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Ceramic–metal composites for heat exchangers in concentrated solar power plants

Nature volume 562, pages 406–409 (2018)Cite this article

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Abstract

The efficiency of generating electricity from heat using concentrated solar power plants (which use mirrors or lenses to concentrate sunlight in order to drive heat engines, usually involving turbines) may be appreciably increased by operating with higher turbine inlet temperatures, but this would require improved heat exchanger materials. By operating turbines with inlet temperatures above 1,023 kelvin using closed-cycle high-pressure supercritical carbon dioxide (sCO2) recompression cycles, instead of using conventional (such as subcritical steam Rankine) cycles with inlet temperatures below 823 kelvin1,2,3, the relative heat-to-electricity conversion efficiency may be increased by more than 20 per cent. The resulting reduction in the cost of dispatchable electricity from concentrated solar power plants (coupled with thermal energy storage4,5,6) would be an important step towards direct competition with fossil-fuel-based plants and a large reduction in greenhouse gas emissions7. However, the inlet temperatures of closed-cycle high-pressure sCO2 turbine systems are limited8 by the thermomechanical performance of the compact, metal-alloy-based, printed-circuit-type heat exchangers used to transfer heat to sCO2. Here we present a robust composite of ceramic (zirconium carbide, ZrC) and the refractory metal tungsten (W) for use in printed-circuit-type heat exchangers at temperatures above 1,023 kelvin9. This composite has attractive high-temperature thermal, mechanical and chemical properties and can be processed in a cost-effective manner. We fabricated ZrC/W-based heat exchanger plates with tunable channel patterns by the shape-and-size-preserving chemical conversion of porous tungsten carbide plates. The dense ZrC/W-based composites exhibited failure strengths of over 350 megapascals at 1,073 kelvin, and thermal conductivity values two to three times greater than those of iron- or nickel-based alloys at this temperature. Corrosion resistance to sCO2 at 1,023 kelvin and 20 megapascals was achieved10 by bonding a copper layer to the composite surface and adding 50 parts per million carbon monoxide to sCO2. Techno-economic analyses indicate that ZrC/W-based heat exchangers can strongly outperform nickel-superalloy-based printed-circuit heat exchangers at lower cost.

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Fig. 1: Fabrication of dense, channelled ZrC/W plates.
Fig. 2: Corrosion resistance of a Cu-bearing ZrC/W composite to a buffered supercritical CO/CO2-bearing fluid at 1,023 K.
Fig. 3: Calculated power density of a printed-circuit-type heat exchanger versus allowed stress at 1,073 K.

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Data availability

Data generated or analysed during this study are available from the corresponding author on reasonable request. Data reported are available within the paper. The Ricardo Excel model of ZrC/W-based heat exchanger processing costs is available from the corresponding author on reasonable request.

References

  1. Dostal, V., Hejzlar, P. & Driscoll, M. J. The supercritical carbon dioxide power cycle: comparison to other advanced power cycles. Nucl. Technol. 154, 283–301 (2006).

    Article  CAS  Google Scholar 

  2. Weinstein, L. E. et al. Concentrating solar power. Chem. Rev. 115, 12797–12838 (2015).

    Article  CAS  Google Scholar 

  3. Irwin, L. & Moullec, Y. L. Turbines can use CO2 to cut CO2. Science 356, 805–806 (2017).

    Article  ADS  CAS  Google Scholar 

  4. Pitz-Paal, R. Concentrating solar power: still small but learning fast. Nat. Energy 2, 17095 (2017).

    Article  ADS  Google Scholar 

  5. Lilliestam, J., Labordena, M., Patt, A. & Pfenninger, S. Empirically observed learning rates for concentrating solar power and their responses to regime change. Nat. Energy 64, 17094 (2017).

    Article  ADS  Google Scholar 

  6. Nithyanandam, K. & Pitchumani, R. Cost and performance analysis of concentrating solar power systems with integrated thermal energy storage. Energy 64, 793–810 (2014).

    Article  CAS  Google Scholar 

  7. Williams, J. H. et al. The technology path to deep greenhouse gas emissions cuts by 2050. The pivotal role of electricity. Science 335, 53–59 (2012).

    Article  ADS  CAS  Google Scholar 

  8. American Society of Mechanical Engineers (ASME) 2017 ASME Boiler and Pressure Vessel Code. Section II, Part D Properties (Metric) https://www.asme.org/products/codes-standards/bpvciid-2017-bpvc-section-iimaterialspart (ASME, New York, 2017).

  9. Sandhage, K. H. & Henry, A. Methods for manufacturing ceramic and ceramic composite components and components made thereby. International patent application number PCT/US17/28091 (2017).

  10. Sandhage, K. H. Method of enhancing corrosion resistance of oxidizable materials and components made therefrom. International patent application number PCT/US17/56015 (2017).

  11. Denholm, P. & Maureen, H. Grid flexibility and storage required to achieve very high penetration of variable renewable electricity. Energy Pol. 39, 1817–1830 (2011).

    Article  Google Scholar 

  12. Pfenninger, S. et al. Potential for concentrating solar power to provide baseload and dispatchable power. Nat. Clim. Change 4, 689–692 (2014).

    Article  ADS  Google Scholar 

  13. Denholm, P. & Mehos, M. Enabling greater penetration of solar power via the use of CSP with thermal energy storage. In Solar Energy: Application, Economics, and Public Perception (ed. Adaramola, M.) 99–122 (Apple Academic Press, Waretown, 2014).

    Chapter  Google Scholar 

  14. Baumert, K. A., Herzog, T. & Pershing, J. Navigating the Numbers: Greenhouse Gas Data and International Climate Policy (World Resources Institute, Washington, 2005).

    Google Scholar 

  15. Nagender Naidu, S. V. & Rama Rao, P. Phase Diagrams of Binary Tungsten Alloys (ASM International, Materials Park, 1991).

    Google Scholar 

  16. Okamoto, H. C-Zr (carbon-zirconium). J. Phase Equil. 17, 162 (1996).

    Article  CAS  Google Scholar 

  17. Eremenko, V. N., Velikanova, T. Y., Artyukh, L. V., Aksel’rod, G. M. & Vishnevskii, A. S. In Phase Equilibria Diagrams. Phase Diagrams for Ceramists. Vol. X. (ed. McHale, A. E.) Fig. 9034 (The American Ceramic Society, Westerville, 1994).

  18. Taylor, R. E. Thermal conductivity of zirconium carbide at high temperatures. J. Am. Ceram. Soc. 45, 353–354 (1962).

    Article  CAS  Google Scholar 

  19. Touloukian, Y. S., Powell, R. W., Ho, C. Y. & Klemens, P. G. in Thermophysical Properties of Matter Vol. 1 (Plenum Press, New York, 1970).

    Chapter  Google Scholar 

  20. Touloukian, Y. S., Kirby, R. K., Taylor, R. E. & Lee, T. Y. R. in Thermophysical Properties of Matter Vol. 13 (Plenum Press, New York, 1977).

    Chapter  Google Scholar 

  21. Touloukian, Y. S., Kirby, R. K., Taylor, R. E. & Desai, P. D. in Thermophysical Properties of Matter Vol. 12 (Plenum Press, New York, 1975).

    Chapter  Google Scholar 

  22. Dickerson, M. B. et al. Near net-shaped, ultra-high melting, recession-resistant ZrC/W-based rocket nozzle liners via the displacive compensation of porosity (DCP) method. J. Mater. Sci. 39, 6005–6015 (2004).

    Article  ADS  CAS  Google Scholar 

  23. Leipold, M. H. & Nielsen, T. H. Mechanical properties of hot-pressed zirconium carbide tested to 2600 °C. J. Am. Ceram. Soc. 47, 419–424 (1964).

    Article  Google Scholar 

  24. Lassner, E. & Schubert, W.-D. Tungsten—Properties, Chemistry, Technology of the Element, Alloys and Chemical Compounds 22 (Springer, Boston, 1999).

    Google Scholar 

  25. Joint Committee on Powder Diffraction Standards (JCPDS) JCPDS International Center for Diffraction Data File 00–035–0784 for ZrC, 00–025–1047 for WC, 00–004–0806 for W, http://www.icdd.com/index.php/pdf-4 (JCPDS International Center for Diffraction Data, Newtown Square, 2007).

  26. American Society for Testing and Materials (ASTM) ASTM Standard Test Method for Thermal Diffusivity by the Flash Method E1461–13 (ASTM International, West Conshohocken, 2013).

    Google Scholar 

  27. American Society for Testing and Materials (ASTM) Standard Test Method for Flexural Strength of Advanced Ceramics at Ambient Temperature C1161–18 (ASTM International, West Conshohocken, 2018).

    Google Scholar 

  28. American Society for Testing and Materials (ASTM) Standard Test Method for Flexural Strength of Advanced Ceramics at Elevated Temperatures C1211–18 (ASTM International, West Conshohocken, 2018).

    Google Scholar 

  29. Gasparrini, C., Chater, R. J., Horlait, D., Vandeperre, L. & Lee, W. L. Zirconium carbide oxidation: kinetics and oxygen diffusion through the intermediate layer. J. Am. Ceram. Soc. 101, 2638–2652 (2018).

    Article  CAS  Google Scholar 

  30. Sikka, V. K. & Rosa, C. J. The oxidation kinetics of tungsten and the determination of oxygen diffusion coefficient in tungsten trioxide. Corros. Sci. 20, 1201–1219 (1980).

    Article  CAS  Google Scholar 

  31. Lipke, D. W., Zhang, Y., Liu, Y., Church, B. C. & Sandhage, K. H. Near net shape/net dimension ZrC/W-based composites with complex geometries via rapid prototyping and displacive compensation of porosity (DCP). J. Eur. Ceram. Soc. 30, 2265–2277 (2010).

    Article  CAS  Google Scholar 

  32. Joint Committee on Powder Diffraction Standards (JCDPS) JCPDS International Center for Diffraction Data File 00-004-0836 for Cu, 01-071-3645 for Cu2O, 00-048-1827 for WO2 and 01-070-2491 for monoclinic ZrO2, http://www.icdd.com/index.php/pdf-4/ (JCPDS International Center for Diffraction Data, Newtown Square, 2007).

  33. Barin, I. Thermochemical Data of Pure Substances 3rd edn (VCH, Weinheim, 1995).

    Book  Google Scholar 

  34. Narula, M. L., Tare, V. B. & Worrell, W. L. Diffusivity and solubility of oxygen in solid copper using potentiostatic and potentiometric techniques. Metall. Trans. B 14, 673–677 (1983).

    Article  Google Scholar 

  35. Sieverts, A. The absorption of gases by metals. Z. Metallk. 21, 37–46 (1929).

    CAS  Google Scholar 

  36. Grjotheim, K., Holm, J. L. & Roetnes, M. Phase diagrams of the systems sodium chloride-magnesium chloride and potassium chloride-magnesium chloride. Acta Chem. Scand. 26, 3802–3803 (1972).

    Article  CAS  Google Scholar 

  37. Sohal, M. S., Ebner, M. A., Sabharwall, P. & Sharpe, P. Engineering Database of Liquid Salt Thermophysical and Thermochemical Properties. Technical Report INL/EXT-10-18297 https://www.osti.gov/biblio/980801-engineering-database-liquid-salt-thermophysical-thermochemical-properties (Idaho National Laboratory, Idaho Falls, 2010).

  38. Moisseytsev, A., Sienicki, J. J., Cho, D. H. & Thomasa, M. R. Comparison of heat exchanger modeling with data from CO2-to-CO2 printed circuit heat exchanger performance tests. In Proc. Int. Congress Adv. Nucl. Power Plants (ICAPP) 2010 Paper 2284, 459–468, http://www.ans.org/store/item-700358/ (American Nuclear Society, La Grange Park, 2010).

  39. American Society of Mechanical Engineers (ASME) 2004 ASME Boiler and Pressure Vessel Code. Section VIII, Division 1 NG-3000 (ASME, New York, 2004).

    Google Scholar 

  40. Specialty Metals Corp. Inconel Alloy 740H A Superalloy Specifically Designed For Advanced Ultra Supercritical Power Generation http://www.specialmetals.com/assets/smc/documents/alloys/inconel/inconel-alloy-740-h.pdf (Specialty Metals Corp., New Hartford, 2018).

  41. Specialty Metals Corp. Inconel Alloy 617 http://www.specialmetals.com/assets/smc/documents/alloys/inconel/inconel-alloy-617.pdf (Specialty Metals Corp., New Hartford, 2018).

Download references

Acknowledgements

This work was supported by the US Department of Energy, Office of Energy Efficiency and Renewable Energy (award number DE-EE0007117). We thank S. H. Hwang for assistance with electron microscopy and I. Itskou for assistance with the preparation of Cu-encased ZrC/W specimens.

Reviewer information

Nature thanks L. F. Cabeza, O. Graeve, C. Turchi and the other anonymous reviewer(s) for their contribution to the peer review of this work.

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Author notes

  1. These authors contributed equally: M. Caccia, M. Tabandeh-Khorshid, G. Itskos, A. R. Strayer

Authors and Affiliations

  1. School of Materials Engineering, Purdue University, West Lafayette, IN, USA

    M. Caccia, M. Tabandeh-Khorshid, G. Itskos, A. R. Strayer, A. S. Caldwell, S. Singnisai, S. Sahoo, N. R. Kadasala & K. H. Sandhage

  2. George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, GA, USA

    S. Pidaparti, A. D. Rohskopf, D. Jarrahbashi, T. Kang, D. Ranjan & A. Henry

  3. Department of Engineering Physics, University of Wisconsin, Madison, WI, USA

    A. M. Schroeder & M. H. Anderson

  4. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    A. Marquez-Rossy & E. Lara-Curzio

  5. Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    A. Henry

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Contributions

M.T.-K., A.R.S. and S. Singnisai conducted the WC preform processing and analyses, with assistance from N.R.K. and with K.H.S. providing guidance. M.C. conducted the melt infiltration processing, and analysed the microstructure and chemistry of the resulting ZrC/W composites, with A.R.S., M.T.-K. and A.S.C. providing assistance and with K.H.S. providing guidance. Mechanical tests of ZrC/W composites were conducted and analyzed by S. Sahoo, G.I. and A.M.-R., with E.L.-C. providing guidance. Cu-encased ZrC/W corrosion test specimens were prepared by M.T.-K. Corrosion tests of the Cu-encased ZrC/W specimens were conducted by A.M.S., with M.H.A. providing guidance. Specimen cross-sectional analyses after the corrosion tests were conducted by A.S.C., with assistance from N.R.K. and with K.H.S. providing guidance. Thermodynamic and kinetic calculations associated with corrosion were conducted by K.H.S. Performance calculations of ZrC/W heat exchangers were conducted by S.P., T.K. and D.J., with assistance from K.H.S. and A.H., and with D.R. providing guidance. Economic analyses were conducted by A.D.R., S.P., and A.H., with A.R.S., M.C., G.I. and K.H.S. providing assistance. M.C., G.I., A.H. and K.H.S. drafted the majority of the manuscript. All authors contributed to the writing and review of the manuscript. K.H.S. supervised the overall effort.

Corresponding author

Correspondence to K. H. Sandhage.

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Competing interests

A.H. and K.S. are inventors on patent applications related to this work that have been filed by (and are owned by) Purdue University and the Georgia Institute of Technology (see refs 10,11). Patent application number PCT/US17/28091 includes the fabrication and use of ZrC/W composites for heat exchangers. Patent application PCT/US17/56015 includes enhancement of the high-temperature oxidation resistance of ZrC/W composites through the use of carbon monoxide-bearing supercritical carbon dioxide and a copper surface layer. The other authors declare no competing interests.

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Extended data figures and tables

Extended Data Fig. 1 Schematic illustration of a concentrated solar power plant.

The thermal energy storage medium is KCl-MgCl2 molten salt (67% mol%–33 mol%36,37) and the plant uses a sCO2 Brayton cycle for power generation.

Extended Data Fig. 2 More channels in the heat exchanger reduce the values of pressure drop.

Variations of the channel length, and the values of the pressure drop for the molten salt and sCO2 streams, are plotted as a function of the number of channels for each fluid.

Extended Data Fig. 3 Higher allowed stresses reduce the required plate thickness and channel spacing.

Values of the minimum plate thickness and minimum channel spacing associated with a given allowed stress are plotted for a compact, printed-circuit-type heat exchanger.

Extended Data Table 1 Characteristics of the reaction for fabrication of the heat exchanger plates
Full size table
Extended Data Table 2 Material characteristics for ZrC/W, Inconel 740H and Inconel 617
Full size table
Extended Data Table 3 Operating conditions representative of an intermediate heat exchanger for a 10-MWe concentrated solar power plant
Full size table

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Caccia, M., Tabandeh-Khorshid, M., Itskos, G. et al. Ceramic–metal composites for heat exchangers in concentrated solar power plants. Nature 562, 406–409 (2018). https://doi.org/10.1038/s41586-018-0593-1

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