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Direct Evidence Of Chemical Reactions Induced By Shear-Strains

Published online by Cambridge University Press:  01 February 2011

John J. Gilman*
Affiliation:
Materials Science and Engineering, University of California at Los Angeles, Los Angeles, CA 90095
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Abstract

After a brief review of the history of mechanochemistry, and of the theoretical principles of chemical reactivity, four examples are described of reactions that demonstrate the importance of elastic shear strains compared with hydrostatic compressive strains (volume changes). Techniques for separating shear strains from volume changes, and for isolating elastic strains from plastic deformation are described. The latter (isolation) is achieved simply by localizing a strained region making it too small for dislocation nucleation. Shear strain acts by reducing the chemical hardness (activation energy) of a reactant. The four examples are: (1) “hammer chemistry” in which physisorped methane is struck by argon atoms with enough kinetic energy to cause chemisorption; (2) enhanced oxidation of silicon at stressed crack tips; (3) selective dissolution of crystals at screw dislocations; and (4) increased rates of catalyzed reactions when surface acoustic waves are passed through the catalyst.

Type
Research Article
Copyright
Copyright © Materials Research Society 2004

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References

REFERENCES

1. Manaa, M. R., (2003), “Shear-induced Metallization of Triamino-trinitrobenzene Crystals”, Appl. Phys. Lett., 83, #3, 1352.Google Scholar
2. Takacs, L. (2003), “M. Carey Lea, The Father of Mechanochemistry”, Bull. for History of Chem., 28, #1, 26.Google Scholar
3. Lea, M. C.. (1892). “Disruption of the Silver Haloid Molecule by Mechanical Force”, Phil. Mag., 34 (5th Series), 46. Also, “On Endothermic Decompositions Obtained by Pressure”, 37, 31. And, “Transformations of Mechanical into Chemical Energy. Action of Shearing Stress”, 37, 470.Google Scholar
4. Takacs, L., (2000), “Quicksilver from Cinnabar: The First Documented Mechanochemical Reaction”, Jour. Metals, p. 12.Google Scholar
5. Gilman, J. J., (1995), “Mechanism of Shear-induced Metallization”, Czech. J. Phys., 48, 913.Google Scholar
6. Sornette, D., (1999), “Earthquakes: from Chemical Alteration to Mechanical Rupture”, Physics Reports, 313, 237.Google Scholar
7. Bridgman, P W, (1935), “Effects of High Shearing Stress Combined with High Hydrostatic Pressure”, Phys. Rev., 48, 825.Google Scholar
8. Boldyrev, V. V., (1990), “Mechanochemistry and Mechanical Activation of Solids”, Bull. Div. Chem. Sci., Akad. Nauk SSSR, 39, 2029.Google Scholar
9. Enikolopyan, N. S., Vol'eva, V. B., Khzardzhyan, A. A., and Ershov, V V, (1987), “Explosive Chemical Reactions in Solids”, Dokl. Akad. Nauk SSSR, 292, 1165.Google Scholar
10. Zharov, A. A., (1994), Chapter 7 in High Pressure Chemistry and Physics of Polymers, Ed. by Kovarskii, A. L., CRC Press, Boca Raton, FL.Google Scholar
11. Heinicke, G., (1984), Tribochemistry, Carl Hanser Verlag, Munich.Google Scholar
12. Boldyrev, V., (1986), “Mechanical Activation of Solids and Its Application to Technology”, Jour. Chim. Physique, 83, 821.Google Scholar
13. Sohma, J., (1989), “Mechanochemistry of Polymers”, Prog. Polymer Sci., 14, 451.Google Scholar
14. Fernández-Bertran, J. F., (1999), “Mechanochemistry: An Overview”, Pure Appl. Chem., 71, #4, 581.Google Scholar
15. Latanision, R. M., (1983), “General Overview - Atomistics of Environmentally-Induced Fracture”, in Atomistics of Fracture, NATO Conf. Series, Vol. VI - 5, Ed. by Latanision, R. M. and Pickens, J. R., p. 3, Plenum Press, NY.Google Scholar
16. Osada, Y. and Gong, J. P., (1993), “Stimuli-responsive Polymer Gels and Their Application to Chemomechanical Systems”, Prog Polymer Sci., 18, #2, 187.Google Scholar
17. Ceyer, S.T., (1990), “New Mechanisms for Chemistry at Surfaces”, Science, 249, 133.Google Scholar
18. Muhlstein, C. L., Stach, E. A., and Ritchie, R. O., (2002), “Mechanism of Fatigue in Micron-scale Films of Polycrystalline Silicon for Micromechanical Systems”, Appl. Phys. Lett., 80, #9, 1532.Google Scholar
19. Gilman, J. J., Johnston, W. G., and Sears, G. W., (1958), “Dislocation Etch Pit Formation in Lithium Fluoride”, Jour. Appl. Phys., 29, #5, 747.Google Scholar
20. Inoue, Y., Matsukawa, M., and Sato, K., (1989), “Effect of Surface Acoustic Wave Generated on Ferroelectric Support upon Catalysis”, J. Amer. Chem. Soc., 111, #24, 8965.Google Scholar
21. Gilman, J. J., (1995), “Shear-induced Chemical Reactivity”, in Metal-insulator Transitions Revisited, Edited by Ramakrishnan, Edwards, and Taylor, Rao & Francis, London, p. 269.Google Scholar
22. Pearson, R. G., (1997), Chemical Hardness, Wiley-VCH Verlag, Weinheim, Germany.Google Scholar
23. Burdett, J. K., (1995), Chemical Bonding in Solids, Chapter 8, Oxford Univ Press, NY.Google Scholar
24. Parr, R. G., and Yang, W., (1989), Density-Functional Theory of Atoms and Molecules, Oxford University Press, New York, p. 99.Google Scholar
25. Gilman, J. J., (1997), “Chemical and Physical ‘Hardness’”, Mat. Res. Innovations, 1, 71.Google Scholar
26. Zhou, Z. And Parr, R. G., (1990), “Activation Hardness: New Index for Describing the Orientation of Electrophilic Aromatic Substitution”, J. Am. Chem. Soc., 112, 5720.Google Scholar
27. Strössner, K., Ves, S., Kim, C. K., and Cardona, M., 1986, “Dependence of the Direct and Indirect Gap of AlSb on Hydrostatic Pressure”, Phys. Rev. B, 33, 4044.Google Scholar
28. Gilman, J. J., (1996), “Mechanochemistry”, Science, 274, 65.Google Scholar
29. Chen, J., (1991), “Attractive Interatomic Force as a Tunneling Phenomenon”, J. Phys.-Condensed Matter, 3, 1227.Google Scholar
30. Zener, C., (1934), “A Theory of the Electrical Breakdown of Solid Dielectrics”, Proc. Roy. Soc. Lond., 145, 523.Google Scholar
31. Lawn, B. R., (1993), Fracture of Solids - Second Edition, Cambridge University Press, p. 162.Google Scholar
32. Kelling, S. And King, D. A., (1998),“Acoustic Wave Enhancement of Catalytic Reaction Rates 0ver Platinum Surfaces”, Platinum Met. Rev., 42, 8.Google Scholar
33. Nishiyama, H., and Inoue, Y., (2003), “Opposite Changes in Work Function of Low and High Index Copper Surfaces with Surface Acoustic Wave Propagation”, J. Phys. Chem. B, 107, #34, 8738.Google Scholar
34. Kolsky, H., (1963), Stress Waves in Solids, Dover Publications, New York, p1623.Google Scholar