The Mechanical Behaviour of Polyimide/Copper Laminates Part 2: Peel Energy Measurements

The mechanical peel behaviour of laminates consisting of polyimide films adhered to copper foil using a modified acrylic adhesive has been studied over a wide range of test rates and temperatures. The laminates were prepared from polyimide films which had been subjected to either a “high-thermal history” or a “low-thermal history” treatment during the production of the film. The measured peel energies of the laminates could be superimposed to give a master curve of peel energy versus the reduced rate of peel test, Ra_T , where R is the rate of peel test and a_T is the time-temperature shift factor. The appropriate shift factors were a function of the test temperature and were mainly deduced from tensile tests conducted on the bulk adhesive. The “high-thermal history” laminates gave higher peel energies and the locus of failure of the laminates was mainly by cohesive fracture through the adhesive layer. At low values of log₁₀ Ra_T , i.e. Low rates of peel and high test temperatures, the “low-thermal history” laminates also failed in the adhesive layer and possessed similar peel energies to those measured for the “high-thermal history” laminates. However, at high log₁₀ Ra_T values, the peel energies measured for the “low-thermal history” laminates were lower and showed a wider scatter. These arose from a different locus of failure occurring in these “low-thermal history” laminates when tested under these conditions. Namely, it was found that most of these laminates failed in a weak boundary layer in the outer regions of the “low-thermal history” polyimide film.     

COMPREHENSIVE STUDY OF THE GAS HOLD UP AND BUBBLE SIZE DISTRIBUTION IN HIGHLY VISCOUS LIQUIDS I. GLYCEROL SOLUTIONS

The overall gas hold up, E_G, and bubble size distribution were separated into the particular gas hold up, E_GK, and Sauter diameter. d_SG. due to “small bubbles” as well as E_GG and d_SG, due to “intermediate to large bubbles.” Bubbles are defined to be “small” if they remain in the bubbling layer 15 seconds after the gas flow is turned off. The bubbles which leave the layer during this time are considered to be “intermediate to large bubbles.” The time dependences of E_G E_GK and E_GG, as well as of bubble size distribution after initiating the aeration of the liquid, is investigated. The steady state E_G, E_GK and E_GG, Sauter diameter and specific geometrical surface area of “small” and “intermediate to large” bubbles as well as of the entire bubble population were determined in bubble columns employing 50, 70, 90 and 95% glycerol solutions and perforated plates with different hole diameters (d_H = 0.5. 1.0 and 3.0 mm) respectively. In highly viscous media the “small” and “very large” bubble fractions are high. A comparison of the specific geometrical bubble surface areas with the corresponding volumetric mass transfer coefficients, k_La's, measured earlier indicate that the “small” bubbles do not contribute to k_La. The influence of the “small” bubbles on the fluiddynamics of the two phase system is discussed.     

The Fatigue and Durability Behaviour of Automotive Adhesives. Part I: Fracture Mechanics Tests

A fracture mechanics approach has been successfully used to examine the cyclic fatigue behaviour of adhesively-bonded joints, which consisted of aluminium-alloy or electro-galvanised (EG) steel substrates bonded using toughened-epoxy structural paste-adhesives. The adhesive systems are typical of those being considered for use, or in use, for bonding load-bearing components in the automobile industry. The results were plotted in the form of the rate of crack growth per cycle, da/dN, versus the maximum strain-energy release rate, G_max, applied in the fatigue cycle, using logarithmic axes. Of particular interest was the presence of a threshold value of the strain-energy release rate, G_th, applied in the fatigue cycle, below which fatigue crack growth was not observed to occur. The cyclic fatigue tests conducted in a relatively dry environment of 23°C, and 55%; RH were shown to cause crack propagation at far lower values of G_max compared with the value of the adhesive fracture energies, G_c, which were determined from monotonically-loaded fracture tests. Cyclic fatigue tests were also conducted in a “wet” environment, namely immersion in distilled water at 28 C. The “wet” fatigue tests clearly revealed the further significant effect an aggressive, hostile environment may have upon the mechanical performance of adhesive joints, and highlighted the important influence that the surface pretreatment, used for the substrates prior to bonding, has upon joint durability. The development and standardisation of “wet” fatigue tests may provide the basis for a very effective accelerated-ageing test.     

New and Improved Tests for Adhesion

Three new methods are discussed for measuring the work G_a, required to detach unit area of an adhering material from a substrate. The first is a simple modification of the Outwater double-torsion test for long rectangular plates, bonded together. This method is suitable for evaluating aluminum-epoxy bonds, for example, or the transverse strength of fibrous composites. The second is a pull-off test for long strips adhering to a rigid surface. It seems suitable for adhesive tapes and laminates. The third is a reconsideration of the “blister” test for films and coatings, in which a circular debond at the interface is made to grow by internal pressure. The relation obtained between pull-off force F for a strip, or blow-off pressure P for a layer, takes the unusual form:

F⁴ (or P⁴) ∞ KG³_a

where K is the tensile stiffness of the detaching layer. This dependence arises from the non-linear (cubic) relation between load or pressure and deflection in these configurations. Nevertheless, the product Fθ, where θ is the angle of detachment of a strip, or Py, where y is the height of a “blister”, give direct measures of the strength of adhesion G_a, independent of the stiffness of the adhering material and of the extent of detachment.     

The Use of Large Diameter Monofilament for Improving Peel Resistance of a Brittle High Temperature Adhesive

Peel force measurements as a function of adherend thickness are reported for adhesively bonded specimens based on a cyanate ester resin and aluminium adherends. It has been demonstrated that by incorporating large diameter (0.28mm) PTFE monofilament within the adhesive bond then the peel force and associated fracture energy can be increased significantly over that for specimens based on adhesive alone. Fracture energy measurements are derived for specimens with peeling adherend thickness of up to about 0.6 mm using the 90° peel test. Fracture energies are also derived for peeling of more practically-representative 1.6mm thickness adherends using a single cantilever beam experiment. In-situ photoelasticity and SEM microextensomctry experiments are reported which show the stress fields and displacements associated with the presence of the monofilament. It is believed that the reported increase in measured fracture energy is partly due to the crack pinning effect of the monofilament, and partly due to the monofilament creating a “load shadowed” region between adherend and monofilament which prevents the interfacial crack from propagating between adherend and adhesive.     

A Survey of Rheological Properties of One-Component Epoxy Adhesives

Flow characteristics of seven commercially available one-component epoxy adhesive pastes were measured using a controlled shear stress rheometer and a controlled shear rate rheometer over a temperature range from 5°C to 60°C. Combining data obtained from both controlled rate and controlled stress experiments over a wide range of shear rates, we observed Newtonian flow (shear stress proportional to shear rate) at very low shear rates, a plateau “shear thinning” region at intermediate shear rates, and a second region of linear dependence of shear stress on shear rate at high shear rates. The adhesive pastes exhibited a very broad range of rheological behavior. Two flow parameters important to adhesive application technology, the plastic viscosity and the apparent yield stress, were measured for each adhesive. The plastic viscosity ranged from 11.6 to 329.5 Pa. s; the apparent yield stress ranged from 56.2 to 413 Pa. The temperature dependence of the rheological parameters of the epoxy adhesive pastes was also determined. The results are reported as the activation energies, E_η and E_σ, of plastic viscosity and apparent yield stress, respectively. The apparent yield stress of each adhesive paste was much less sensitive to changes in temperature than was the plastic viscosity. This suggests that the processing characteristics are likely to show qualitative as well as quantitative changes with temperature.     

Polyimide Adhesives and Aluminum

This study examines the effect of thioether sulfur in the polyimide backbone, polyimide T_g, and adherend surface pre-treatment on aluminum bond strengths as determined with both peel and wedge specimens. Surface pretreatment and T_g had more of an effect on peel strength than the presence of sulfur in the polyimide backbone. NaOH etching and comparatively low T_g polyimides combined to produce the highest peel strengths. Together, these factors combined the removal of surface oxide from the adherend with a flexible polyimide which could better relieve stress during testing. Little difference was observed between the peel strengths of sulfur and non-sulfur containing polyimides, and no oxidation of sulfur was observed in the peel samples. NaOH etching also caused both wedge and peel specimens to fail more within the polyimide than in the oxide layer of the adherend. Thus, the NaOH etch appeared to increase interfacial adhesion between the aluminum and the polyimide. The low T_g polyimides performed better than the high T_g polyimides in the wedge test, with the polyimide derived from 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride and 4,4'-diaminodiphenyl ether (BDSDA/ODA) performing the best. This observation could be due to a metal-sulfur interaction since oxidized sulfur was surprisingly observed on the failed surfaces of these bonds regardless of the environment or surface pretreatment. A metal component in the aluminum alloy rather the aluminum is believed to promote the sulfur oxidation.     

A Fracture Mechanics Approach to Characterizing Cyclic Debonding of Varied Thickness Adhesive Joints to Electroprimed Steel Surfaces

Applications of adhesive bonding for automotive structures have been increasing in recent years due to improvements in the types of adhesives available and in improved knowledge of bonding procedures. Consequently, there exists a demand for design techniques to assess the influence of bondline thickness on adhesive joint strength. One design approach currently being used is based on limiting shear stresses in the adhesive while designing to eliminate peel stresses. Another design approach is based on fracture mechanics and accounts for shear and peel stresses and both static and fatigue modes of failure. The present study applies fracture mechanics to investigate the mixed-mode response of cracked-lap-shear (CLS) joints bonded with unprimed and electroprimed steel surfaces. Three bondline thicknesses equal to 0.254, 0.813, and 1.27 mm were evaluated for unprimed and primed bondlines. For the experimental portion of the study, debond growth rates (da/dN) were measured using a remote imaging system over a range of applied cyclic loads. Corresponding changes in the strain release rates (ΔG) were calculated, through finite element analyses, as a function of debond length and applied load level. The computations for ΔG applied a finite element formulation to determine both the peel component, ΔG_i, and the shear component, ΔG_ii. When computed ΔG values were plotted against the measured debond growth rates, da/dN, the results showed a power law relationship which characterizes the debond behavior of a given material system and bondline thickness.     

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.     

The effect of flexible substrates on pressure-sensitive adhesive performance

The adhesive fracture energy (fracture toughness) of tapes during globally elastic unpeeling is often calculated from the relation “G=P/b(1−cos θ)”. We show that while this expression is correct for elastic peeling from rigid substrates, it gives misleading results when peeling from reversible flexible substrates. A two-dimensional analysis is presented for peeling from non-linear elastic substrates that give consistent fracture energies from experimental data.     

Application of the Island Blister Test for Thin Film Adhesion Measurement

The island blister test has recently been proposed as an adhesion test which allows the peel of thin, well-adhered films without exceeding the tensile strength of the film. The island blister test site is a modification of the standard blister test site, consisting of a suspended membrane of film with an “island” of substrate at the film center. The membrane support and island are secured to a rigid plate and the film is pressurized, peeling the film inward off the island. A model for this inward or “annular” peel indicates that even for systems of good adhesion, peel can be initiated at low enough pressures to prevent film failure by making the center island sufficiently small relative to the size of the film.

We have fabricated island blister test sites using micromachining techniques and have used them to measure the debond energy of polymer films on various substrates. The peel data obtained from these island sites match well to the behavior predicted by a simple fracture mechanics analysis. This paper reports the fabrication of the island test sites, the experimental verification of the test, and the results of application of the test to polyimide films on metallic and polymeric substrates.     

Changes in the Peeled Surfaces of Copper Thin Films Deposited on Polyimide Substrates After Heat Treatment

Peel strength between a copper (Cu) thin film and a polyimide (pyromellitic dianhydride-oxydianiline, or PMDA-ODA) substrate is reduced by heat treatment at 150°C in air. In this work, we investigated the peel strength, the morphology of the interface between Cu films and polyimide substrates using optical microscopy and electron microscopy, and chemical change of the interface using Auger electron spectroscopy (AES) and micro X-ray photoelectron spectroscopy (XPS). The analysis showed that CuO “lumps” were present on the peeled surface of PMDA-ODA after heat treatment at 150°C in air. The peeled surfaces of other polyimide substrates were also analyzed: biphenyl dianhydride-para phenylene diamine (BPDA-PDA) and biphenyl dianhydride-oxydianiline (BPDA-ODA). CuO lumps were present on the peeled surface of BPDA-ODA after the heat treatment, but not that of BPDA-PDA. Compared with the adhesion strength for the Cu thin film, the adhesion strength was high for the Cu/PMDA-ODA and Cu/BPDA-ODA laminates, but the adhesion strength was very low for the Cu/BPDA-PDA laminate. This low strength is the reason that CuO lumps were not detected on the peeled surface of the BPDA-PDA substrate. These CuO lumps were related to the adhesion degradation of the Cu/polyimide laminates after the heat treatment.     

Mechanical Properties of Acrylic Pressure Sensitive Adhesives and Their Relationships to Industry Standard Testing

Dynamic mechanical and tensile stress-strain properties were measured for four sets of acrylic pressure sensitive adhesives, and were compared to industry standard “applications” peel and shear properties. Correlations were established showing that more than half of the range of performance shown by commercial PSA's is controlled by the bulk mechanical properties of the adhesive polymer. A few exceptions stand out clearly. Also, room temperature performance properties were found to correlate better with DMA at higher temperatures than with room temperature DMA. The contribution of tensile properties to peel strength and failure mode is discussed. The results can be used to relate PSA performance to well-known concepts in other areas of materials science, e.g. fracture toughness, rubber elasticity, and rheology, and to key variables in the adhesive formulation or selection process.     

COMPREHENSIVE STUDY OF THE GAS HOLD UP AND BUBBLE SIZE DISTRIBUTION IN HIGHLY VISCOUS LIQUIDS II. CMC SOLUTIONS

Following properties of short bubble columns employing CMC solutions (1.0, 1.4 and 2.0%) and perforated plates (0.5, 1.0 and 3.0 mm hole diameters) were determined: relative mean gas hold up, E_G, bubble size distribution, Sauter bubble diameter, d_s, and the specific geometrical bubble surface areas, a' and a' due to the “intermediate to large bubbles.” The a' values were compared with the corresponding volumetric mass transfer coefficients, k_La's and the mass transfer coefficients, k_L, were estimated. The properties of these systems were investigated as function of the superficial gas velocity, W_SG, CMC concentration and aerator type.     

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 Multi-valued Surface Properties of PMMA Films

An apparent link between the surface properties of polar group-containing polymers, such as PMMA and Styrene/Acrylic copolymers, and the thermodynamic quality of solvents used in solutions from which the polymers were cast, was described in earlier papers.^1,2 In these polymers, significant variations have been observed in critical surface tensions(γ_c), and in the thermodynamic interaction parameters for selected vapor-polymer pairs, when the configuration of the polymer in solution was varied through the suitable selection of solvents of differing thermodynamic quality. The “solvent history” effect on surface properties of solid film was not detected however for non-polar polymers such as polystyrene (PS).^1,2 Apparently the distinct chain configurations adopted in solution by PMMA are carried over into the solid and result in different proportions of non-polar (backbone) and polar (side chain) moieties being located in the surface layer of the solid. Since only one surface state can correspond to a thermodynamic equilibrium, it may be expected that the film surface properties will change with time, as the thermodynamically preferred state is attained. As a consequence, use properties of these films should also display (initially) the “solvent history” effect, and should vary similarly with time. The present communication is concerned with these points.     

Properties of the Photon Emission Accompanying the Peeling of a Pressure-Sensitive Adhesive

During the peeling of pressure-sensitive adhesives, it is well known that visible light is emitted from the region near the detachment zone. This photon emission due to adhesive failure is a unique form of triboluminescence. In this paper, we further investigate the properties of this light from the peeling of a filament tape with a natural rubber-resin adhesive from its backing at various peel speeds. We show conclusively that small electrostatic discharges are the major source of this radiation. Total intensity vs time measurements show that the light consists of very intense bursts with typical duration of 50 ns which frequently induce additional discharges for times as long as 50—100μs. Time resolved spectra of these emissions show them to be dominated by the line spectrum of molecular nitrogen for both the initial burst and those that follow in the next 0.1—100μs. Thus, the “after-emission” is not due to phosphorescence of the polymer(s), but due to these additional electrostatic discharges.     

Stress Transfer in Single Fiber/ Resin Tensile Tests

Microscale (25 mm gauge length) “dogbone” resin specimens with single carbon fibers embedded through the length of the specimen have been studied as a method for determining the fiber-resin interphase strength. The specimens are pulled in tension until the fiber fragments to a critical length, l_c. Evidence is presented here, based primarily on the relaxation of stress birefringence around the fiber fragment, that this test may not be an unambiguous measure of fiber-resin adhesion. Data obtained for various production lots of AS-4, AS-6, and IM-6 fibers indicate an increase in l_cd with laminate tensile strength. Although there is theoretical justification for this correlation, it requires that the interphase shear strength is relatively constant.

In those instances where interfacial adhesion was expected to be low, i.e., surface contamination or unsurface treated fiber, there was a significant increase in l_c/d and usually a distinct difference in stress birefringence compared to “good” adhesion. However, the distinction in stress birefringence was not always clear cut.     

The Fracture Mechanics of the Pin and Collar Test for High Temperature Anaerobic Adhesives

A mechanical test method for the studies of high-temperature anaerobic adhesives has been established, based on fracture mechanics, by modifying the standard test method of collar and pin test. Linear Elastic Fracture Mechanics approach was applied to the establishment of the relationship between adhesive fracture surface energy “R”, fracture load and crack length. Hence, from the joints containing a given artificial flaw the adhesive fracture surface energy can be determined; alternatively, from the strength of the joints without artificial flaws the inherent flaw size “a_i” can be calculated to account for the decrease of joint strength.

The experimental techniques were applied to examine the mechanical behaviour of the joint system based on high temperature anaerobic adhesives. It was found that the joints cured at room-temperature had higher adhesive fracture surface energy but lower joint strength than the joints postcured at high temperatures. The “a_i” data explained this interesting phenomenon. The joints cured at room-temperature had extraordinarily large “a_i”, which was found to be formed by the uncured adhesive near the edges of the joints and the adhesive further cured in the postcure processes to reduce the “a_i”. Also, the growth of intrinsic flaw was found to be responsible for the deterioration of the joints in a short-term, high-temperature ageing process.     

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.