International Journal Of Computational Engineering Research (<strong>ijcer</strong>online.com) Vol. 2 Issue. 8The degree of perfection is a second law efficiency measure that can be used to identify opportunities for improvementand to compare with other processes. To illustrate, consider the 2004 version of the idealized HiPco process with ideal reversiblethermal treatment and pressurization stages, but operated in an open loop i.e. without recycling of the CO gas. The degree ofperfection would be given by (39.1 kJ/g) / (12,500g x 9.82 kJ/g +12,040 kJ/g) = 2.9 x 10-4. This low value is due to therequirement for large amounts of input CO and complete destruction of the physical exergy that was previously invested into theCO gas stream. Now if CO recycling can reduce the input CO from 12,500 grams to 4.67 grams (the minimum stoichiometricquantity as given by (1)) this would improve the degree of perfection to (39.1kJ/g)/ (4.67g x 9.82kJ/g + 12,040kJ/g) = 3.2 x 10-3.This is about an order of magnitude improvement, but still low because of the complete loss of the invested physical exergy. Afurther improvement could involve the preheating of the incoming CO gas stream using some of this lost exergy. In general, thedegree of perfection measure for the performance of other synthesis reactions for CNT are also quite low (on the order of 10-3 to10-4) owning to; 1) the one time use of large quantities of high exergy material inputs – primarily the carbon source inputs, and 2)the high physical exergy requirements – most processes are performed at high temperatures. However, these low values are stillquite highcompared to some semi conductor processes, which can be in the range of 10-5 and 10-6 for SiO2 processes, see [5],[6]. The main difference is due to the relatively high standard chemical exergy of CNTs.VII. Closing CommentsOne purpose of this paper was to examine the minimum exergy requirements to make carbon nanotubes. We find thatwhile the exergy requirements are high, they are falling at a rather fast rate due to process improvements and could fall still morein the future. This exercise underlines the challenges of trying to perform a Life Cycle Assessment of an evolving technology.Early in the life of a new technology one may be following a moving target. We believe that the results given here help explainsome of the variation seen in early LCI reports as given in Table 1.Note that the values reported here are only for the synthesis part of the nanotube production process. Furthermore thesevalues are for minimum exergy requirements, not actual. To make a full estimate one would have to consider: 1) the exergyrequired to make the input materials. Because of the purity requirements for some of these inputs, this is likely to be very large.For example according to Williams et al [16] for gases with purities in the 0.1 ppm level, the energy required for purification canin the range of 20 – 200 GJ/g. (These are very high energy requirements indeed!) In addition, 2) the carbon nanotube purificationstep needs to be added, including the effect of yield losses. And 3) the minimum synthesis values given here need to be increasedto account for losses in the synthesis step. Finally, 4) additional energy required for infrastructure needs to be added(environmental conditioning etc), and 5) losses at the electric utility need also to be added. Taking this into account it is quitereasonable to expect an order of magnitude estimate of the embodied energy requirements for carbon nanotubes to be in theregion of 0.1-1.0 TJ/kg. Such a high value compared to other materials would make this one of the most energy intensivematerials known to humankind. See for example [1], [18]. Ironically this enormous specific energy requirement constitutes only avery small fraction of the manufacturing costs (< 1% as discussed by Healy [2] and Isaacs [15]). For example, say the energy costfor making carbon nanotubes is on the order of 36GJ of electricity per kilogram or 36MJ/g.This is equal to 10 kWh/g. Now at 7 cents a kilowatt hour this yields a cost of 70 cents per gram. But carbon nanotubescan sell for around $300/g. In other words, the electricity cost in this case is on the order of 0.2% of the price, and according to arecent cost study, energy costs for all manufacturing processes for nanotubes result in about 1% of the cost [15]. It appears thatnew manufacturing processes can produce novel products with high demand resulting in a value that far exceeds the energy(electricity) cost. At the same time however, since our current electricity supply comes primarily from fossil fuels, most of theenvironmental impacts associated with these materials (e.g. global warming, acidification, mercury emissions) are related to thisuse of electricity [15]. How can we reconcile this inconsistency? One comment would be that the current price for carbonnanotubes may well be inflated due to the rather substantial government funds for nanotechnology research worldwide. Anothercomment, of course, is that, from an environmental perspective, electricity from fossil fuels is vastly underpriced. That is, theenvironmental and health externalities associated with the use of fossil fuels are not included in the price of electricity.||Issn <strong>2250</strong>-<strong>3005</strong>(online)|| ||December||2012 Page 165
International Journal Of Computational Engineering Research (<strong>ijcer</strong>online.com) Vol. 2 Issue. 8References[1] J.A. Isaacs, A. Tanwani, and M. L. Healy.“Environmental assessment of SWNT production.” Proceedings of the 2006IEEE International Symposium on Electronics and the Environment. 8-11 May 2006: pp. 38-41.[2] M.L Healy, L. J. Dahlben and J. A. Isaacs,“Environmental assessment of single-walled carbon nanotube processes”,Journal of Industrial Ecology, Vol. 12, No. 3, June 2008, , pp. 376-393.[3] D. Kushnir, and Bjorn A. Sanden, “Energy requirements of carbon nanoparticle production”, Journal of IndustrialEcology, Vol. 12, No. 3, June 2008, pp. 360 -375.[4] V. Khanna, B. R. Bakshi and L. James Lee, “Carbon nanofiber production – life cycle energy consumption andenvironmental impact”, Journal of Industrial Ecology, Vol. 12, No. 3, June 2008, pp. 394 -410.[5] M. Branham, “Semiconductors and sustainability: energy and materials use in the integrated circuit industry”. Departmentof Mechanical Engineering, M.I.T. MS Thesis, 2008.[6] T.G. Gutowski, M. S. Branham, J. B. Dahmus, A. J. Jones, A. Thiriez and D. Sekulic, “Thermodynamic analysis ofresources used in manufacturing processes”, Environmental Science and Technology, 43, January 29, 2009, pp 1584-90.[7] M.J. Bronikowski, P. A. Willis, D. T. Colbert, K.A. Smith and R. E. Smalley, “Gas-phase production of carbon singlewallednanotubes from carbon monoxide via the HiPco process: A parametric study”, J. Vac. Sc. Technol. A 19(4),American Vacuum Society, Jul/Aug. 2001, pp. 1800-1805.[8] P. Nikolaev, M.J. Bronikowski, R. K. Bradley, F. Rohmund, D.T. Colbert, K.A. Smith and R. E. Smalley, “Gas-phasecatalytic growth of single-walled carbon nanotubes from carbon monoxide”, Chemical Physics Letters 313, , Elsevier,November 1999, pp. 91-97.[9] R.E. Smalley, K.A. Smith, D.T. Colbert, P. Nikolaev, M.J. Bronikowski, R.K. Bradley, and F. Rohmund,” Single WallCarbon Nanotubes from High Pressure CO”. U.S. Patent No. US7,204,970, April 17, 2007.[10] J. Szargut,, D. R. Morris and F. R. Steward, Exergy Analysis of Thermal Chemical and Metallurgical Processes,Hemisphere Publishing Corporation, 1988. [11] Cherry B. W., Polymer Surfaces, Cambridge University Press 1981[12] J.Abrahamson, “The surface energies of graphite”, Carbon, Vol. 11, No. 4-E, Pergamon Press, 1975. , pp. 357-362.[13] Qiang Lu and Rui Huang, “Nonlinear mechanics of single-atomic-layer graphene sheets”, International Journal of AppliedMechanics, Vol. 1. No. 3, Imperial College Press, 2009, pp. 443-467.[14] T.G.Gutowski and D.P. Sekulic, “The thermodynamic analysis of manufacturing processes”, chapter in Thermodynamicsand the Destruction of Resources, B.R. Bakshi, T.G. Gutowski and D.P. Sekulic Cambridge University Press, to appear2010 IEEE, International Symposium on Sustainable Systems and Technologies, Washington D.C., May 16-19, 2010[15] J.A.Isaacs, A. Tanwani, M.L. Healy, “Economic assessment of single-walled carbon nanotube processes”, J. NanopartRes. DOI 10.007/s11051-009-9673-3, Research Paper published on line, Springer, June 2009.[16] E. Williams, N. Krishnan, and S. Boyd Case Studies in Energy Use to Realize Ultra- High Purities in SemiconductorManufacturing, ISEE, IEEE 2008[17] V. Smil, Energy in Nature and Society, MIT Press 2008.[18] M.F. Ashby, Materials and the Environment – Eco- Informed Material Choice, Elsevier Inc., 2009. Fig. 2 Evolution of theHiPco process development over time in terms of the calculated minimum theoretical physical exergy requirements andestimated actual exergy over a nine year period. IEEE, International Symposium on Sustainable Systems andTechnologies, Washington D.C., May 16-19, 2010 Fig. 3a. Energy intensity (J/kg) Vs process rate (kg/hr) for 20 differentprocesses. Data and References cited in the figure are from Ref. [6]. Fig 3b. Energy intensity (J/kg) Vs process rate(kg/hr) for the production for Carbon Nano-fibers. See Table 3 and text.||Issn <strong>2250</strong>-<strong>3005</strong>(online)|| ||December||2012 Page 166
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