klett, T. Burchell, Pitch Based Carbon Foam Heat Sink with Phase Change Material, US Patent 6,399,149, 2002.
  34. J. Klett, T. D. Burchell, Science and Technology of Carbon, Strasbourg, France, July 8-9 1998.
  35. J. Klett, C. Walls, T. D. Burchell, Carbon '99, Charleston, SC, July 11-16 1999.
  36. J. W. Klett, A. McMillan, N. Gallego, “Carbon Foam for Electronics Cooling” (National Laboratory Fuel Cell Annual Report, FY 2002).