Hot Melt Adhesive Model: Interfacial Adhesion and Polymer/Tackifier/Wax Interactions

This work continues our study of the hot melt adhesive (HMA) model published earlier [1]. This HMA model was developed based on the pressure sensitive adhesive (PSA) tack model established previously [2]:

P = P₀BD (1)

where P is the adhesive bond strength, P₀ is the interfacial (intrinsic) adhesion term, B is the bonding term and D is the debonding term. The previous paper [1] describes the B and D terms in detail. However, only a brief discussion of the P₀ term was given. The present paper will provide a more in-depth but still rather qualitative study of the P₀ term within the framework of the adhesion model described in Eq. (1). HMAs studied are ethylene/vinyl acetate copolymer (EVA)/tackifier/wax blends. Substrates studied are untreated and corona-discharge-treated polyolefins such as polypropylene (PP) and polyethylene (PE). First, it has been found that the tackifier surface tension could be roughly correlated with one of its thermodynamic parameters: the solubility parameter dispersion component. Secondly, except for EVA/tackifier binary blends, the compatibility of any two of these three components, the EVA polymer, the tackifier and the wax, in a HMA can be estimated from surface tension and X-ray photoelectron spectroscopy (XPS) measurements. Thirdly, based on the study of the EVA/mixed aliphatic-aromatic tackifier/wax model HMA system, it has been observed that the HMA/polyolefin substrate interfacial composition depends on the wax/substrate compatibility. The cause of an inferior peel strength of a HMA containing a high wax content to a polyolefin substrate is possibly due to the formation of a weak boundary layer (WBL) of wax at the interface and/or low dissipative properties of the HMA.

Also, the relationship between EVA/tackifier/wax interactions and HMA peel strength will be discussed. A correlation between the EVA/tackifier compatibility measured by cloud point and viscoelastic experiments to the debonding term, D, in Eq. (1) has been found.     

Shear Strength of Pressure Sensitive Adhesives and its Correlation to Mechanical Properties

Correlations between shear resistance and the mechanical properties of pressure sensitive adhesives are studied by measuring the deformation behaviour in the static and the dynamic shear test and determining the dynamic shear modulus of the adhesive. For polymers with low or moderate viscosities, the shear strain vs. time characteristics in a static shear test and, accordingly, the static shear strength, can be evaluated from the master curves of the dynamic shear modulus or the dynamic viscosity. The dynamic shear strength also can be calculated. These exact calculations cannot be applied to highly viscous or slightly crosslinked polymers. On the basis of the model experiments, empirical correlations between shear strength and the dynamic shear modulus are established which seem to be generally valid.     

MODELING THE PEEL PERFORMANCE OF PRESSURE-SENSITIVE ADHESIVES

This article presents an approach to analyzing the peel behavior of pressure-sensitive adhesives (PSAs) using the finite element method. The rheological properties and the peel strength of four natural-rubber-based PSAs were experimentally measured to provide input for and comparison with the finite element modeling. A criterion based on stored elastic energy density was used to describe the interfacial debonding. It was shown that the finite element predictions essentially captured the general features of the peel behavior of the PSAs. However, the peel forces predicted were lower than the experimental measurements at intermediate and high peel rates. This might be related to the fact that the nonlinear viscoelastic behavior of the PSAs at large deformation was not considered in this study.     

MODELING THE PEEL PERFORMANCE OF PRESSURE-SENSITIVE ADHESIVES

This article presents an approach to analyzing the peel behavior of pressure-sensitive adhesives (PSAs) using the finite element method. The rheological properties and the peel strength of four natural-rubber–based PSAs were experimentally measured to provide input for and comparison with the finite element modeling. A criterion based on stored elastic energy density was used to describe the interfacial debonding. It was shown that the finite element predictions essentially captured the general features of the peel behavior of the PSAs. However, the peel forces predicted were lower than the experimental measurements at intermediate and high peel rates. This might be related to the fact that the nonlinear viscoelastic behavior of the PSAs at large deformation was not considered in this study.     

Pressure Sensitive Adhesives Based on VectorR SIS Polymers I. Rheological Model and Adhesive Design Pathways

Dexco Polymers (a Dow/Exxon partnership) has been manufacturing Vector^R SIS polymers since 1990.¹ This paper describes experiments carried out to study Vector SIS polymers and model pressure sensitive adhesive (PSA) formulations based on Exxon Chemical's Escorez^R 1310LC tackifier. The adhesive behavior of tackified polymers was quantitatively analyzed by applying the rheological principle of time-temperature superposition² and the mapping approach,^3,4 and the pressure sensitive rheological model⁵ developed earlier. This model⁵ was developed by expanding and modifying an equation [adhesive fracture strength = (intrinsic adhesion) × (bulk energy dissipation)] proposed by Gent et al.^6,7 and Andrews et al.^8,9 This study delivers two key results. The first is that the fracture strength of the PSA/steel bond is the multiplication of three terms: the intrinsic (or interfacial) adhesion, the bonding and the debonding terms (Fig. 1). The debonding term is correlated with the logarithm of the loss modulus at the PSA debonding frequency or with the logarithm of the monomeric friction coefficient of the block copolymer/tackifier system. Both the loss modulus and the monomeric friction coefficient measure the energy dissipation in the bulk adhesive. The second is that PSA design pathways can be established by a mapping approach in the rheological space of the plateau modulus versus the loss modulus peak position in the frequency scale (Fig. 2). Plateau modulus is the bonding parameter because it measures the wetting capability of the adhesive with the substrate surface. The loss modulus peak position is the debonding parameter because it corresponds approximately to the time scale (or the frequency scale) in which one deforms the adhesive to maximize energy dissipation. Therefore, the tackifier and oil combination lowers the plateau modulus, but increases the T_g of the polyisoprene phase of the SIS polymer. This increase in T_g is equivalent to the lowering of the rate of local rearrangement (frequency of segment jumps) of the polyisoprene chains of the block copolymer. An optimal “tackification pathway” in this rheological space is achieved by tailoring the tackifier type and T_g, and the amount of oil used in the PSA.

In brief, the PSA rheological model and mapping approach described in this work for Vector SIS polymers give a comprehensive understanding and adhesive design pathways. This concept and approach not only allow raw material suppliers to improve and design better tackifier and polymer products, but also provide PSA formulators a quantitative tool to achieve PSA end property results.     

Peeling of Elastic Tapes: Effects of Large Deformations,Pre-Straining,and of a Peel-Zone Model

A peel model for non-linear elastic tapes is presented which accounts for large deformations and for pre-straining. The large deformation setting is a new feature of modelling, which would be of interest for applications related to soft polymers and tissues. The conditions for having quasistatic-steady debonding or dynamic catastrophic debonding are determined in terms of the loading variables (peel angle and peeling force). The decohesion energy associated with a given process-zone model is included in the formulation of the peeling model. The predictions of various decohesion laws are discussed with respect to experimental results in the literature. Finally, the adhesion of a gecko is analysed and the maximum adhesion force of a single spatula is evaluated. The result correlates well with the maximum experimental pulling force reported in the literature for a gecko's seta.     

Effect of Cross-Linking on Tack and Peel Strength of Polymers

In this work the influence of cross-linking on the adhesive fracture energy and the peel strength is studied choosing polydimethylsiloxane (PDMS) as a model polymer. A series of samples was prepared by electron-beam irradiation which covers the whole range from a viscoelastic liquid to a cross-linked rubber. The mechanical behaviour of these PDMS samples was characterized by mechanical spectroscopy. Tack measurements with an instrument described elsewhere⁵ and peel measurements show that the adhesive fracture energy after short contact times as a measure of tack and the peel strength have a pronounced maximum in the range above the gel point, where the PDMS consists of a very loose and imperfect network and a high fraction of soluble polymer. In this range debonding is connected with the formation of fibrillar structures within the polymer.     

PSA Release Force Profiles from Silicone Liners: Probing Viscoelastic Contributions from Release System Components

Release force profiles of an acrylic- and rubber-based pressure sensitive adhesive (PSA) from silicone release coatings containing different levels of a high-release additive (HRA) were measured. The profiles of release force differed dramatically for the two different adhesive types. The general trends of either increasing or decreasing release force profiles with peel rate were predominantly attributed to the relative ability of the adhesive component to dissipate and store energy (i.e., tan δ) over the operating frequency range. The addition of HRA enhanced the dissipative character (G' and tan δ increased) of the release coating which resulted in higher release forces. An empirical model based on the viscoelastic properties of the adhesive and release coating was proposed to describe release force profiles and initial estimates for the fitting parameters were determined. The release model was shown to predict successfully the impact of adhesive thickness on the release force profile using an acrylic PSA which was not used for the model development. Some evidence was also obtained for the validity in omitting the contributions of the elastic backing components from the model.     

Grafting poly(ethylenimine) on aluminum-boron double oxide whisker and its effects on whisker-PVC composites

An apparatus for measuring the peel adhesion behavior is developed on the basis of the circular motion of the compound pendulum. The peel force versus peel rate characteristics at the increasing and decreasing rates of peeling can be measured in a half cycle of rotation of the pendulum. A personal computer plays the important roles of operating the automated apparatus and processing data in real time. To test practical performance of the apparatus, the relation between peel force and rate of peeling was investigated for various pressuresensitive adhesive (PSA) tapes over a wide peel rate range. The respective curves in peel force versus peel rate in the increasing and decreasing rate processes are consistent with each other in the rate regions where cohesive or interfacial failures occur; while in the transition region between their failures, it appears that a peel hysteresis exists. Furthermore, the conventional testing under constant rate was repeated, and good agreement with the results from the present apparatus was obtained.     

EXPERIMENTS AND INELASTIC ANALYSIS OF THE LOOP TACK TEST FOR PRESSURE-SENSITIVE ADHESIVES

The loop tack test is studied experimentally and numerically using a model system. The ends of a steel strip are clamped together, giving a teardrop shape, and the loop is pushed downward onto an acrylic foam tape and then pulled upward off the tape. In the finite element analysis, the strip is represented by beam elements and a bilinear elastic-plastic constitutive law. The traction-separation relationship for the pressure-sensitive adhesive (PSA) is modeled with a trapezoidal cohesive zone. Viscoelastic behavior of the PSA is included in one case. Curves of the pulling force versus the top displacement (i.e., tack curves) exhibit a sharp peak just before separation of the loop from the strip. The effects of the PSA parameters, contact length, loop length and thickness, and loading rate are investigated. The numerical results compare more favorably with the experimental results than do those from a previous elastic analysis.     

Interfacial Energy and Adhesion between Acrylic Pressure Sensitive Adhesives and Release Coatings

The interfacial adhesive behavior between acrylic pressure sensitive adhesive-like networks (PSA-LNs) and poly(vinyl N-alkyl carbamate) release coatings was studied using a contact mechanical method and peel tests. Surface energy and interfacial energy were directly measured in JKR tests using a novel sample construction. The surface energy of the poly(vinyl N-alkyl carbamates) was found to be around 20 mJ/m². Interfacial energies between PSA-LNs and the release coatings were found to be quite high - between 7 and 24 mJ/m². Changes in adhesion dynamics were governed by acid-base interactions between the carbamate in the release coating and the acid groups in the PSA-LN. The length of the alkyl chain in the release coating moderated this effect. We also found a correlation between fundamental adhesion energy and peel strength. Examination of this phenomenon provides a basis for understanding the poor storage stability of PSA tapes made using alkyl carbamates and acid-containing PSAs.     

Fundamental Understanding in Rolling Ball Tack of Tackified Block Copolymer Adhesives

In the pressure sensitive adhesive (PSA) industry, rolling ball tack is a very common tack test, which is simple, inexpensive and easy to operate. This work attempts to search for key parameter(s), which will affect the rolling ball tack of a PSA based on a blend of styrene-isoprene-styrene triblock copolymer(SIS) and hydrocarbon tackifier(s). We want to better understand whether this particular PSA performance is controlled by the surface or bulk properties of the adhesive.

Firstly, to test the contribution from the surface properties, we employ a model system of SIS/aliphatic tackifier in 1/1 wt. ratio as the control. Part of the tackifier in this PSA is then replaced by various amounts of low molecular weight diluents with different surface tensions. The idea is to vary the surface properties of the PSA because these low surface tension and low molecular weight diluents tend to migrate to the PSA surface. It is observed that the incorporation of a lower surface tension and a lower molecular weight diluent in the PSA tends to produce a larger increase in rolling ball tack compared with the unmodified PSA. On the other hand, the incorporation of a higher surface tension and a more compatible diluent tends to produce a larger increase in loop, peel and quick stick. Each diluent lowers the shear adhesion failure temperature (SAFT) of the diluent-modified PSA. These observations are explained in terms of tackifier molecular weight, and surface tension and compatibility of the various components (polyisoprene, tackifier, diluent and oil) in the adhesive formulation.

Secondly, to test the contribution from the bulk properties, we derive an equation for rolling ball tack in terms of the bulk viscoelastic behavior of the block copolymer PSA. However, experimental values of rolling ball tack do not follow this equation. Also, with increasing tackifier concentration in SIS, rolling ball tack has very different behavior compared with loop, peel, quick stick and probe tack. The latter set of performance criteria is known to be related to PSA bulk viscoelastic behavior. Therefore, these suggest that rolling ball tack is related more to the surface properties than to the bulk properties of the adhesive based on these results and those of the diluent-modified PSA systems.     

Viscoelastic Properties of Pressure-Sensitive Adhesives

Recent studies on the correlation of viscoelastic properties of pressure-sensitive adhesive (PSAs) with industry standard performances such as peel, tack and shear are reviewed and discussed. One notewothy feature in these correlations is the separation of the bonding and debonding steps in PSA adhesion, which specifies the characteristic bonding and debonding frequencies of different PSA tests. Viscoelastic windows (VW) for different types of pressure-sensitive adhesives (PSAs) proposed by these workers are also compared and discussed. The observed good correlations reaffirm the importance of bulk viscoelastic properties to PSA adhesion performances.     

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.     

Finite element analysis of load transfer at a fibre–matrix interface during pull-out loading

Load transfer ability of the fibre–matrix interface is well known to mainly control the mechanical behaviour of fibre-reinforced materials. This load transfer phenomenon is of great importance in dentistry when a post is used for fixing a ceramic crown on the tooth. The pull-out test has been well accepted as the most important micromechanical test for evaluating the interaction properties between the fibre and matrix. In this study, a finite element model is developed to analyse the pull-out process of a steel fibre from an epoxy matrix. Based on the pull-out force–displacement curves, developed in our previous experimental work, specific load transfer laws at the fibre–matrix interface have been proposed for each stage of the pull-out process, i.e., before and after fibre–matrix debonding. Predicted initial extraction forces for different implantation lengths were fitted to experimental values and an initial interference fit of 4 μm was determined. An interfacial shear strength of 21 MPa was then determined by fitting the predicted debonding forces for different implantation lengths to the experimental values. According to the load transfer laws considered, analysis of the interfacial shear stress indicates that fibre–matrix debonding initiates simultaneously at both the lower and upper extremities of the interface.     

Fundamental Understanding in Rolling Ball Tack of Tackified Block Copolymer Adhesives

In the pressure sensitive adhesive (PSA) industry, rolling ball tack is a very common tack test, which is simple, inexpensive and easy to operate. This work attempts to search for key parameter(s), which will affect the rolling ball tack of a PSA based on a blend of styrene-isoprene-styrene triblock copolymer(SIS) and hydrocarbon tackifier(s). We want to better understand whether this particular PSA performance is controlled by the surface or bulk properties of the adhesive.

Firstly, to test the contribution from the surface properties, we employ a model system of SIS/aliphatic tackifier in 1/1 wt. ratio as the control. Part of the tackifier in this PSA is then replaced by various amounts of low molecular weight diluents with different surface tensions. The idea is to vary the surface properties of the PSA because these low surface tension and low molecular weight diluents tend to migrate to the PSA surface. It is observed that the incorporation of a lower surface tension and a lower molecular weight diluent in the PSA tends to produce a larger increase in rolling ball tack compared with the unmodified PSA. On the other hand, the incorporation of a higher surface tension and a more compatible diluent tends to produce a larger increase in loop, peel and quick stick. Each diluent lowers the shear adhesion failure temperature (SAFT) of the diluent-modified PSA. These observations are explained in terms of tackifier molecular weight, and surface tension and compatibility of the various components (polyisoprene, tackifier, diluent and oil) in the adhesive formulation.

Secondly, to test the contribution from the bulk properties, we derive an equation for rolling ball tack in terms of the bulk viscoelastic behavior of the block copolymer PSA. However, experimental values of rolling ball tack do not follow this equation. Also, with increasing tackifier concentration in SIS, rolling ball tack has very different behavior compared with loop, peel, quick stick and probe tack. The latter set of performance criteria is known to be related to PSA bulk viscoelastic behavior. Therefore, these suggest that rolling ball tack is related more to the surface properties than to the bulk properties of the adhesive based on these results and those of the diluent-modified PSA systems.     

Rheological, Interfacial and Thermal Control of Polymer Adhesion. I. Isothermal Theoryf

We have developed an isothermal theory of separation in polymer-solid adhering systems. The model used is based on the (observed) drawing of filaments between a bulk polymer and a solid. In the isothermal theory, a criterion is set up, demarcating filament elongation vs. detachment of the filament base from the solid. It employs a dimensionless parameter, ω, that relates free energy of adhesion, elongational viscosity or yield strength of the polymer, and filament size, to adhesive performance. The isothermal theory can be applied directly to the separation processes that occur with pressure-sensitive adhesives. Certain observations by Aubrey and Sherriff, by Gardon and by Kaelble are explained. The validity of the demarcation is believed to extend beyond pressure-sensitive systems, to all thermoplastic adhesives and/or coatings.     

Relationship between Viscoelastic and Peeling Properties of Model Adhesives. Part 1. Cohesive Fracture

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*(ω), as a function of frequency, ω and peeling properties through the variations of peeling force (F) as a function of peeling rate (V).

After showing the objective character of the peeling curves obtained, the variations of the peeling force and peeling geometry have been studied as a function of volume fraction of the tackifying resin.

In this first paper, the analysis is focused on the first domain of the peeling curves, i.e. the cohesive fracture region. In this region, the peeling properties have been related to the viscoelastic properties in the terminal region of relaxation. It is shown that the longest relaxation time, τ_o, is a reducing parameter of the peeling curves, so a peeling master curve-which is independent of temperature, resin volume fraction and polymer molecular weight-may be defined. Furthermore, the variations of the test geometry as a function of peeling rate have been investigated: the variations of the radius of curvature of the aluminium foil have been analyzed with respect to the viscoelastic behavior of the adhesive, which in fact governs the test geometry.

A detailed analysis of all these features leads to a model which allows one to calculate the peeling curves in the cohesive domain from the adhesive formulation.     

Effect of Cross-Linking on Tack and Peel Strength of Polymers

In this work the influence of cross-linking on the adhesive fracture energy and the peel strength is studied choosing polydimethylsiloxane (PDMS) as a model polymer. A series of samples was prepared by electron-beam irradiation which covers the whole range from a viscoelastic liquid to a cross-linked rubber. The mechanical behaviour of these PDMS samples was characterized by mechanical spectroscopy. Tack measurements with an instrument described elsewhere⁵ and peel measurements show that the adhesive fracture energy after short contact times as a measure of tack and the peel strength have a pronounced maximum in the range above the gel point, where the PDMS consists of a very loose and imperfect network and a high fraction of soluble polymer. In this range debonding is connected with the formation of fibrillar structures within the polymer.     

Surface and Interfacial Structure of Release Coatings for Pressure Sensitive Adhesives I. Polyvinyl N-Alkyl Carbamates

Polyvinyl N-alkyl carbamates belong to the general class of long alkyl side chain polymers. Such polymers are commonly used as release coatings for pressure sensitive adhesive tapes. In this paper the bulk, surface, and interfacial structures of polyvinyl N-alkyl carbamates having either decyl or octadecyl side chains are examined. The bulk structures and thermal transitions were characterized using X-ray scattering and differential scanning calorimetry. Dynamic mechanical thermal analysis was used to investigate thermal transitions and rheology (i.e., segmental mobility) of the polyvinyl N-alkyl carbamates. The surface energies of polyvinyl N-alkyl carbamate coatings were determined using contact angle methods, while X-ray photoelectron spectroscopy and static secondary ion mass spectrometry were employed to characterize the near-surface compositional profiles of the coatings. The peel force provided by the polyvinyl N-alkyl carbamate coatings, as a function of aging time and temperature, was measured for a tape having an acrylic acid containing alkyl acrylate based pressure sensitive adhesive. The changes in peel force with aging time and temperature were related to the ability to maintain a stable interfacial structure between the PSA and polyvinyl N-alkyl carbamate coatings. Changes in the interfacial composition upon aging were characterized by comparing the surface compositions of the PSA and polyvinyl N-alkyl carbamate coatings initially, prior to contact, as well as after aging and peeling them apart. The increase in peel force upon aging can be attributed, in large part, to a restructuring at the PSA/polyvinyl alkyl carbamate interface. Energetically favorable acid-base interactions between the basic urethane and acetate groups in the polyvinyl alkyl carbamates and the acrylic acid groups in the PSA provide a driving force for the restructuring. If the segmental mobility within the polyvinyl alkyl carbamate is sufficient, restructuring can occur, leading to increased concentrations of these groups at the PSA/polyvinyl alkyl carbamate interface, resulting in higher attractive forces and greater adhesion. The propensity for the polyvinyl N-alkyl carbamate coatings to restructure upon contact with a polar medium was also characterized by monitoring the receding contact angle of water, as a function of water contact time and temperature. A good correlation is seen between the ability of the polyvinyl alkyl carbamate coatings to provide a low peel force for the acrylate PSA tape and the ability of the coatings to maintain a high water receding contact angle.