The chemical effects of ultrasound derive primarily from acoustic cavitation. Bubble collapse in liquids results in an enormous concentration of energy from the conversion of the kinetic energy of the liquid motion into heating of the contents of the bubble. The high local temperatures and pressures, combined with extraordinarily rapid cooling, provide a unique means for driving chemical reactions under extreme conditions. A diverse set of applications of ultrasound to enhance chemical reactivity has been explored with important uses in synthetic materials chemistry. For example, the sonochemical decomposition of volatile organometallic precursors in low-volatility solvents produces nanostructured materials in various forms with high catalytic activities. Nanostructured metals, alloys, oxides, carbides and sulfides, nanometer colloids, and nanostructured supported catalysts can all be prepared by this general route. Another important application of sonochemistry in materials chemistry has been the preparation of biomaterials, most notably protein microspheres. Such microspheres have a wide range of biomedical applications, including their use in echo contrast agents for sonography, magnetic resonance imaging, contrast enhancement, and oxygen or drug delivery. Other applications include the modification of polymers and polymer surfaces.

Applications of ultrasound to materials chemistry

Engineering applications of synthetic polymers are widespread due to their availability, processability, low density, and diversity of mechanical properties (Figure 1a). Despite their ubiquitous nature, modern polymers are evolving into multifunctional systems with highly sophisticated behavior. These emergent functions are commonly described as “smart” characteristics whereby “intelligence” is rooted in a specific response elicited from a particular stimulus. Materials that exhibit stimuli-responsive functions thus achieve a desired output (O, the response) upon being subjected to a specific input (I, the stimulus). Given that mechanical loading is inevitable, coupled with the wide range of mechanical properties for synthetic polymers, it is not surprising that mechanoresponsive polymers are an especially attractive class of smart materials. To design materials with stimuli-responsive functions, it is helpful to consider the I-O relationship as an energy transduction process. Achieving the desired I-O linkage thus becomes a problem in finding how to transform energy from the stimulus into energy that executes the desired response. The underlying mechanism that forms this I-O coupling need not be a direct, one-step transduction event; rather, the overall process may proceed through a sequence of energy transduction steps. In this regard, the network of energy transduction pathways is a useful roadmap for designing stimuli-responsive materials (Figure 1b). It is the purpose of this review to broadly survey the mechanical to chemical * To whom correspondence should be addressed. Phone: 217-244-4024. Fax: 217-244-8024. E-mail: jsmoore@illinois.edu. † Department of Chemistry and Beckman Institute. ‡ Department of Materials Science and Engineering and Beckman Institute. § Department of Aerospace Engineering and Beckman Institute. Chem. Rev. XXXX, xxx, 000–000 A

Mechanically-induced chemical changes in polymeric materials

Regarding the activation of chemical reactions, today’s chemist is used to thinking in terms of thermochemistry, electrochemistry, and photochemistry, which is reflected in the organization and content of the standard physical chemistry textbooks. The fourth way of chemical activation, mechanochemistry, is usually less well-known. The purpose of the present review is to give a survey of the classical works in mechanochemistry and put the key mechanochemical phenomena into perspective with recent results from atomic force microscopy and quantum molecular dynamics simulations. A detailed historical account on the development of mechanochemistry, with an emphasis on the mechanochemistry of solids, was recently given by Boldyrev and Tkáčová.1 The first written document of a mechanochemical reaction is found in a book by Theophrastus of Ephesus (371-286 B.C.), a student of Aristotle, “De Lapidibus” or “On stones”. If native cinnabar is rubbed in a brass mortar with a brass pestle in the presence of vinegar, metallic mercury is obtained. The mechanochemical reduction probably follows the reaction:1-3 * To whom correspondence should be addressed. Telephone: ++49-89-289-13417. Fax: ++49-89-289-13416. E-mail: martin.beyer@ch.tum.de (M.K.B.); Telephone: ++49-89-12651417. Fax: ++49-89-1265-1480. E-mail: clausen-schaumann@ fhm.edu (H.C.-S.). † Technische Universität München. ‡ Institut für Strahlenschutz. § Current address: Munich University of Applied Sciences. HgS + Cu f Hg + CuS (1) Volume 105, Number 8

http://depa.fquim.unam.mx/amyd/archivero/MECANOQUIMICA_3426.pdf

Mechanochemistry: the mechanical activation of covalent bonds.

Transesterification of soybean oil to biodiesel using CaO as a solid base catalyst

Free radical formation induced by ultrasound and its biological implications

Mechanochemistry of polymers

Basic sites and reducing sites of calcium oxide and their catalytic activities

ESR spectra have been observed from several polymers (polyethylene, polypropylene, polymethylmethacrylate, polytetrafluoroethylene, and polybutadiene) which were mechanically fractured in vacuum at 77°K. The spectra permit identification of the free radicals produced in chain scission. It has been demonstrated for the polymers of the type 

such as polypropylene and poly(methyl methacrylate), that the mechanical fracture produces two different scission radicals in pairs, namely, 

The results indicate convincingly that microscopic scission of polymer chains is caused by macroscopic destruction of polymeric material. The critical molecular size for mechanical rupture of polyethylene chains was experimentally determined to be a degree of polymerization between 70 and 100. This size agrees fairly well with the value predicted from a theoretical model.

Junkichi Sohma

Papers

Mechanochemistry of polymers

Basic sites and reducing sites of calcium oxide and their catalytic activities

ESR evidence for main‐chain scission produced by mechanical fracture of polymers at low temperature

Direct evidence of main-chain scissions induced by ultrasonic irradiation of benzene solutions of polymers

ESR study of V2O5 catalyst on carriers