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.     

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.     

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.     

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.     

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.     

Comparison of Analytical, Numerical, and Experimental Methods in Deriving Fracture Toughness Properties of Adhesives Using Bonded Double Lap Joint Specimens

Stress and fracture analysis of bonded double lap joint (DLJ) specimens have been investigated in this paper. Numerical and analytical methods have been used to obtain shear- and peel-stress distributions in the DLJ. The generalized analytical solution for the peel stress was calculated for various forms of the DLJ geometry and, by using crack closure integral (CCI) and by means of the J-integral approach, the analytical strain energy-release rate, G, was calculated. Experimental fracture tests have also been conducted to validate the results. The specimens were made of steel substrates bonded by an adhesive and loaded under tension. Specimens with cracks on both sides and at either end of the DLJ interface were tested to compare the fracture behavior for the two crack positions where tensile and compressive peel stresses exist. Tests confirmed that the substrates essentially behave elastically. Therefore, a linear elastic solution for the bonded region of the DLJ was developed. The fracture energy parameter, G, calculated from the elastic experimental compliance for different crack lengths, was compared with numerical and analytical calculations using the experimental fracture loads. The stresses from analytical analysis were also compared with those from the finite element results. The strain energy-release rate for fracture, G_f, for the adhesive has been shown to have no R-curve resistance, was relatively independent of crack length, and compared well with those obtained from numerical and analytical solutions. However, it was found that fracture energy for the crack starter in the position where the peel stress was tensile was about 20% lower than where the crack was positioned at the side, where the peel stress was found to be compressive.     

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.     

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.     

Fracture Mechanics: A Tool for Evaluating Structural Adhesives

Some of the basic concepts of fracture mechanics are reviewed, emphasizing those aspects of the discipline that are applicable to the evaluation of structural adhesives.

Test methods for measuring both the plane strain fracture toughness of joints, i.e. G_ic, and the resistance of joints to crack extension in the presence of an aggressive environment, i.e. G_iscc, are also described.     

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.     

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.     

CRACK GROWTH OF STRUCTURAL ADHESIVE JOINTS IN HUMID ENVIRONMENTS

The adhesive fracture energy, G_c, of aluminiumalloy and steel joints bonded with a rubber-toughened epoxy adhesive has been measured using monotonicallyloaded tests. Such tests have been conducted at different levels of relative humidity, and two surface pretreatments have been employed for the substrates prior to bonding: a simple grit-blast and degrease (GBD) pretreatment or a silane primer (GBS) pretreatment. When G_c was plotted against the crack velocity, three regions of fracture behaviour could be distinguished. At low rates of displacement the crack grew in a stable manner, visually along the interface, and relatively low crack velocities could be readily measured. This was termed “Region I”, and here the value of the adhesive fracture energy was relatively low and decreased steadily as the relative humidity was increased. On the other hand, at relatively high rates of displacement the crack grew in a stick-slip manner mainly cohesively in the adhesive layer at approximately 20 km/min. This was termed “Region III”, and here the value of G_c was relatively high and independent of the relative humidity. In this region the crack was considered to grow faster than the water molecules were able to reach the crack tip, which explains the independence of G_c upon the test environment. In between Region I and Region III a transition region was observed, which was designated “Region II”. The major effect of the GBS pretreatment, compared to which the GBD pretreatment, was to increase the value of G_c both in Regions I and III, although the presence of the silane primer had the greater effect in Region I.     

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     

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.     

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.     

Corona-discharge Treatment of Polypropylene films-Effects of Process Parameters

Corona treatment of films, mainly polypropylene (PP)-copolymers, was studied at commercial levels in a 2.7 kVA treater. The films were produced on a flat-film extruder with chill rolls. Degree of treatment was characterized by power of the generator divided by web speed and width of film (m Ws/cm²).

The effectiveness of the treatment was measured in terms of the polar and dispersion components of surface-energy, the peel adhesion of pressure sensitive tape (similar to ASTM Adhesion Ratio) and the peel adhesion of polyurethane adhesives.

The polar component of surface energy is a measure of the effectiveness of corona pretreatment. For a given degree of treatment, the polar surface energy component becomes greater as the film cooling rate increases (and the degree of crystallization falls).

A comparison of homopolymers and copolymers does, however, reveal that even where these have the same density or the same degree of crystallization one cannot count on them having equally-sized polar components.

Peel strengths of pressure-sensitive tapes and polyurethane-bonded patches confirm the influence of cooling conditions on wetting properties.

Contrary to the case for tape adhesion, the polyurethane adhesive strengths reach their maximum value at much lower treatment intensities, i.e. with much lower polar surface energy components, and thus question the validity of the ASTM tests for adhesion properties.     

The Fracture Resistance of a Toughened Epoxy Adhesive

The fracture resistance of a rubber-modified epoxy adhesive has been studied using a continuum fracture-mechanics analysis. The fracture energy, G_Ic, has been ascertained over a range of test temperatures and rates, both in bulk and in adhesive joints, as a function of specimen geometry. The results obtained are described and a semi-quantitative model discussed for predicting the joint failure behaviour from the bulk adhesive properties.     

Peel Adhesion of Solid Films-The Surface and Bulk Effects

The peel strength of rubber and paint films has been measured over a range of peeling velocities using a dead weight method. At low peel rates the peel force is fairly constant but rises rapidly at higher peeling speeds.

Experiments show that the peel strength is a function both of the energy of interfacial bonds which must be broken as peeling proceeds and of bulk energy losses in a viscoelastic peeling material.

The interfacial effect has two components: an equilibrium surface force which accounts for the peel strength at low velocities, and a viscous peeling force which depends on the peeling rate. This viscous interfacial force explains the increase in peel strength of purely elastic films at higher peeling velocities.

The energy loss in the bulk of the peeling film introduces two additional effects: a magnification of the peel strength in steady peeling over a certain velocity range, and a slowing down or stopping of peeling as transient relaxation occurs shortly after the application of the peel force.