- Email: [email protected]
Carbon Fiber “Nanocreep” in Creep-Tested Cf-SiC Composites
Scripta Materialia, Vol. 38, No. 6, pp. 937–943, 1998 Elsevier Science Ltd Copyright © 1998 Acta Metallurgica Inc. Printed in the USA. All rights reserved. 1359-6462/98 $19.00 1 .00
Pergamon PII S1359-6462(97)00567-8
CARBON FIBER “NANOCREEP” IN CREEP-TESTED Cf-SiC COMPOSITES G. Boitier, J. Vicens and J.L. Chermant LERMAT, URA CNRS 1317, ISMRA, 6 bd Mal Juin, 14050 Caen cedex, France (Received November 18, 1997) (Accepted December 17, 1997)
Introduction Creep studies of ceramic composites (CMCs) are of crucial importance for the design engineers in order to predict their lifetime under severe conditions of stress and temperature. However, only few results have already been published on the creep behavior of such materials (1–5), partly due to the experimental difficulties raised in achieving accurate long term thermomechanical characterizations (6). Nevertheless, previous studies on CMCs have revealed the occurrence of a so-called damage-creep mechanism (4,5,7) involving microcracking coupled with creep of the constituents (i.e. fiber, matrix and/or interphase). As a result of such a complexity, the mechanisms responsible for creep strain of CMCs are not well-understood yet. The only way to solve this problem seems to require a microstructural investigation at different scales down to the nanometric one. In this context, the tensile creep behavior of a 2.5D Cf-SiC composite has been studied between 1273K and 1673K for stress levels ranging from 110 to 220 MPa (8,9). Regarding the results of Abbe´ (1) on SiCf-SiC composites and Adami (2) on Al2O3f-SiC composites, the creep behavior of both composites has appeared governed by the creeping fibers. For this reason, we sought for structural changes upon creep tests of the carbon fibers in Cf-SiC composites, via a nanoscale investigation in high resolution electron microscopy (HREM). This paper presents HREM characterization of the carbon fibers in as-received and creep-tested composites, under 220 MPa, at 1473K and 1673K.
Material and Experimental Procedure The material under investigation is a 2.5D Cf-SiC composite fabricated by SEP Company (Bordeaux, France) according to the CVI process (10). The preform is made of a stack of five plain woven clothes of high strength ex-PAN carbon fibers with a certain interlocking between them leading to the 2.5D architecture. For high strength ex-PAN carbon fibers, Guigon has proposed a microstructural model (Fig. 1) resulting from TEM and HREM studies (11,12). In longitudinal sections, the fiber is made of small elemental domains called basic structural units (BSUs) corresponding to 2–3 carbonaceous layers of about 1 nm in diameter. The BSUs weld edge to edge with small angle distortions to form areas of local molecular orientation (LMO). The LMOs associate face to face and edge to edge with high angle 937
938
CARBON FIBER NANOCREEP
Vol. 38, No. 6
Figure 1. Guigon’s model for high strength ex-PAN carbon fibers.
distortions. As a result, the structure of the fiber is made of transversally disoriented carbon sheets, longitudinally oriented parallely to the fiber axis. So, the nanostructure of a high strength carbon fiber can be fully described using TEM and HREM in both longitudinal and transversal sections. Longitudinal samples were cut parallely to the surface of the tensile specimen within its thickness with a low-speed diamond saw, then polished to a thickness of ;100 mm. Disc-shaped samples (A 5 3 mm) were mechanically ground, then dimpled (Gatan, Dimple Grinder) to a ;10 mm thickness. Transversal samples (10 3 2.4 3 0.8 mm) were cut perpendicularly to the specimen section and stuck in a brass tube (A 5 3 mm). Thin slices of the tube (;200 mm) were cut, polished and dimpled as described above to a thickness of ;10 mm. Both types of samples (longitudinal and transversal) were finally thinned by ion-milling (Ar1, 5kV), (Gatan, Dual Ion Mill). Two microscopes operating at 200 kV were used to characterize the microstructure: a Jeol 2010 and a Topcon EM 002B. The nanotexture of the carbon fibers in the as-received 2.5D Cf-SiC composite is described in both transversal and longitudinal sections. For creep-tested composites, two specimens were considered corresponding to the higher stress level (i.e. 220 MPa) and to temperatures of 1473K and 1673K. By considering the toughest conditions of stress and temperature we expected the structural changes to be maximized. This study is only concentrated on the load-bearing fibers (i.e. parallel to the loading direction). Results The nanostructure of the carbon fibers in the as-received 2.5D Cf-SiC composite has been previously described by using electron diffraction, dark field and high resolution images (9,13). The obtained results were fully consistent with Guigon’s model for high strength ex-PAN carbon fibers. BSUs have
Vol. 38, No. 6
CARBON FIBER NANOCREEP
939
Figure 2. HREM micrograph of a longitudinal section of a carbon fiber in a as-received 2.5D Cf-SiC composite evidencing BSUs and LMOs.
shown to be isometric, made of 2 to 3 carbon layers with a diameter of 0.8 –1 nm. In HREM, the edge to edge association of BSUs into LMOs parallel to the fiber axis has been observed (Fig. 2). The LMOs length and thickness are 12.5 nm and 2.5 nm respectively. The disoriented transversal structure, imaged in HREM (Fig. 3), is admitted to be responsible for the high strength value by the number of bonds it provides. After creep test at 1473K under 220 MPa, the nanotexture of the fibers (Fig. 4) is very similar to the one observed in the as-received material. The diameter of the BSUs remains unchanged in our experimental accuracy domain, whereas the mean diameter of the LMOs increases slightly up to 14 nm. After creep test at 1673K under 220 MPa, the structural evolution of the fibers is more significant. The diameter of the BSUs increases slightly (1–1.5 nm) whereas the mean diameter of the LMOs rises
Figure 3. HREM micrograph of a transversal section of a carbon fiber in a as-received 2.5D Cf-SiC composite evidencing disoriented BSUs.
940
CARBON FIBER NANOCREEP
Vol. 38, No. 6
Figure 4. HREM micrograph of a longitudinal section of a carbon fiber in a 2.5D Cf-SiC composite creep-tested at 1473K under 220 MPa.
up to 18 nm (Fig. 5). The texture of the whole fiber seems enhanced with a better orientation of the (0002) planes parallely to the fiber axis. The structural evolutions of BSUs and LMOs upon creep tests are summarized in Table 1. The observation of the transversal section of the fibers after creep test at 1673K under 220 MPa, confirms the textural evolution. Compared to a transversal section of the fibers in the as-received composite (Fig. 3), the radius of curvature of the carbon sheets appears larger (Fig. 6), which is consistent with the longitudinal features mentioned above.
Figure 5. HREM micrograph of a longitudinal section of a carbon fiber in a 2.5D Cf-SiC composite creep-tested at 1673K under 220 MPa.
Vol. 38, No. 6
CARBON FIBER NANOCREEP
941
TABLE 1 Evolution Upon Creep Tests of the Mean Longitudinal Diameter of BSUs, La(BSU), and LMOs, La(LMO), of the Carbon Fibers in 2.5D Cf-SiC Composites T
K
273 1473 1673
s MPa — 220 220
La(BSU)
nm
0.8–1.0 0.8–1.0 1.0–1.5
La(LMO)
nm
12.5 14.0 18.0
Discussion If we consider the results of the literature relative to the creep behavior of carbon fibers, they mainly concern high modulus (most often pitch-based) fibers tested at temperatures greater than 2373K, for stresses above 700 MPa (14 –18). For such fibers, Sines et al. (16 –18) have determined a stress exponent of 7.5– 8 and an activation energy of 1000 –1200 kJ.mol21. TEM investigations have evidenced the creep mechanism, consistent with these values, which operates by sliding of crystallites, controlled by bulk diffusion of individual carbon atoms. This sliding promotes face to face and edge to edge association of crystallites leading to much larger carbon sheets within the fibers. For 2.5D Cf-SiC composites, we have determined an apparent activation energy of 60 – 80 kJ.mol21 and a stress exponent of 1.8 –2 (9). Considering these values, the macroscopic creep of the fibers and then their contribution to the macroscopic creep strain of the whole composite are not likely to occur. Nevertheless, a restructuration of the fibers upon tests has been evidenced, characterized by an increase of the mean longitudinal diameter of LMOs and of the radius of curvature of the carbon sheets. Moreover, Guigon has demonstrated that when the test temperature overcomes the fabrication temperature of a PAN-based carbon fiber, a structural evolution is possible, as far as the fiber still contains nitrogen (12). As a result, the LMOs diameter can increase in the 1373–1973K temperature range by lateral welding of BSUs according to Watt’s denitrogenation mechanism (Fig. 7), (19).
Figure 6. HREM micrograph of a transversal section of a carbon fiber in a 2.5D Cf-SiC composite creep-tested at 1673K under 220 MPa.
942
CARBON FIBER NANOCREEP
Vol. 38, No. 6
Figure 7. Lateral welding between carbonaceous cycles according to Watt’s denitrogenation mechanism.
Thus, we have attributed the restructuration effect of the carbon fibers, in the creep-tested 2.5D Cf-SiC composites, to a lateral junction of two LMOs, or of one LMO with the adjacent BSUs, by denitrogenation according to Watt’s mechanism activated by the combined effects of stress and temperature. We propose to define this growing of LMOs during such creep tests as carbon fiber “nanocreep,” which corresponds to the first changes in the microstructure upon creep tests. Conclusion Using HREM, the nanostructure of the carbon fibers has been fully characterized in as-received 2.5D Cf-SiC composites and in creep tested samples under 220 MPa at 1473K and 1673K. The diameter of BSUs almost remains unchanged while the mean longitudinal diameter of LMOs increases from 12.5 to 18 nm. Such a structural evolution during creep tests of this ceramic matrix composite is defined as “nanocreep” of the carbon fibers. However, the contribution of the fiber to the macroscopic creep strain of the whole composite appears to be negligible in the stress and temperature domains considered here. To distinguish the influence of the temperature from the role of the applied stress, further nanostructural investigations have to be conducted on composites tested at lower stress levels. The mechanisms responsible for the creep strain of the whole composite will be discussed later. Acknowledgments The authors wish to thank the Socie´te´ Europe´enne de Propulsion (SEP, Bordeaux, France) for providing fellowship (G.B.) and composite specimens. Special thanks are due to Pr M. Guigon (UTC, Compie`gne, France) for fruitful discussions and helpful advises. References 1. 2. 3. 4. 5.
F. Abbe´, The`se de Doctorat of the University of Caen (1990). J. N. Adami, The`se de Doctorat e`s Sciences, Ecole Polytechnique Fe´de´rale de Lausanne (1992). The work was performed at the Institute for Advanced Materials, Joint Research Center, Petten (The Netherlands). J. W. Holmes and X. Wu, in High Temperature Mechanical Behavior of Ceramic Composites, ed. S. V. Nair and K. Jakus, p. 199, Butterworth-Heinemann, London (1995). H. Maupas, The`se de Doctorat of the University of Caen (1996). D. Kervadec, The`se de Doctorat of the University of Caen (1992).
Vol. 38, No. 6
6. 7. 8. 9. 10.
CARBON FIBER NANOCREEP
943
G. Boitier, H. Maupas, H. Cubero, and J. L. Chermant, Rev. Comp. Mat. Avance´s. 7, in press (1997). J. L. Chermant, Sil. Ind. 60, 261 (1995). G. Boitier, J. Vicens, and J. L. Chermant, Scripta Mater. 37, in press (1997). G. Boitier, The`se de Doctorat of the University of Caen (1997). F. Christin, R. Naslain, and C. Bernard, in Proceedings of the 7th International Conference on CVD, ed. T. O. Sedwick and H. Lydtin, p. 499, The Electrochemical Society, Princeton (1979). 11. M. Guigon, A. Oberlin, and G. Desarmot, Fib. Sci. Tech. 20, 55 (1984). 12. M. Guigon, The`se de Doctorat e`s Sciences, University of Compie`gne (1985). 13. G. Boitier, J. Vicens, and J. L. Chermant, J. Mat. Sci. Lett. 16, 1402 (1997). 14. H. M. Hawthorne, J. Mat. Sci. 11, 97 (1976). 15. R. J. Zaldivar and G. S. Rellick, Carbon. 29, 1155 (1991). 16. G. Sines, Z. Yang, and B.D. Vickers, Carbon. 27, 403 (1989). 17. K. Kogure, G. Sines, and J. G. Lavin, Carbon. 32, 1469 (1994). 18. K. Kogure, G. Sines, and J. G. Lavin, J. Am. Ceram. Soc. 79, 46 (1996). 19. W. Watt, D. J. Johnson, and E. Parker, in Proceedings of the International Carbon Fibres Conference, p. 3, The Plastic Institute, London, (1974).
Pergamon PII S1359-6462(97)00567-8
CARBON FIBER “NANOCREEP” IN CREEP-TESTED Cf-SiC COMPOSITES G. Boitier, J. Vicens and J.L. Chermant LERMAT, URA CNRS 1317, ISMRA, 6 bd Mal Juin, 14050 Caen cedex, France (Received November 18, 1997) (Accepted December 17, 1997)
Introduction Creep studies of ceramic composites (CMCs) are of crucial importance for the design engineers in order to predict their lifetime under severe conditions of stress and temperature. However, only few results have already been published on the creep behavior of such materials (1–5), partly due to the experimental difficulties raised in achieving accurate long term thermomechanical characterizations (6). Nevertheless, previous studies on CMCs have revealed the occurrence of a so-called damage-creep mechanism (4,5,7) involving microcracking coupled with creep of the constituents (i.e. fiber, matrix and/or interphase). As a result of such a complexity, the mechanisms responsible for creep strain of CMCs are not well-understood yet. The only way to solve this problem seems to require a microstructural investigation at different scales down to the nanometric one. In this context, the tensile creep behavior of a 2.5D Cf-SiC composite has been studied between 1273K and 1673K for stress levels ranging from 110 to 220 MPa (8,9). Regarding the results of Abbe´ (1) on SiCf-SiC composites and Adami (2) on Al2O3f-SiC composites, the creep behavior of both composites has appeared governed by the creeping fibers. For this reason, we sought for structural changes upon creep tests of the carbon fibers in Cf-SiC composites, via a nanoscale investigation in high resolution electron microscopy (HREM). This paper presents HREM characterization of the carbon fibers in as-received and creep-tested composites, under 220 MPa, at 1473K and 1673K.
Material and Experimental Procedure The material under investigation is a 2.5D Cf-SiC composite fabricated by SEP Company (Bordeaux, France) according to the CVI process (10). The preform is made of a stack of five plain woven clothes of high strength ex-PAN carbon fibers with a certain interlocking between them leading to the 2.5D architecture. For high strength ex-PAN carbon fibers, Guigon has proposed a microstructural model (Fig. 1) resulting from TEM and HREM studies (11,12). In longitudinal sections, the fiber is made of small elemental domains called basic structural units (BSUs) corresponding to 2–3 carbonaceous layers of about 1 nm in diameter. The BSUs weld edge to edge with small angle distortions to form areas of local molecular orientation (LMO). The LMOs associate face to face and edge to edge with high angle 937
938
CARBON FIBER NANOCREEP
Vol. 38, No. 6
Figure 1. Guigon’s model for high strength ex-PAN carbon fibers.
distortions. As a result, the structure of the fiber is made of transversally disoriented carbon sheets, longitudinally oriented parallely to the fiber axis. So, the nanostructure of a high strength carbon fiber can be fully described using TEM and HREM in both longitudinal and transversal sections. Longitudinal samples were cut parallely to the surface of the tensile specimen within its thickness with a low-speed diamond saw, then polished to a thickness of ;100 mm. Disc-shaped samples (A 5 3 mm) were mechanically ground, then dimpled (Gatan, Dimple Grinder) to a ;10 mm thickness. Transversal samples (10 3 2.4 3 0.8 mm) were cut perpendicularly to the specimen section and stuck in a brass tube (A 5 3 mm). Thin slices of the tube (;200 mm) were cut, polished and dimpled as described above to a thickness of ;10 mm. Both types of samples (longitudinal and transversal) were finally thinned by ion-milling (Ar1, 5kV), (Gatan, Dual Ion Mill). Two microscopes operating at 200 kV were used to characterize the microstructure: a Jeol 2010 and a Topcon EM 002B. The nanotexture of the carbon fibers in the as-received 2.5D Cf-SiC composite is described in both transversal and longitudinal sections. For creep-tested composites, two specimens were considered corresponding to the higher stress level (i.e. 220 MPa) and to temperatures of 1473K and 1673K. By considering the toughest conditions of stress and temperature we expected the structural changes to be maximized. This study is only concentrated on the load-bearing fibers (i.e. parallel to the loading direction). Results The nanostructure of the carbon fibers in the as-received 2.5D Cf-SiC composite has been previously described by using electron diffraction, dark field and high resolution images (9,13). The obtained results were fully consistent with Guigon’s model for high strength ex-PAN carbon fibers. BSUs have
Vol. 38, No. 6
CARBON FIBER NANOCREEP
939
Figure 2. HREM micrograph of a longitudinal section of a carbon fiber in a as-received 2.5D Cf-SiC composite evidencing BSUs and LMOs.
shown to be isometric, made of 2 to 3 carbon layers with a diameter of 0.8 –1 nm. In HREM, the edge to edge association of BSUs into LMOs parallel to the fiber axis has been observed (Fig. 2). The LMOs length and thickness are 12.5 nm and 2.5 nm respectively. The disoriented transversal structure, imaged in HREM (Fig. 3), is admitted to be responsible for the high strength value by the number of bonds it provides. After creep test at 1473K under 220 MPa, the nanotexture of the fibers (Fig. 4) is very similar to the one observed in the as-received material. The diameter of the BSUs remains unchanged in our experimental accuracy domain, whereas the mean diameter of the LMOs increases slightly up to 14 nm. After creep test at 1673K under 220 MPa, the structural evolution of the fibers is more significant. The diameter of the BSUs increases slightly (1–1.5 nm) whereas the mean diameter of the LMOs rises
Figure 3. HREM micrograph of a transversal section of a carbon fiber in a as-received 2.5D Cf-SiC composite evidencing disoriented BSUs.
940
CARBON FIBER NANOCREEP
Vol. 38, No. 6
Figure 4. HREM micrograph of a longitudinal section of a carbon fiber in a 2.5D Cf-SiC composite creep-tested at 1473K under 220 MPa.
up to 18 nm (Fig. 5). The texture of the whole fiber seems enhanced with a better orientation of the (0002) planes parallely to the fiber axis. The structural evolutions of BSUs and LMOs upon creep tests are summarized in Table 1. The observation of the transversal section of the fibers after creep test at 1673K under 220 MPa, confirms the textural evolution. Compared to a transversal section of the fibers in the as-received composite (Fig. 3), the radius of curvature of the carbon sheets appears larger (Fig. 6), which is consistent with the longitudinal features mentioned above.
Figure 5. HREM micrograph of a longitudinal section of a carbon fiber in a 2.5D Cf-SiC composite creep-tested at 1673K under 220 MPa.
Vol. 38, No. 6
CARBON FIBER NANOCREEP
941
TABLE 1 Evolution Upon Creep Tests of the Mean Longitudinal Diameter of BSUs, La(BSU), and LMOs, La(LMO), of the Carbon Fibers in 2.5D Cf-SiC Composites T
K
273 1473 1673
s MPa — 220 220
La(BSU)
nm
0.8–1.0 0.8–1.0 1.0–1.5
La(LMO)
nm
12.5 14.0 18.0
Discussion If we consider the results of the literature relative to the creep behavior of carbon fibers, they mainly concern high modulus (most often pitch-based) fibers tested at temperatures greater than 2373K, for stresses above 700 MPa (14 –18). For such fibers, Sines et al. (16 –18) have determined a stress exponent of 7.5– 8 and an activation energy of 1000 –1200 kJ.mol21. TEM investigations have evidenced the creep mechanism, consistent with these values, which operates by sliding of crystallites, controlled by bulk diffusion of individual carbon atoms. This sliding promotes face to face and edge to edge association of crystallites leading to much larger carbon sheets within the fibers. For 2.5D Cf-SiC composites, we have determined an apparent activation energy of 60 – 80 kJ.mol21 and a stress exponent of 1.8 –2 (9). Considering these values, the macroscopic creep of the fibers and then their contribution to the macroscopic creep strain of the whole composite are not likely to occur. Nevertheless, a restructuration of the fibers upon tests has been evidenced, characterized by an increase of the mean longitudinal diameter of LMOs and of the radius of curvature of the carbon sheets. Moreover, Guigon has demonstrated that when the test temperature overcomes the fabrication temperature of a PAN-based carbon fiber, a structural evolution is possible, as far as the fiber still contains nitrogen (12). As a result, the LMOs diameter can increase in the 1373–1973K temperature range by lateral welding of BSUs according to Watt’s denitrogenation mechanism (Fig. 7), (19).
Figure 6. HREM micrograph of a transversal section of a carbon fiber in a 2.5D Cf-SiC composite creep-tested at 1673K under 220 MPa.
942
CARBON FIBER NANOCREEP
Vol. 38, No. 6
Figure 7. Lateral welding between carbonaceous cycles according to Watt’s denitrogenation mechanism.
Thus, we have attributed the restructuration effect of the carbon fibers, in the creep-tested 2.5D Cf-SiC composites, to a lateral junction of two LMOs, or of one LMO with the adjacent BSUs, by denitrogenation according to Watt’s mechanism activated by the combined effects of stress and temperature. We propose to define this growing of LMOs during such creep tests as carbon fiber “nanocreep,” which corresponds to the first changes in the microstructure upon creep tests. Conclusion Using HREM, the nanostructure of the carbon fibers has been fully characterized in as-received 2.5D Cf-SiC composites and in creep tested samples under 220 MPa at 1473K and 1673K. The diameter of BSUs almost remains unchanged while the mean longitudinal diameter of LMOs increases from 12.5 to 18 nm. Such a structural evolution during creep tests of this ceramic matrix composite is defined as “nanocreep” of the carbon fibers. However, the contribution of the fiber to the macroscopic creep strain of the whole composite appears to be negligible in the stress and temperature domains considered here. To distinguish the influence of the temperature from the role of the applied stress, further nanostructural investigations have to be conducted on composites tested at lower stress levels. The mechanisms responsible for the creep strain of the whole composite will be discussed later. Acknowledgments The authors wish to thank the Socie´te´ Europe´enne de Propulsion (SEP, Bordeaux, France) for providing fellowship (G.B.) and composite specimens. Special thanks are due to Pr M. Guigon (UTC, Compie`gne, France) for fruitful discussions and helpful advises. References 1. 2. 3. 4. 5.
F. Abbe´, The`se de Doctorat of the University of Caen (1990). J. N. Adami, The`se de Doctorat e`s Sciences, Ecole Polytechnique Fe´de´rale de Lausanne (1992). The work was performed at the Institute for Advanced Materials, Joint Research Center, Petten (The Netherlands). J. W. Holmes and X. Wu, in High Temperature Mechanical Behavior of Ceramic Composites, ed. S. V. Nair and K. Jakus, p. 199, Butterworth-Heinemann, London (1995). H. Maupas, The`se de Doctorat of the University of Caen (1996). D. Kervadec, The`se de Doctorat of the University of Caen (1992).
Vol. 38, No. 6
6. 7. 8. 9. 10.
CARBON FIBER NANOCREEP
943
G. Boitier, H. Maupas, H. Cubero, and J. L. Chermant, Rev. Comp. Mat. Avance´s. 7, in press (1997). J. L. Chermant, Sil. Ind. 60, 261 (1995). G. Boitier, J. Vicens, and J. L. Chermant, Scripta Mater. 37, in press (1997). G. Boitier, The`se de Doctorat of the University of Caen (1997). F. Christin, R. Naslain, and C. Bernard, in Proceedings of the 7th International Conference on CVD, ed. T. O. Sedwick and H. Lydtin, p. 499, The Electrochemical Society, Princeton (1979). 11. M. Guigon, A. Oberlin, and G. Desarmot, Fib. Sci. Tech. 20, 55 (1984). 12. M. Guigon, The`se de Doctorat e`s Sciences, University of Compie`gne (1985). 13. G. Boitier, J. Vicens, and J. L. Chermant, J. Mat. Sci. Lett. 16, 1402 (1997). 14. H. M. Hawthorne, J. Mat. Sci. 11, 97 (1976). 15. R. J. Zaldivar and G. S. Rellick, Carbon. 29, 1155 (1991). 16. G. Sines, Z. Yang, and B.D. Vickers, Carbon. 27, 403 (1989). 17. K. Kogure, G. Sines, and J. G. Lavin, Carbon. 32, 1469 (1994). 18. K. Kogure, G. Sines, and J. G. Lavin, J. Am. Ceram. Soc. 79, 46 (1996). 19. W. Watt, D. J. Johnson, and E. Parker, in Proceedings of the International Carbon Fibres Conference, p. 3, The Plastic Institute, London, (1974).