A Review of Contemporary Views of Theories of Adhesion

The once distinct and independent theories of adhesion have been losing their isolation and converging. Ideas of the effects of surface roughness, once dismissed as irrelevant except in the case of textiles, have been revised; albeit on a smaller scale as details of surfaces have been revealed by sophisticated techniques. Electrostatic interactions across an interface have been more deeply explored and their significance recognised and expounded. Diffusion of groupings and chain segments within a polymer have been related to the possibilities of interaction with a variety of surfaces. Perhaps most important, theories of adsorption have been extended in depth. The precise nature of the molecular interactions have been recognised and quantified. In doing this the contribution of diffusion and elastoplastic phenomena have been integrated. These developments are collated and analysed to present the present understanding of the concepts.     

A Review of Adhesion Mechanisms Using the Peel Test in Air and Liquid Media

This paper deals with the analysis of peel energy of assemblies measured in different environments, i.e. in air and in the presence of liquids, and constitutes a brief review of the work of Professor Schultz' team in this domain. It is shown how such measurements can lead to a better knowledge of the nature as well as of the magnitude of fundamental interactions established at the interface between two solids. Earlier experiments have shown that peel energy can be expressed as a product of three terms corresponding, respectively, to the reversible energy of interfacial adhesion, the hysteretic losses of the bulk materials and the molecular dissipation near the crack front during peeling. This approach is well-verified when only physical interactions (van der Waals) are involved at the interface. However, more complex cases correspond to systems where specific interactions are also established between both materials, in particular acid-base interactions and creation of chemical bonds. In both cases, peel measurements in liquid media can lead to the determination of fundamental parameters, such as the interfacial density of specific interactions at the interface and the acid-base or chemical components of the work of adhesion. Finally, the effect of interdiffusion phenomena on peel energies can also be investigated in the case of elastomer/elastomer assemblies.     

Model Studies of the Effect of Surface Roughness and Mechanical Interlocking on Adhesion

The apparent strength of adhesion has been measured for a soft elastic layer adhering to model porous substrates, consisting of rigid plates containing regular arrays of cylindrical holes. Two contributions to the apparent strength have been identified and compared with the predictions of a simple theoretical treatment. The first is adhesion to the surface itself. Because “rough” surfaces have greater area for bonding, the strength of adhesion was increased by as much as twenty-fold. The second arises from the work of breaking deeply embedded or entangled strands in order to detach the overlayer. Contributions from this mechanism were as much as several hundred times the (low) intrinsic strength of adhesion. Satisfactory agreement was obtained with theory in both cases. Measurements were also made using cloth substrates, when the adhering layer penetrated the cloth completely. The work of detaching and breaking permeating strands was again much larger than the intrinsic strength of adhesion, in reasonable agreement with theoretical predictions.     

Application of Acoustic Emission Measurements to Investigate Adhesion in Filled Polymeric Composites

Adhesion in filled polymeric composites is characterized by an acoustic technique in which specimens of the composites are subjected to a ramped uni-axial tensile stress while particle-matrix debonding events are detected acoustically. The maximum in a fitted distribution of debonding events as a function of applied stress is related to the interfacial strength using elasticity theory. Results are reported for different silanetreated and untreated glass and aluminum spheres embedded in a poly(vinyl butyral) matrix. Silane treatment profoundly affects the adhesive strength, with the strongest bonds being formed when acid-base interactions between the particle surface and the matrix polymer are promoted. Significant differences are also found between the aluminum-particle and glass-particle cases, attributable in part to differences in mechanical interlocking.     

Application of Acoustic Emission Measurements to Investigate Adhesion in Filled Polymeric Composites

Adhesion in filled polymeric composites is characterized by an acoustic technique in which specimens of the composites are subjected to a ramped uni-axial tensile stress while particle-matrix debonding events are detected acoustically. The maximum in a fitted distribution of debonding events as a function of applied stress is related to the interfacial strength using elasticity theory. Results are reported for different silanetreated and untreated glass and aluminum spheres embedded in a poly(vinyl butyral) matrix. Silane treatment profoundly affects the adhesive strength, with the strongest bonds being formed when acid-base interactions between the particle surface and the matrix polymer are promoted. Significant differences are also found between the aluminum-particle and glass-particle cases, attributable in part to differences in mechanical interlocking.     

Some Fundamental Issues in Adhesion: A Conceptual View

The role of interfacial interactions in determining the global response of joint systems is discussed in relation to the question of true interfacial failure and the ubiquitous occurrence of interphases. The discussion is from the point of view of systems involving adhesives, coatings and composites rather than, e.g., particle-particle or particlesubstrate systems and is strictly conceptual in nature. It is proposed that interfacial interactions, rather than directly exerting an effect on the global response of joint systems, are instead the driving force for the many and varied processes that create interphases. It is such interphases, or transition zones between phases, which affect the global mechanical response of joint systems.     

Some Fundamental Issues in Adhesion: A Conceptual View

The role of interfacial interactions in determining the global response of joint systems is discussed in relation to the question of true interfacial failure and the ubiquitous occurrence of interphases. The discussion is from the point of view of systems involving adhesives, coatings and composites rather than, e.g., particle-particle or particlesubstrate systems and is strictly conceptual in nature. It is proposed that interfacial interactions, rather than directly exerting an effect on the global response of joint systems, are instead the driving force for the many and varied processes that create interphases. It is such interphases, or transition zones between phases, which affect the global mechanical response of joint systems.     

Adhesion at Poly(Butylacrylate)-Poly(Dimethylsiloxane) Interfaces

We present an investigation of the adhesion modulation mechanisms of silica-like nanoparticles (MQ resins) incorporated in polydimethylsiloxane (PDMS) elastomers and acrylic adhesives. The Johnson-Kendall-Roberts (JKR) test has been used to gain information on the both zero velocity and the velocity dependence of the adhesive strength, avoiding as much as possible contributions to the adhesive strength of bulk dissipation in the adhesive (which is not the case with peel tests). As the incorporation of the MQ resins into the elastomers deeply affects their own mechanical properties, the loading and unloading curves of small poly(butylacrylate) (PBA) lenses on either PDMS elastomers, adsorbed PDMS and pure MQ resin layers are compared in a systematic manner. The PBA chains are observed to have a neat affinity for the MQ resin nanoparticles. When MQ resins are present at the interface, they tend to prevent facture propagation, thus producing a larger deformation of the PBA lens. The modulation of adhesion is then dominated by the corresponding dissipation inside the acrylic adhesive.     

A Review of Cell Adhesion Studies for Biomedical and Biological Applications

Cell adhesion is essential in cell communication and regulation, and is of fundamental importance in the development and maintenance of tissues. The mechanical interactions between a cell and its extracellular matrix (ECM) can influence and control cell behavior and function. The essential function of cell adhesion has created tremendous interests in developing methods for measuring and studying cell adhesion properties. The study of cell adhesion could be categorized into cell adhesion attachment and detachment events. The study of cell adhesion has been widely explored via both events for many important purposes in cellular biology, biomedical, and engineering fields. Cell adhesion attachment and detachment events could be further grouped into the cell population and single cell approach. Various techniques to measure cell adhesion have been applied to many fields of study in order to gain understanding of cell signaling pathways, biomaterial studies for implantable sensors, artificial bone and tooth replacement, the development of tissue-on-a-chip and organ-on-a-chip in tissue engineering, the effects of biochemical treatments and environmental stimuli to the cell adhesion, the potential of drug treatments, cancer metastasis study, and the determination of the adhesion properties of normal and cancerous cells. This review discussed the overview of the available methods to study cell adhesion through attachment and detachment events.     

Adhesion Between Hydrated Aluminium and Ethylene Copolymers Containing Methoxy Silane Groups

The peel strength between ethylene copolymers and aluminium has been investigated. The polymers were ordinary LDPE, copolymer with butyl acrylate (EBA), copolymer with vinyltrimethoxysilane (EVS), and copolymer with both comonomers (EVSBA). The aluminium was modified by hydration in boiling water up to 120 s. The strength of melt-pressed laminates was tested with a T-peel test and the failure mechanism was evaluated by FTIR and SEM. The hydration leads to a porous pseudoboehmite with an increased content of Al-OH groups, which causes considerable increases in peel strength for all polymers, in particular for EVS and EVSBA. The mode of failure varied between adhesive and cohesive depending on the surfaces. The introduced porosity contributes with mechanical keying while the Al-OH groups enable polar interactions for EBA and the formation of interfacial covalent bonds for EVS and EVSBA.     

Adhesion Between Hydrated Aluminium and Ethylene Copolymers Containing Methoxy Silane Groups

The peel strength between ethylene copolymers and aluminium has been investigated. The polymers were ordinary LDPE, copolymer with butyl acrylate (EBA), copolymer with vinyltrimethoxysilane (EVS), and copolymer with both comonomers (EVSBA). The aluminium was modified by hydration in boiling water up to 120 s. The strength of melt-pressed laminates was tested with a T-peel test and the failure mechanism was evaluated by FTIR and SEM. The hydration leads to a porous pseudoboehmite with an increased content of Al-OH groups, which causes considerable increases in peel strength for all polymers, in particular for EVS and EVSBA. The mode of failure varied between adhesive and cohesive depending on the surfaces. The introduced porosity contributes with mechanical keying while the Al-OH groups enable polar interactions for EBA and the formation of interfacial covalent bonds for EVS and EVSBA.     

Some Contributions of Surface Analysis to the Development of Adhesion Theories

A concise historical account of the development of adhesion theories and a critical discussion of their contemporary relevance are given.

The pioneering work of McBain and Hopkins in 1925 led to the development of the modern adsorption and mechanical theories of adhesion. Somewhat later, there were important contributions from Russia where workers introduced the electrostatic theory (Deryaguin) and the diffusion theory of adhesion (Voyutskii).

Recent developments in contact mechanics, molecular dynamics, and, in particular, surface analysis have provided considerable insight into the nature of the interface and interfacial region in adhesive joints. These suggest that adsorption, mechanical, and even diffusion effects cannot be completely isolated from one another. It is argued that each theory is best regarded as emphasising a different aspect of a more comprehensive model which, in principle, relates molecular dispositions in the region of the interface to macroscopic properties of an adhesive joint.     

Some Contributions of Surface Analysis to the Development of Adhesion Theories

A concise historical account of the development of adhesion theories and a critical discussion of their contemporary relevance are given.

The pioneering work of McBain and Hopkins in 1925 led to the development of the modern adsorption and mechanical theories of adhesion. Somewhat later, there were important contributions from Russia where workers introduced the electrostatic theory (Deryaguin) and the diffusion theory of adhesion (Voyutskii).

Recent developments in contact mechanics, molecular dynamics, and, in particular, surface analysis have provided considerable insight into the nature of the interface and interfacial region in adhesive joints. These suggest that adsorption, mechanical, and even diffusion effects cannot be completely isolated from one another. It is argued that each theory is best regarded as emphasising a different aspect of a more comprehensive model which, in principle, relates molecular dispositions in the region of the interface to macroscopic properties of an adhesive joint.     

Adhesion of Polypropylene Fiber to Cement Matrix

Abstract

In this research, the adhesion of polypropylene (PP) fibers to cementitious matrix has been investigated and the chemical bonding and mechanical interlocking between PP fiber and hardened cement paste has been studied. Furthermore, thermodynamic work of adhesion and loss-function (dissipation energy) has been calculated in the PP-cement matrix model system. To investigate the work of adhesion, the pull-out test has been used. Also, the surface free energy and contact angle of the PP monofilaments and cement matrix have been measured using a tensiometer and the fiber–cement interfacial interactions and thermodynamic work of adhesion and loss-function were calculated. Scanning electron microscopy (SEM) analysis was used to study the fiber–cement matrix interfacial transition zone (ITZ). The results showed that the application of theories of polymer–polymer adhesion in fiber–cement matrix systems was feasible. To verify the accuracy of the method, the adhesion of two other fibers (nylon 6,6 and acrylic polymer) was studied.     

Adhesion of Wax Droplets to Porous Polymer Surfaces

An experimental study was done to measure the force of adhesion of molten wax droplets, 3.1 mm in diameter, dropped from heights ranging from 20 to 50 mm onto porous polyethylene and Teflon surfaces. The Teflon surface had 0.25-mm holes drilled in it and the three polyethylene surfaces had random pores with mean diameters of 35, 70, and 125 μm, respectively. The force required to remove the solidified ink from the surface was measured using a pull test. Wax splats were attached to the substrate by both adhesive and cohesive forces. The cohesive force was calculated by multiplying the ultimate tensile strength of the wax (2.2 MPa) by the cross-sectional area of the wax penetrating into surface pores. The adhesive force was obtained by multiplying the contact area between the wax and substrate by the adhesion strength per unit area, estimated to be 0.2 MPa for polyethylene and 0.1 MPa for Teflon surfaces. The contact area between splats and the substrate was typically about 60–70% of the splat area. The edges of splats lifted up, preventing complete contact.     

Durability of Adhesion Between Metals and Polymers

Adequate adhesion between metals and polymers is primarily the result of chemical bonds in the boundary layer. This region, however, is subject to degradation by moisture. Three modes of deterioration are observed. The first is a largely reversible weakening effect in the polymer layer near the metal oxide surface. The structure of this layer differs from that of the bulk and is influenced by the chemical and physical properties of the surface. The second is a slow transformation of the oxide by hydration and a diffusion of oxide constituents into the polymer. This process is irreversible and is influenced by the state of the surface and chemical properties of the polymer. The third is a fast deterioration of the oxide by primary corrosion usually initiating at an unprotected edge but occasionally arising within the body of a joint.     

Adhesion Effects of Intermediate Layers on the Densification of Ceramic Powders

In the ceramic technology the first step to produce sintered bodies is the manufacturing of powders which then are densified. The adhesion mechanisms between the single particles and the agglomerates produced from them determine the densification process. Starting from theoretical considerations adhesion mechanisms, such as solid bridge formation, adhesive bonding and glide-promoting effects, are discussed in principle. Subsequently, the effects of surface-active substances on the densification behaviour of clay-ceramics and oxide-ceramic bodies are discussed. Further, the evaluation of the action of additives to the powder mixtures on the microstructure of the compacts, such as porsity and texture, leads to a compaction equation which describes the transition from the powder pile to a densified green body.     

The Mechanical Theory of Adhesion—Changing Perceptions 1925-1991

The changing fortunes of the mechanical theory of adhesion are traced from McBain and Hopkin's work in the 1920s to that of Venables in the 1970s and 1980s. Some comments are made on the factors which were associated with changes, during the period surveyed, in the accepted view of the importance of the theory.     

Surface Roughness on Adhesion of Silver Colloids to a Polyimide Substrate

The adhesion of silver colloids to a polyimide (PI) substrate was investigated in this study. This issue would be of concern when one tried to print electronic circuits on a flexible PI substrate. To enhance the adhesion between them, the PI surface was first roughened by using the sandblasting technique, and varying degrees of roughness were achieved using various sizes of alumina particles and various air pressures for sandblasting. The adhesion strength of silver colloids to the PI substrate after sintering was then measured according to both ASTM D4541 and ASTM 3359 standards. The results indicated that adhesion strength increased proportionally with surface roughness; however, this enhancement effect was lessened when the roughness was above 880 nm. Sintering temperature was also beneficial in increasing adhesion to the substrate; however, the electrical resistance of the silver colloids after sintering also increased with the degree of roughness. This implied that the packing of silver colloids was also affected by surface roughness. Consequently, values of surface roughness were optimal when adhesion strength and electrical resistivity were balanced.     

Adhesion to Sodium Naphthalenide Treated Fluoropolymers. Part III. Mechanism of Adhesion

Adhesion of fluoropolymers to copper and to other polymers is examined using a range of fluoropolymer types (PTFE, PFA, extruded, skived and cast films), surface modification techniques such as sodium naphthalenide (Na/naphth), acid stripping and lamination to produce surfaces of controlled roughness, and three tests of adhesion (90 degree peel tests, torsional shear tests and stripping of transmission electron microscopy (TEM) replicas). A combination of chemical and physical modification is required to produce good adhesion, with the relative importance of each dependent upon the specific adhesion test used. For relatively smooth-surfaced films, Na/naphth appears to function by increasing both the chemical functionality and the mechanical integrity of a surface layer. Untreated PTFE and PFA show interfacial failure and negligible adhesion. Smooth-surfaced PTFE with superficial surface modification, e.g. after lamination to shiny copper foil or after acid stripping of defluorinated material, often fails by fibrillation of the fluoropolymer surface. For short sodium etch times, adhesion is improved and the failure mode is interfacial. For long etch times, there is a mixed mode of failure. Fibrillation in smooth-surfaced PFA systems was not observed. Adequate adhesive strength in these systems could only be achieved by an increase in the surface roughness. The best adhesion could be achieved by surface roughening, followed by Na/naphth treatment. For such PTFE surfaces plated with copper, peel and shear tests showed a mixed mode of failure, with copper and fluoropolymer found on both failure surfaces by x-ray photoelectron spectroscopy (XPS) and energy dispersive x-ray spectroscopy (EDS). Extensive fibrillation occurred at the locus of failure. Provided chemical modification is adequate to allow wetting, the roughness of the surface dominates the properties of the adhesive bond. Prolonged Na/naphth treatment (e.g. one hour) causes a reduction in peel strengths.