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.

An improved analytical model for the double cantilever beam fracture specimen is developed by treating a finite length beam which is partly free and partly supported by an elastic foundation. The results obtained are shown to be in excellent agreement with established data for initial crack extension. Some preliminary computational results for unstable crack propagation are also presented.

An augmented double cantilever beam model for studying crack propagation and arrest

In the present paper, the following topics are reviewed in detail: (a) the available adhesives, as well as their recent advances, (b) thermodynamic factors affecting the surface pretreatments including adhesion theories, wettability, surface energy, (c) bonding mechanisms in the adhesive joints, (d) surface pretreatment methods for the adhesively bonded joints, and as well as their recent advances, and (e) combined effects of surface pretreatments and environmental conditions on the joint durability and performance. Surface pretreatment is, perhaps, the most important process step governing the quality of an adhesively bonded joint. An adhesive is defined as a polymeric substance with viscoelastic behavior, capable of holding adherends together by surface attachment to produce a joint with a high shear strength. Adhesive bonding is the most suitable method of joining both for metallic and non-metallic structures where strength, stiffness and fatigue life must be maximized at a minimum weight. Polymeric adhesives may be used to join a large variety of materials combinations including metal-metal, metal-plastic, metal-composite, composite-composite, plastic-plastic, metal-ceramic systems. Wetting and adhesion are also studied in some detail in the present paper since the successful surface pretreatments of the adherends for the short- and long-term durability and performance of the adhesive joints mostly depend on these factors. Wetting of the adherends by the adhesive is critical to the formation of secondary bonds in the adsorption theory. It has been theoretically verified that for complete wetting (i.e., for a contact angle θ equal to zero), the surface energy of the adhesive must be lower than the surface energy of the adherend. Therefore, the primary objective of a surface pretreatment is to increase the surface energy of the adherend as much as possible. The influence of surface pretreatment and aging conditions on the short- and long-term strength of adhesive bonds should be taken into account for durability design. Some form of substrate pretreatment is always necessary to achieve a satisfactory level of long-term bond strength. In order to improve the performance of adhesive bonds, the adherends surfaces (i.e., metallic or non-metallic) are generally pretretead using the (a) physical, (b) mechanical, (c) chemical, (d) photochemical, (e) thermal, or (e) plasma method. Almost all pretreatment methods do bring some degree of change in surface roughness but mechanical surface pretreatment such as grit-blasting is usually considered as one of the most effective methods to control the desired level of surface roughness and joint strength. Moreover, the overall effect of mechanical surface treatment is not limited to the removal of contamination or to an increase in surface area. This also relates to changes in the surface chemistry of adherends and to inherent drawbacks of surface roughness, such as void formations and reduced wetting. Suitable surface pretreatment increases the bond strength by altering the substrate surface in a number of ways including (a) increasing surface tension by producing a surface free from contaminants (i.e., surface contamination may cause insufficient wetting by the adhesive in the liquid state for the creating of a durable bond) or removal of the weak cohesion layer or of the pollution present at the surface, (b) increasing surface roughness on changing surface chemistry and producing of a macro/microscopically rough surface, (c) production of a fresh stable oxide layer, and (d) introducing suitable chemical composition of the oxide, and (e) introduction of new or an increased number of chemical functions. All these parameters can contribute to an improvement of the wettability and/or of the adhesive properties of the surface.

Adhesively-bonded joints and repairs in metallic alloys, polymers and composite materials: Adhesives, adhesion theories and surface pretreatment

Due to the smoothness of the surfaces in surface micromachining, large adhesion forces between fabricated structures and the substrate are encountered. Four major adhesion mechanisms have been analysed: capillary forces, hydrogen bridging, electrostatic forces and van der Waals forces. Once contact is made adhesion forces can be stronger than the restoring elastic forces and even short, thick beams will continue to stick to the substrate. Contact, resulting from drying liquid after release etching, has been successfully reduced. In order to make a fail-safe device stiction during its operational life-time should be anticipated. Electrostatic forces and acceleration forces caused by shocks encountered by the device can be large enough to bring structures into contact with the substrate. In order to avoid in-use stiction adhesion forces should therefore be minimized. This is possible by coating the device with weakly adhesive materials, by using bumps and side-wall spacers and by increasing the surface roughness at the interface. Capillary condensation should also be taken into account as this can lead to large increases in the contact area of roughened surfaces.

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Stiction in surface micromachining

The toughness of a glass/'epoxy interface was measured over a wide range of mode mixes. A toughening effect was associated with increasing positive and negative in-plane shear components. Optical interference measurements of normal crack opening displacements near the crack front and complementary finite element analyses were used to examine near-front behavior during crack initiation. Estimates of the tough­ening based on plastic dissipation, bulk viscoelastic dissipation, and interface asperity shielding did not fully account for the measured values. The results suggest that the inelastic behavior of the epoxy, frictional, and, perhaps, three-dimensional effects should be considered. 1 Introduction Interfacial crack growth occurs in a number of applications of technological importance. Because of the fact that the frac­ture path is constrained irrespective of the orientation of the globally applied loads and also because of the mismatch of material properties across the interface, crack growth is in­herently mixed mode. Critical and subcritical crack growth must then be governed by some combination of mode I, II, and III fracture parameters. The simplest approach, using one parameter, seeks to determine an effective parameter that can account for all mode mixes in a unifying manner. This is particularly useful for subcritical crack growth where corre­lations of crack growth rates fall on one curve for all mode mixes when the proper parameter is found. An alternative is to consider a two-parameter approach where one parameter represents the mode mix or direction and the other a magni­tude. For critical crack growth, the magnitude will generally be a function of mode mix. The form the function is usually determined experimentally but may, as mechanisms are better understood, even be predicted. The most common approach for examining interfacial crack initiation has been to consider the interfacial fracture tough­ness, G

Asymmetric Shielding in Interfacial Fracture Under In-Plane Shear

Continuum fracture concept indicating essential surface energy interpretation difference in otherwise similar adhesive and cohesive failures

The continuum interpretation for fracture and adhesion.

In studies of fracture mechanics the adhesive fracture energy is regarded as a fundamental property of the adhesive system. It is pointed out that the value of the adhesive fracture energy depends on surface preparation, curing conditions, and absorbed monolayers. A test method reported makes use of a disk whose peripheral part is bonded to a substrate material. Pressure is injected into the unbonded central part of the disk. At a certain critical pressure value adhesive failure can be observed. A numerical stress analysis involving arbitrary geometries is conducted.

Adhesive fracture mechanics

Electron paramagnetic resonance (EPR) techniques were used to determine the number of free radicals produced during deformation leading to fracture of nylon 6 fibers. A reaction‐rate molecular model is proposed to explain some of the deformation and bond‐rupture behavior leading to fracture. High‐strength polymer fibers are assumed to consist of a sandwich structure of crystalline‐block and amorphous‐flaw regions along the fiber axis. In the flaw regions, tie chains connecting the crystalline blocks are assumed to have a statistical distribution in length. These chains are, therefore, subjected to different stresses. The length distribution was determined by EPR. The probability of bond rupture was assumed to be controlled by reaction‐rate theory with a stress‐aided activation energy and behavior of various loadings determined by numerical techniques. The model is successfully correlated with experimental stress, strain, and bond‐rupture results for creep, constant‐rate‐of‐loading, and cyclic‐stress tests.

Reaction‐Rate Model for Fracture in Polymeric Fibers

Complementing an earlier paper which utilized an energy balance criterion for a continuum mechanics analysis of adhesive failure in a pressurized blister at the interface of an elastic material and a rigid substrate, the analysis is extended to include an additional elastic interlayer between them. An infinite lateral-length elastic plate strip bonded through a Winkler elastic foundation to a rigid substrate is assumed, in which the plate is separated from the adhesive layer by internal pressure. It is found that the important design parameters are the tensile modulus-to-thickness ratio of the adhesive layer and the adhesive fracture energy of separation of the respective materials. The results provide a basis for investigating changes in the chemical microstructure of the adhesive.

The fracture threshold for an adhesive interlayer

Electron paramagnetic resonance (EPR) techniques are used to determine the number of free radicals produced during deformation leading to fracture of nylon 6 fibers. A reaction rate molecular model is proposed to explain some of the deformation and bond rupture behavior leading to fracture. High-strength polymer fibers are assumed to consist of a sandwich structure of disordered and ordered regions along the fiber axis. In the disordered or critical flaw regions, tie chains connecting the ordered or crystalline block regions are assumed to have a statistical distribution in length. These chains are, therefore, subjected to different stresses. The effective length distribution was determined by EPR. The probability of bond rupture was assumed to be controlled by reaction-rate theory with a stress-aided activation energy and behavior of various loadings determined by numerical techniques. The model is successfully correlated with experimental stress, strain, and bond rupture results for creep, constant rate loadings, cyclic stress, stress relaxation and step strain tests at room temperature.

M. L. Williams

Papers

The continuum interpretation for fracture and adhesion.

Adhesive fracture mechanics

Reaction‐Rate Model for Fracture in Polymeric Fibers

The fracture threshold for an adhesive interlayer

Fracture behavior in nylon 6 fibers