Comparison of Peel Tests for Metal–Polymer Laminates for Aerospace Applications

Standard peel tests for aerospace laminates based on metal–polymer systems, namely floating-roller and climbing-drum peel methods, have been accommodated in a unified theory of peeling. This theory also accommodates more basic peel tests such as T-peel and fixed-arm peel and also newer methods such as mandrel peel. These five methods have been applied to two aerospace laminate systems to critically examine their use in the determination of adhesive strength. The theory has been used to unify the outputs from the tests in terms of adhesive fracture toughness. In this way, the comparative merits of the methods can be commented on.

The validity of the standard methods has been put in doubt because of the absence of a correction for plastic bending energy and also because of the poor conformance of the peel arm to the roller system used in these methods. The unified theory and some measurements of peel-arm curvature help but not completely overcome some of these difficulties.

A further complication that arises in peel is a change in the plane of fracture. This reflects a transition from cohesive fracture in the adhesive to an adhesive fracture at the interfaces among adhesive, primer, and substrate. It is likely that such plane-of-fracture phenomena are intrinsic to evaluation of the laminate and that contemplation of cohesive fracture toughness for the adhesive cannot accommodate such events.     

Protocols for the Measurement of Adhesive Fracture Toughness by Peel Tests

This article reports on the work of the European Structural Integrity Society Technical Committee 4 (ESIS TC4) and its activities in the development of test protocols for peel fracture. Thirteen laboratories have been working on peel test methods in ESIS TC4 since 1997 and their activities are ongoing.

The aim of the work is to develop robust and credible test methods for the determination of adhesive fracture toughness by peel tests. Several geometric configurations have been used, namely, multi-angle fixed arm peel, T-peel, and roller assisted peel in the form of a mandrel test.

The starting point of their work is an established analysis of a peel method that is often developed from a global energy approach. The adopted analysis is combined with an experimental approach in order to resolve ambiguities in the determination of adhesive fracture toughness (G_A). The test methods involve the measurement of peel strength in order to calculate the total input energy for peel (G) and the calculation of the plastic bending energy (G_P) during peel. The latter is often obtained from a measurement of the tensile behaviour of the peel arm. Adhesive fracture toughness is then G - G_P.

Four ESIS TC4 projects are described. The first relates to fixed arm peel whilst the second and third involve both fixed arm and T-peel. The fourth project combines mandrel peel and fixed arm peel. Each project uses different types of polymeric adhesives in the form of quite different laminate systems. The selection of the laminate system enables all characteristics of laminate property to be embraced, for example, thin and thick adhesive layers, polymeric, and metallic peel arms and a range of flexibility in the laminates.

The development of the enabling science required to establish the test protocols is described and software for conducting all calculations is referenced.     

THE DEVELOPMENT OF A MANDREL PEEL TEST FOR THE MEASUREMENT OF ADHESIVE FRACTURE TOUGHNESS OF EPOXY–METAL LAMINATES

A mandrel peel test is established for measuring the adhesive fracture toughness of a metal/rubber-toughened epoxy laminate system. By adopting an energy balance analysis it is possible to determine directly both adhesive fracture toughness and plastic work in bending the peel arm around the mandrel. The suitability of the procedure is examined for various types of metal peel arms, which are classified in terms of their ability to deform plastically during the test. The plastic work is also predicted theoretically, and comparisons are made between the measured and calculated values. The fracture energies determined from the mandrel tests are compared with those obtained from 90° fixed-arm peel tests. For the calculations of plastic work in bending in the fixed arm test, various options are used when modelling the tensile stress-strain behaviour of the peel arm material. In addition, the adhesive layer thickness is considered in terms of its influence on the calculation of adhesive fracture toughness.     

THE DEVELOPMENT OF A MANDREL PEEL TEST FOR THE MEASUREMENT OF ADHESIVE FRACTURE TOUGHNESS OF EPOXY-METAL LAMINATES

A mandrel peel test is established for measuring the adhesive fracture toughness of a metal/rubber-toughened epoxy laminate system. By adopting an energy balance analysis it is possible to determine directly both adhesive fracture toughness and plastic work in bending the peel arm around the mandrel. The suitability of the procedure is examined for various types of metal peel arms, which are classified in terms of their ability to deform plastically during the test. The plastic work is also predicted theoretically, and comparisons are made between the measured and calculated values. The fracture energies determined from the mandrel tests are compared with those obtained from 90° fixed-arm peel tests. For the calculations of plastic work in bending in the fixed arm test, various options are used when modelling the tensile stress-strain behaviour of the peel arm material. In addition, the adhesive layer thickness is considered in terms of its influence on the calculation of adhesive fracture toughness.     

Protocols for the Measurement of Adhesive Fracture Toughness by Peel Tests

This article reports on the work of the European Structural Integrity Society Technical Committee 4 (ESIS TC4) and its activities in the development of test protocols for peel fracture. Thirteen laboratories have been working on peel test methods in ESIS TC4 since 1997 and their activities are ongoing.

The aim of the work is to develop robust and credible test methods for the determination of adhesive fracture toughness by peel tests. Several geometric configurations have been used, namely, multi-angle fixed arm peel, T-peel, and roller assisted peel in the form of a mandrel test.

The starting point of their work is an established analysis of a peel method that is often developed from a global energy approach. The adopted analysis is combined with an experimental approach in order to resolve ambiguities in the determination of adhesive fracture toughness (G _A ). The test methods involve the measurement of peel strength in order to calculate the total input energy for peel (G) and the calculation of the plastic bending energy (G _P ) during peel. The latter is often obtained from a measurement of the tensile behaviour of the peel arm. Adhesive fracture toughness is then G – G _P .

Four ESIS TC4 projects are described. The first relates to fixed arm peel whilst the second and third involve both fixed arm and T-peel. The fourth project combines mandrel peel and fixed arm peel. Each project uses different types of polymeric adhesives in the form of quite different laminate systems. The selection of the laminate system enables all characteristics of laminate property to be embraced, for example, thin and thick adhesive layers, polymeric, and metallic peel arms and a range of flexibility in the laminates.

The development of the enabling science required to establish the test protocols is described and software for conducting all calculations is referenced.     

Effect of Peel Load on Stringiness Phenomena and Peel Speed of Pressure-Sensitive Adhesive Tape

The factors governing interfacial separation in lightly cross-linked polymer adhesives at low pulling rates as demonstrated by their stringiness phenomenon are investigated.

Cohesive failure and adhesive/substrate interfacial separation of uncross-linked polymer adhesives have been adequately explained. However, in lightly cross-linked polymer adhesives, where cohesive failure cannot occur because there is no viscous flow, there are two regions of interfacial separation at low rate and this phemonenon cannot be readily explained by present viscoelastic theories.

Investigation of the stringiness phenomenon of peeling pressure-sensitive adhesive tapes at constant loads shows that two peeling speeds exist for any peeling load up to the vicinity of 200 g/25 mm. Also it is clear that stringiness structure differs greatly at each peeling speed. The stringiness phenomenon of each of these two regions is analyzed using Miyagi's observation apparatus. These two measurements are then reversed and a comparison shows that the two peeling speeds correspond to each steady peeling region.

This field of investigation, when added to the present viscoelastic property studies, should lead to a new peeling adhesive theory which, in turn, may lead to the development of new high peel force pressure-sensitive adhesives.     

Adhesive Joint Durability Assessed Using Open-faced Peel Specimens

This paper presents an investigation of the durability of two aluminum-epoxy adhesive systems by means of open-faced peel specimens. A peel analysis model was used to determine the fracture energy from the peel data. Both wet and dry peel tests were conducted in order to distinguish between the reversible and the permanent effects of water. The effects of water on the cohesive properties of the adhesives were also assessed by tension tests. It was found that, for the two-part epoxy adhesive, which plasticized to a large extent, the peel testing should be carried out in a dry state to assess the interfacial weakening. It was also observed that the two-part adhesive was much stiffer in the dry, degraded state, and it was important to take account of such permanent changes in the cohesive properties associated with water uptake when determining the fracture energy from the peel data. In contrast, the one-part epoxy system did not suffer from appreciable cohesive changes, either reversible or permanent. In this case, both wet and dry failure loci were interfacial, and some of the interfacial damage was found to be reversible. Finally, surface analyses of the peel failure surfaces were carried out, and the formation of micro-debonds was identified as a possible mechanism of degradation for the two-part system.     

Peel Strength of Aluminium-Aluminium Joints Bonded by Adhesive Based on Carboxylated Nitrile Rubber-Chlorobutyl Rubber Blend

The peel strength of aluminium-aluminium joints bonded by an adhesive based on carboxylated nitrile rubber and chlorobutyl rubber was found to depend on surface topography and use of a silane primer. Anodization causes a marginal increase in bond strength while the silane primer improves the adhesive joint strength remarkably.

The peel strength was also found to be dependent on test conditions (test rate and temperature). The threshold peel strength value obtained by measurements at low peel rate and high test temperature was found to depend on the type of failure during peeling (cohesive or interfacial) which, in turn, is controlled by the presence of silica filler in the adhesive. Two different threshold values of peel strength were obtained: 60 N/m for interfacial failure (in silica-filled adhesive), 140 N/m for cohesive failure (in unfilled adhesive).     

Relationship between Phenolic Adhesive Chemistry, Cure and Joint Performance. Part I. Effects of Base Resin Constitution and Hardener on Fracture Energy and Thermal Effects During Cure

In this study the relationships between the composition of phenol resorcinol-formaldehyde resins and paraformaldehyde concentration in the adhesive were explored, using DSC, IR, GPC, and solubility measurements. Differences of chemical composition between base resins and adhesives were compared to the fracture toughness of adhesive bonds.

The cure temperature and cure time effects upon fracture toughness were also investigated. Fracture toughness tests were performed with bonded hard maple tapered double-cantilever beam cleavage specimens.     

Adhesive Joint Durability Assessed Using Open-faced Peel Specimens

This paper presents an investigation of the durability of two aluminum-epoxy adhesive systems by means of open-faced peel specimens. A peel analysis model was used to determine the fracture energy from the peel data. Both wet and dry peel tests were conducted in order to distinguish between the reversible and the permanent effects of water. The effects of water on the cohesive properties of the adhesives were also assessed by tension tests. It was found that, for the two-part epoxy adhesive, which plasticized to a large extent, the peel testing should be carried out in a dry state to assess the interfacial weakening. It was also observed that the two-part adhesive was much stiffer in the dry, degraded state, and it was important to take account of such permanent changes in the cohesive properties associated with water uptake when determining the fracture energy from the peel data. In contrast, the one-part epoxy system did not suffer from appreciable cohesive changes, either reversible or permanent. In this case, both wet and dry failure loci were interfacial, and some of the interfacial damage was found to be reversible. Finally, surface analyses of the peel failure surfaces were carried out, and the formation of micro-debonds was identified as a possible mechanism of degradation for the two-part system.     

Bonding of Natural Rubber to Steel: Surface Roughness and Interlayer Structure

This paper is concerned with two aspects of the adhesion produced by the vulcanisation bonding of a simple natural rubber (N.R.) compound to mild steel. Adhesion was measured using a 45° peel test.

When the N.R. was bonded, using a proprietary bonding agent (Chemlok 205/220), to 'smooth' steel (acid etched) or to 'rough' steel (phosphated) high values of peel energy (≥ 4.5 kJm^-2), and good environmental resistance to water were obtained, with failure cohesive largely within the rubber. The highest values of peel energy (≈ 7.5 kJm^-2) were associated with a phosphated surface which consisted of plate-like crystals which directed the stresses away from the substrate in a way which produced a failure surface within the rubber which showed extensive tearing and cracking.

The nature of the layer formed in the interfacial region by interaction between bonding system and rubber was investigated using a chlorinated rubber as a 'model compound' representing the adhesive and uncompounded N.R. to represent the rubber. When a blend of the two was heated in air at 150°C, evidence was found of a solid state chemical reaction in which carbonyl groups were incorporated into the blend which became visually homogeneous. Further evidence points to the relevance of this change to adhesion in rubber-to-metal bonding.     

COHESIVE ZONE MODELS AND THE PLASTICALLY DEFORMING PEEL TEST

The peel test is a popular test method for measuring the peeling energy between flexible laminates. However, when plastic deformation occurs in the peel arm(s) the determination of the true adhesive fracture energy, G c , from the measured peel load is far from straightforward. Two different methods of approaching this problem have been reported in recently published papers, namely: (a) a simple linear-elastic stiffness approach, and (b) a critical, limiting maximum stress, σmax , approach. In the present article, these approaches will be explored and contrasted. Our aims include trying to identify the physical meaning, if any, of the parameter σmax and deciding which is the better approach for defining fracture when suitable definitive experiments are undertaken.

Cohesive zone models Fracture mechanics Laminates Peel tests Plastic deformation     

On the effect of pulsed laser ablation on shear strength and mode I fracture toughness of Al/epoxy adhesive joints

The present work describes an experimental study about the shear strength and the mode I fracture toughness of adhesive joints with substrates pre-treated by pulsed laser ablation. An ytterbium-doped pulsed fiber laser was employed to perform laser irradiation on AA6082-T4 alloy. Morphological and chemical modifications were evaluated by means of surface profilometry, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Thick adherend shear tests were carried out in order to assess the shear strength while the mode I fracture toughness was determined using the double cantilever beam. For comparison, control samples were prepared using classical surface degreasing. The results indicated that laser ablation has a favorable effect on the mechanical behavior of epoxy bonded joints; however, while a + 20% increase was recorded for shear strength, a remarkable threefold enhancement of fracture toughness was observed with respect to control samples. XPS analyses of treated substrates and SEM observations of the fracture surfaces indicated that laser pre-treatment promoted chemical and morphological modifications able to sustain energy dissipation through mechanical interlocking. As a result cohesive failure within the adhesive bond-line was enabled under predominant peel loading.     

Interlaminar Bond Strength and Failure Mechanisms in Commercial Flexible Polymer-Metal Laminates

An alternative to the 180° “T” peel test (called simply the “T-peel test” in the USA) was developed by Cropper and Young for the measurement of interlaminar bonding in three-ply polypropylene-aluminium-polyester laminates used in food packaging applications. The effect of temperature on the interlaminar bond strength of three laminate systems has since been studied. In particular, the effect of temperature on both the failure mode and on the adhesive's appearance after testing has been determined. It is shown that as the temperature is raised about 23°C, the laminating adhesive begins to soften and the failure mode changes from almost exclusively adhesive failure at the polyurethane adhesive-aluminium interface to cohesive failure of the polyurethane adhesive itself. The change in the failure mode is accompanied by the appearance of a meniscus instability. The temperature at which the meniscus instability patterns become more prominent correspond to the temperature at which the maximum interlaminar bond strength is attained.

It is thought that this new test can be used to characterise the behaviour of laminating adhesives more fully, both in their change in appearance with temperature, and in their effectiveness in bonding layers together as temperatures are increased above ambient conditions.     

Non-destructive Inspection of Adhesively-bonded Joints

The objective of any system of non-destructively examining an adhesive joint must be to obtain a direct correlation between the strength of the joint and some mechanical, physical or chemical parameter which can readily be measured without causing damage. Faults or defects are defined as anything which adversely affect the short or long term strength of a joint. There are two basic areas for examination, the cohesive strength of the polymeric adhesive, and the adhesive strength of the bond between polymer and substrate.

Adhesive strength is very difficult to measure since it is an interfacial phenomenon involving a very thin layer of material, thin even in comparison with bond-line dimensions. Effectively, it would be necessary to assess intermolecular forces and this is not readily possible with existing techniques. This aspect of quality control is usually reduced to assessing the nature of the adherend surfaces prior to bonding.

The cohesive strength of the adhesive is really the only parameter which can be estimated with any degree of confidence, and it is this which features most on destructive tests of bonded joints.

In this paper, defects including porosity, surface un-bonds, zero-volume unbonds, poor cure and so on are discussed, together with the various methods currently used (and some new methods) for physical non-destructive testing.     

Relationship Between Viscoelastic and Peeling Properties of Model Adhesives. Part 2. The Interfacial Fracture Domains

The viscoelastic and peeling properties of polybutadiene/tackifying resin compatible blends have been studied in detail. Viscoelastic properties have been described through the variations of the complex shear modulus, G*(w), as a function of frequency, W, and peeling properties through the variations of peeling force (F) as a function of peeling rate (V).

The first paper of this series presented the cohesive fracture domain and the present paper explores the interfacial fracture domain: (i) rubbery interfacial (interfacial 1); (ii) stick-slip; (iii) glassy interfacial (interfacial 2). After a general survey of the properties in the three domains we present a quantitative relationship between the peeling and linear viscoelastic properties as a function of the adhesive formulation, discussing the use of time-temperature equivalence for adhesive properties. The third part of the paper presents the trumpet model of de Gennes describing the crack shape and propagation: starting from a mechanical analysis of the peeling test, it is shown how one may calculate the variations of the peeling force as a function of peeling rate in the various interfacial fracture domains: this model defines a single interfacial fracture criterion which coexists with the cohesive fracture criterion defined earlier, whatever the fracture location.

We present as a conclusion a critical discussion of the relevance and physical meaning of such a criterion and present a new outlook for the modeling and improvement of adhesive formulations.     

Adhesion and Failure Mechanisms of a Model Hot Melt Adhesive Bonded to Polypropylene

A model hot melt adhesive (HMA) based on an ethylene/vinyl acetate copolymer (EVA), an Escorez® hydrocarbon tackifier, and a wax has been used to bond together polypropylene (PP) films to give equilibrium bonding. Peel strengths were determined over a broad range of peel rates and test temperatures. Contrary to the peel behavior of joints with simple rubbery adhesives [1], peel strengths with this semi-crystalline adhesive are not rate-temperature superposable, and multiple transitions in failure locus occur. The semi-crystalline structure of the HMA also prevents rate-temperature superposition of its dynamic moduli.

At different test temperatures, the dependence of peel strength on peel rate shows some resemblance to the dependence of the loss tangent of the bulk adhesive on frequency. This is consistent with a previous result [2] that the HMA debonding term. D, varies with the loss tangent of a HMA at the T-peel debonding frequency.

This model HMA, similar to block copolymer/tackifier blends [3], consists of two phases: an EVA-rich and a tackifier-rich phase, in its amorphous region. At a low peel rate of 8.33 × 10^-5 m/s, the peel strength shows a maximum at a temperature that corresponds to the transition temperature of the tackifier-rich phase (T₁). At a higher peel rate of 8.33 × 10^-3 m/s, the peel strength rises with increasing test temperature, but becomes essentially constant at temperature T₁'. It is believed that, to optimize the peel strength of a HMA at ambient temperature, it is advantageous to formulate the EVA polymer (or other semi-crystalline polyolefins) with a compatible tackifier that yields a tackifier-rich phase with a transition temperature (T₁') in the vicinity of room temperature.     

Fracture Toughness of Adhesive Joints

To define the influence of the processing variables on the resistance of epoxy joints to brittle crack extension during short loading times, the fracture toughness, g_ic, of the joints was measured as a function of the following variables:

1. Hardener type (TEPA vs. HHPA)

2. Ratio of hardener to resin content

3. Post-cure temperature

and 4. Joint geometry (thickness and width)

It was found that the toughness of the TEPA hardened system varied by a factor of four-to-one as the ratio of hardener to resin content and post-cure temperature varied within what might be considered reasonable limits for manufacturing. The toughness of the HHPA hardened system varied only over the middle half of this same range.

For both systems, toughness increased with joint thickness over the range of 2 to 50 mils.     

Outline of an Algorithm for Computation of the Strength of Polymer Adhesive Joints

An algorithm based on hierarchical polymer structure is proposed for calculation of the adhesive joint strength. This hierarchy enables one to describe the behavior of polymer adhesive joints taking into account specific characteristics of all the levels by combining together physico-chemical concepts of the formation of adhesive systems and their fracture mechanics.

In order to prove the validity of the described approach electroless copper plated ABS-copolymers were studied experimentally.

The developed approach makes it possible to take into consideration the effect of the parameters characterizing the formation of an adhesive joint on its strength properties.     

Crack growth and fracture behavior of fabric reinforced polymer composites

The objective of this study is to understand and characterize crack deflection and sub-crack growth in fabric laminate composites. The theory of crack digression based on the Cook-Gordon mechanism of crack blunting and the criterion developed by Kendall were used to study the crack propagation phenomenon. A simple approach has been developed to evaluate the cohesive and adhesive fracture energies, which play a vital role in the study of strength and toughness of the fabric laminate composites. The effects of strain rate and quasi-static crack velocity on these energy values were identified. This study explored the possibility of selftoughening in an otherwise brittle composite system. Two competing mechanisms have been identified that control crack propagation in fabric laminate composites.