Carbon fibers and composites with epoxy resins: Topography, fractography and interphases

Interphases exist in hybrid materials and significantly influence their mechanical performance. To find a bridge between the microscopic and macroscopic mechanical properties, this work investigates the nanoscopic nature of surface/interphases in terms of topography, fractography, adhesion and stiffness. Here, we show that variations in both adhesive and attractive forces on oxidized high modulus (HM) and intermediate modulus (IM) carbon fiber surfaces appear to result from the coating layer. The coating layer is critical for adhesive interaction with two different epoxy resins. The HM fiber has the apparently higher roughness but lower surface area than the IM fiber on the scanning scale of 200 nm. The surface roughness on a few tens of nanometer scale has no significant contribution to interphase adhesion from ‘mechanical interlocking’. In contrast, the true contact area on the nanometer scale plays a dominant role in interfacial adhesion. Using force volume nanoindentation, the stiffness of the resin region near the finished fiber surface was found to not depend on the distance from the fiber surface. Our observations suggest an energy-geometry link between critical interphase energy release rate by micromechanical testing and detailed fracture surface features.     

Effect of surface pre-treatment on surface characteristics and adhesive bond strength of aluminium alloy

In this work aluminium alloy surfaces have been subjected to three different methods of surface pre-treatments such as solvent degreasing, FPL (Forest Products Laboratory) etching and priming using an epoxy based primer. The treated surfaces were evaluated for surface energy, contact angle, surface topography, surface roughness and adhesive strength characteristics. The influence of surface pre-treatments on the variation of polar, dispersive and total surface energy of the surfaces is addressed. A wettability test was performed on the surfaces using an epoxy adhesive in order to assess the influence of the pre-treatment techniques on substrate/adhesive interaction. Theoretical work of adhesion values for the various pre-treated surfaces were calculated using the contact angle data and further tested experimentally by adhesive bond strength evaluation by tensile testing of a single lap aluminium-epoxy-aluminium assembly. The method of surface pre-treatment showed a profound effect on the surface topography and roughness by AFM. This study reveals that a combination of high surface energy and high surface roughness of the substrate along with good wettability of the adhesive contributed to the highest joint strength for the aluminium alloy through the FPL etching pre-treatment.     

Comparative determination of TiO2 surface free energies for adhesive bonding application

The development of durable bonds using titanium adherens has been investigated from the point of view of surface energy theoretical models measurements. The traditional Chromium Acid Anodization, which provides excellent durability, has to be phased out due to the use of hazardous Cr (VI) in the bath and as a result, special attention is paid to the sodium hydroxide anodizing and other alkaline chemical etchers. There are hardly any references on the surface free energy of adhesive titanium oxide coatings and therefore the objective of this work was to evaluate the surface and interface energy parameters of the various types of alkaline chromate free surface treatments using Neumann, Fowkes and van Oss–Chaudhury–Good methods in order to determine which method provides greatest differentiation between the coatings. Results show that Fowkes method produced the greatest variance in surface energies of the compared surface treatments and hence can be considered as better suited for more accurate discrimination between the oxide surface treatments on Ti–6Al–4V alloy. Although, in the case of model liquids, i.e. water and diiodomethane, the trends obtained for contact angles, surface energies, works of adhesion and solid/liquid interface energies all correlated between each other, a disagreement between the trends of solid/liquid interface energies calculated using Fowkes and van Oss–Chaudhury–Good methods for surface treatment/adhesive resin was obtained. In case of real adhesive systems, the use of work of adhesion appears more adequate in order to discriminate the surface treatments. Based on these findings the anodization in the tested alkaline bath after a previous alkali etching in the same bath is recommended, although adhesion test has to be still performed.     

A new technique for evaluating ink–cellulose interactions: initial studies of the influence of surface energy and surface roughness

Ink–cellulose interactions were evaluated using a new technique in which the adhesion properties between ink and cellulose were directly measured using a Micro-Adhesion Measurement Apparatus (MAMA). The adhesion properties determined with MAMA were used to estimate the total energy release upon separating ink from cellulose in water. The total energy release was calculated from interfacial energies determined via contact angle measurements and the Lifshitz–van der Waals/acid–base approach. Both methods indicated spontaneous ink release from model cellulose surfaces, although the absolute values differed because of differences in measuring techniques and different ways of evaluation. MAMA measured the dry adhesion between ink and cellulose, whereas the interfacial energies were determined for wet surfaces. The total energy release was linked to ink detachment from model cellulose surfaces, determined using the impinging jet cell. The influences of surface energy and surface roughness were also investigated. Increasing the surface roughness or decreasing the surface energy decreased the ink detachment due to differences in the molecular contact area and differences in the adhesiom properties.     

Characterization of the surface energies of functionalized multi-walled carbon nanotubes and their interfacial adhesion energies with various polymers

The surface energies of pristine multi-walled carbon nanotubes (MWCNTs) and MWCNTs functionalized with carboxylic acid (MWCNT-COOH), acyl chloride and ethyl amine were characterized, and the effects of the changes in MWCNT surface energies on the interfacial adhesion and reinforcement of the composites were explored. When the surface energy of pristine MWCNTs was compared to that of functionalized MWCNTs, a decrease in the dispersive surface energy and an increase in the polar surface energy were observed. Interfacial adhesion energies between MWCNTs and various polymers were estimated from surface energy values of MWCNTs and various polymers. Among the MWCNTs, polyethylene, polystyrene and bisphenol-A polycarbonate (PC) had the highest interfacial energy with pristine MWCNTs, while nylon 6,6 and polyacrylamine exhibited the highest interfacial energy with MWCNT-COOH. When tensile properties and adhesion at the interface of PC and nylon 6,6 composites containing MWCNTs were examined, composites having high interfacial adhesion energy exhibited greater adhesion at the interface and reinforcement.     

The effect of bond formation on the tack of polymers

The tack of polymers to be used as adhesives is measured by a two-stage process of bond formation and bond separation. Bond formation is governed by the contact time, the contact force, the roughness of the surfaces, surface and interfacial tensions, and the mechanical or viscoelastic properties of the adhesive and substrate. This paper presents experimental studies of the contact formation of various model polymers on steel surfaces with well-defined and different degrees of roughness. The tack was measured with an instrument of the probe tack type, which determines the adhesive (interfacial) fracture energy per unit of interface as a measure of the tack and by means of which the most important parameters during bond formation and separation, such as the contact time, contact force, rate of separation, and temperature, can be adjusted and measured over sufficiently wide ranges. In the typical time interval for the contact time, the polymers are found in the plateau range of their viscoelastic spectrum. This means that entanglements strongly affect their bonding behaviour. Good agreement was found between the experimental results presented in this study and a model of contact formation on rough surfaces, published recently by Creton and Leibler [1], especially concerning the dependence of the adhesive fracture energy on the contact force and the contact time for smooth and rough substrate surfaces. The influence of the surface roughness becomes significant at low contact forces, where full contact is not yet developed on a rough substrate surface, and for polymers with comparatively high moduli. The fracture energy increases with the contact time and shows the same time dependence as the reciprocal modulus.     

Influence of Acrylic Adhesive Viscosity and Surface Roughness on the Properties of Adhesive Joint

In adhesion, the wetting process depends on three fundamental factors: the surface topography of the adherend, the viscosity of the adhesive, and the surface energy of both. The aim of this paper is to study the influence of viscosity and surface roughness on the wetting and their effect on the bond strength. For this purpose, an acrylic adhesive with different viscosities was synthesized and some properties, such as viscosity and surface tension, were studied before adhesive curing took place. Furthermore, the contact angle and the lap-shear strength were analyzed using aluminum adherends with two different roughnesses. Scanning electron microscopy was used to determine the effect of the viscosity and the roughness on the joint interface. The results showed that the adhesive exhibits an optimal value of viscosity. Below this value, at low viscosities, the low neoprene content produces poor bond strength due to the reduced toughness of the adhesive. Additionally, it also produces a high shrinkage during curing, which leads to the apparition of residual stresses that weakens the interfacial strength. However, once the optimum value, an increase in the viscosity produces a negative effect on the joint strength as a result of an important decrease in the wettability.     

London-van der Waals adhesiveness of rough particles

Van der Waals forces often dominate interactions and adhesion between fine particles and, in turn, decisively influence the bulk behaviour of powders. However, so far there is no effective means to characterize the adhesive behaviour of such particles. A complication is that most powder particles have rough surfaces, and it is the asperities on the surfaces that touch, confounding the actual surface that is in contact. Conventional approaches using surface energy provide limited information regarding adhesion, and pull-off forces measured through atomic force microscope (AFM) are highly variable and difficult to interpret. In this paper we develop a model which combines the Rumpf-Rabinovich and the JKR-DMT theories to account simultaneously for the effects of surface roughness and deformation on adhesion. This is applied to a ‘characteristic asperity’ which may be easily obtained from AFM measurements. The concept of adhesiveness, a material property reflecting the influences of elastic deformability, surface roughness, and interfacial surface energy, is introduced as an efficient and quantitative measure of the adhering tendency of a powder. Furthermore, a novel concept of specific adhesiveness is proposed as a convenient tool for characterizing and benchmarking solid materials. This paper provides an example to illustrate the use of the proposed theories.     

Surfactant modification of the surface energetics of hydrophobic polymers and protein adsorption

A low interfacial free energy between a polar surface and water is expected to lead to a smaller amount of protein adsorbed. However, nonpolar surfaces have high interfacial free energies with water. They can acquire lower interfacial free energies by modifying the polar and dispersion components of their surface free energy so that they approach those of water. The two-phase method, in which an aqueous solution of surfactant and chloroform constitute the two-phase system, can be used for the modification of the hydrophobic surface. The hydrophobic polymer is immersed for a short time in chloroform (which is a solvent for the polymer). This allows disentanglement of the surface chains. Subsequently, the polymer is pulled out through the solvent-water interface and further through the water phase. The monolayer of adsorbed surfactant present at the water-chloroform interface is thus transferred to the surface of the polymer. The hydrophobic chains of the surfactant and polymer entangle and the polar head groups orient towards the water phase. Protein adsorption experiments carried out with albumin and fibrinogen showed that the amounts of protein adsorbed on unmodified PMMA surfaces can be significantly higher than those on SDS- and Brij 35-modified surfaces. The sequence for adsorption is unmodified surface > SDS-modified surface > Brij 35-modified surface.     

Über den Einfluß der Grenzflächenspannung auf die Haftfestigkeit

The values of adhesion between four diffrent adhesive,and (i) steel substrates whose surface energy had been altered by adsorption, and (ii) several polymer having different surface energies, had been measured. The results show that the adhesion has a maximum value when the surface energy of the hardened adhesive is equals to that of the substrate, i.e. when the interfacial energy adhesive/substrate is a minimum. The adhesion of the adhesives to the polymer was much smaller than to the steel sprcimens and the dependence of the adhesion onm the interfacial energy was sharper in the case of the polymers. The decrease of the adhesion with increasing interfacial energy was fiund to be greater if the liquid adhesive wets the substrate badly than the steel speciman.     

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.     

Improved interfacial adhesion in carbon fiber/poly (ether ether ketone) composites with the sulfonated poly (ether ether ketone) sizing treatment

A water-soluble sulfonated poly (ether ether ketone) (SPEEK) sizing agent is prepared and applied to improve the interfacial adhesion of carbon fiber/poly (ether ether ketone) (CF/PEEK) composites. The surface morphology, surface roughness, surface chemistries, and surface free energy of SPEEK sized CF are obtained to understand the sizing effect. The results reveal the increased surface free energy and surface roughness of SPEEK sized CF. In addition, a chemical reaction between the CF surface and sizing layer is proved based on the results of XPS, IR, and ¹H NMR. The interfacial structure of CF/PEEK composites is further ascertained by AFM and the appearance of gradient interface could be verified for SPEEK sized CF/PEEK composites. The formation of the gradient interface is due to the chemical reaction between the CF and sizing agent as well as the improved compatibility between the sized CF and matrix, which benefits the improvement of interfacial adhesion.     

Role of acid-base interfacial bonding in adhesion

The strength of macroscopic adhesive bonds of polymers is known to be directly proportional to the microscopic exothermic interfacial energy changes of bond formation, as measured by Dupre's 'work of adhesion'. Since the work of adhesion can be very appreciably increased by interfacial acid-base bonding with concomitant increases in adhesive bond strength, it is important to understand the acid-base character of polymers and of the surface sites of substrates or of the reinforcing fillers of polymer composites. The best known acid-base bonds are the hydrogen bonds; these are typical of acid-base bonds, with interaction energies dependent on the acidity of the hydrogen donor and on the basicity of the hydrogen acceptor. The strengths of the acidic or basic sites of polymers and of inorganic substrates can be easily determined by spectroscopic or calorimetric methods, and from this information one can start to predict the strengths of adhesive bonds. An important application of the new knowledge of interfacial acid-base bonding is the predictable enhancement of interfacial bonding accomplished by surface modification of inorganic surfaces to enhance the interfacial acid-base interactions.     

The influence of surface morphology on the interfacial adhesion and fracture behavior of vacuum infused carbon fiber reinforced polymeric repairs

The current work is focused on the adhesion characteristics of vacuum infused repair patches on variously pretreated composite surfaces, given that the impregnation resin acts both as a consolidation agent of the reinforcement as well as a very thin bonding medium on a composite substrate. Initially, the pretreated surfaces, on which the repair patches were infused, were characterized with a number of surface analysis techniques such as X‐ray Photoelectron Spectroscopy (XPS), scanning electron microscopy (SEM), laser profilometry, dynamic contact angle and surface energy analysis. Double cantilever beam (DCB) repairs were then considered as the macroscopic method of assessment by infusing layers of carbon woven fabric onto the surface pretreated composite laminates. The behavior of the asymmetric DCB configuration was also studied by finite element modeling, for cohesive crack growth within the bondline, using the virtual crack extension (VCE) method. DCB testing results showed that the fracture resistance curves obtained from the repairs were lower than the numerical resistance curves. This was attributed to the preferential crack trajectory at the receptive infusion resin/pretreated composite interface. Correlation of the experimental fracture energies with the surface property data, revealed an explicit relationship between the surface roughness and the interfacial adhesion of the repair patches during crack initiation and propagation. The strain energy release rates of the DCB repairs were increased with increased surface roughness without dramatic change of the failure mode, as verified by the post‐failure examination of the fractured surfaces using scanning electron micrographs. POLYM. COMPOS., 29:92–108, 2008. © 2007 Society of Plastics Engineers     

Crack Path Selection in Adhesively-Bonded Joints: The Role of Material Properties

This paper investigates the role of material properties on crack path selection in adhesively bonded joints. First, a parametric study of directionally unstable crack propagation in adhesively-bonded double cantilever beam specimens (DCB) is presented. The results indicate that the characteristic length of directionally unstable cracks varies with the Dundurs' parameters characterizing the material mismatch. Second, the effect of interface properties on crack path selection is investigated. DCB specimens with substrates treated using various surface preparation methods are tested under mixed mode fracture loading to determine the effect of interface properties on the locus of failure. As indicated by the post-failure analyses, debonding tends to be more interfacial as the mode II fracture component in the loading increases. On the other hand, failures in specimens prepared with more advanced surface preparation techniques appear more cohesive for given loading conditions. Using a high-speed camera to monitor the fracture sequence, DCB specimens are tested quasi-statically and the XPS analyses conducted on the failure surfaces indicate that the effect of crack propagation rate on the locus of failure is less significant when more advanced surface preparation techniques are used. The effect of asymmetric interface property on the behavior of directionally unstable crack propagation in adhesive bonds is also investigated. Geometrically-symmetric DCB specimens with asymmetric surface pretreatments are prepared and tested under low-speed impact. As indicated by Auger depth profile results, the centerline of the crack trajectory shifts slightly toward the interface with poor adhesion due to the asymmetric interface properties. Third, through varying the rubber content in the adhesive, DCB specimens with various fracture toughnesses are prepared and tested. An examination of the failure surfaces reveals that directionally unstable crack propagation is more unlikely to occur as the toughness of the adhesive increases, which is consistent with the analytical predictions that were discussed using an energy balance model.     

Strength and bonding characteristics of adhesive joints with surface-treated titanium-alloy substrates

This paper presents a study on the effect of surface treatments on the mechanical behavior of adhesively bonded titanium alloy joints. Several different treatments were selected for the preparation of Ti-6Al-4V alloy faying surfaces, and bonded joints were fabricated using surface-treated titanium alloy substrates and a film adhesive. Tensile tests were performed on single-lap specimens to evaluate the joint strength and to assess the failure mode, i.e. cohesive failure, adhesive (interfacial) failure or a mix of both. Contact angle measurements were also carried out, and the surface free energies of titanium alloys and the thermodynamic works of adhesion for the adhesive/titanium alloy interfaces were obtained. A three-dimensional finite element analysis was used to predict the strength of the specimens exhibiting cohesive failure. In addition, an expression of the relationship between the joint strength corresponding to interfacial failure and the thermodynamic work of adhesion was introduced based on the cohesive zone model (CZM) concept. It is shown that two surface treatments, Itro treatment and Laseridge, lead to cohesive failure and a significant increase in the joint strength, and the numerically predicted strength values are fairly close to the experimental values. These surface treatments are possible replacements for the traditional surface treatment processes. For degreasing, emery paper abrasion, atmospheric plasma treatment, sulfuric acid anodizing, nano adhesion technology and high-power lasershot, the specimens fail at the adhesive/substrate interface and the joint strength increases linearly with the thermodynamic work of adhesion as expected from our CZM-based expression.     

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.     

Physico-Chemical Criteria for Maximum Adhesion. Part II: A New Comprehensive Thermodynamic Analysis

In this paper, two parameters defined as the relative work of adhesion [W_A/γ_L] and the relative interfacial energy [γ_SL/γ_L] have been examined for their assumed usefulness in correlating the thermodynamic properties of the components of the system substrate/ adhesive with its practical performance (strength). It is shown that the minimum value of [γ_SL/γ_L] relevant to conditions for the maximum adhesion becomes zero only for those systems (relatively rare) for which interaction factor Φ₀ is equal to 1.0.

Several transition points were identified for boundary conditions acquired at θ = 0° and θ = 90° which can be used to predict the properties and performance of an adhesive joint. These transition points are: a_MIN—energy modulus of the system (E. M. S.), relevant to the minimum interfacial energy; a_S—E. M. S. where self-spreading of adhesive occurs; a_CRIT—E. M. S. relevant to conditions under which the thermodynamic work of adhesion becomes negative and the system exhibits a tendency for self-delaminating or has “zero-strength”; a_CF—E. M. S. beyond which the geometry of the interface at any interfacial void or boundary of the joint may be regarded as a crack tip.

It is shown that only in those systems for which Φ₀ = 1.0 can a minimum contact angle of 0° indicate a condition for the maximum strength. If Φ₀ is known, the optimum contact angle can be estimated and hence the optimum surface energy of the substrate (adjusted by surface treatment, etc.) for the maximum adhesion.     

Aspects of surface characterization of polyurethane adhesives

The performances of adhesives is strongly dependent on the contributions to overall surface energies from dispersion and nondispersion forces. In this work, surface energies have been studied for polyurethanes representing the categories of aliphatic and aromatic polyethers and aliphatic polyesters. The surface energies of the polymers were measured by static and dynamic contact angle methods. In addition to determining the energy values for polymers as received, evaluations were also made on the polymers following modification by an aminopropyl silance (APS), present at concentrations ranging from 0.1 to 20 wt %. The dispersion surface energies of the three polymers were roughly equal; however, the nondispersive surface energies strongly differentiated among them. Organic liquids were used for calculations of energy parameters from static contact angles. Data for water failed to follow theoretical expectations and were used instead to compute a work of adhesion parameter for the polymer/water interface. This correlated with nondispersion surface energies of the polyurethanes. Somewhat different values of the nondispersion surface energy were obtained from static and dynamic contact angles, an effect attributed to the tendency of polyurethanes to restructure when their surfaces were in prolonged contact with water during dynamic analysis. This behavior may be important to the type of adhesive bond formed by the polymers and to variations in bond characterstics with time. The use of APS was found to influence both static and dynamic contact angle values, with primary changes occuring in nondispersion contributions. The effects of APS addition were fully developed at concentrations of 1 wt % or less, raising doubts about the efficiency of using this additive at higher concentrations. © 1994 John Wiley & Sons, Inc.     

Peel Adhesion: Influence of Surface Energies and Adhesive Rheology

The adhesion properties of polymers are known to be influenced by both intermolecular forces operative at the interface and the rheological history of both bonding and unbonding. Recent adsorption and viscoelastic theories of adhesion and cohesion are implemented in a comprehensive examination of these phenomena. Eight peel force “master curves” extending over 14 decades of reduced rate and representing glassy state to flow region rheology are superimposed to provide a composite response envelope. Each master curve represents rate-temperature reduced adhesion of an alkyl acrylate adhesive (γ_c = 26 dyne/cm) to substrates ranging from low adhesion fluorinated polymers (γ_c = 15 to 17 dyne/cm) to polar poly-amide surfaces (γ_c = 45 dyne/cm) and glass. The rate dependent transition from interfacial to cohesive failure, a subject not treated by adsorption theory, is shown to be coincident with the onset of entanglement slippage within the polymeric adhesive. Thermodynamic criteria of polymer adhesion are shown to be applicable only to the flow region of polymeric response. This study indicates that measured surface tensions or calculated surface energies of polymeric solids do not properly account for the contributions of three dimensional network structure of the polymeric bulk phase to its total work of cohesion. Evidence of true interfacial failure of a polymer-polymer bond is supported by critical surface tension measurements.