Surface Characterization of Vulcanized Rubber Treated with Sulfuric Acid and its Adhesion to Polyurethane Adhesive

Modifications produced on a vulcanized styrene -butadiene rubber surface by treatment with sulfuric acid were studied and several experimental variables were considered.

The treatment of R1 rubber with sulfuric acid produced a noticeable decrease in contact angle which was mainly ascribed to an increase in surface energy due to the formation of sulfonic acid moieties and C=O bonds, and the removal of zinc stearate. The rubber surface swelled and became brittle as a result of the treatment, and when flexed microcracks were created. A rubber surface layer modification was produced with a consequent decrease in tensile strength and elongation-at-break values. The treatment enhanced the T-peel strength of R1 rubber/polyurethane adhesive joints and the locus of failure was cohesive in the rubber.

The optimum immersion time in H₂SO₄ solution was less than 1 min., and the reaction time in air was not found to be critical; the neutralization with ammonium hydroxide and the high concentration of the sulfuric acid (95 wt%) were essential to produce adequate effectiveness of the treatment.     

The Interfacial Bond Strength in Glass Fibre-Polyester Resin Composite Systems Part 2. The Effect of Surface Treatment

The effect of surface treatments on the bond strength in glass fibre-polyester resin composites has been investigated using single fibre interfacial shear strength specimens and the short beam shear test for interlaminar shear strength.

A range of bond strengths was obtained by using, either alone or in combination, the various components of the size formulation which is normally applied to the fibres, so that the interaction between the glass surface and the polyester ranged from Van de Waal forces through hydrogen bonding to covalent bonding, the bond strength increasing in that order.

The relative contribution to bond strength of mechanical bonding due to thermo-mechanical mismatch between the two components and of chemical bonding or physical interaction between the three phases, glass-surface treatment-resin, has been evaluated and found to be one third and two thirds respectively.     

Fibre Surface Energy Characterization

A new technique has been developed to study the surface energy characteristics of small diameter fibres. This method is tensiometric and based on wetting properties in a two phase liquid system. Two types of carbon fibre have been investigated under both static and dynamic conditions in immersion and emersion.

The high strength fibre, which was found to have a polymeric coating, gave reproducible results consistent with typical values for a polymer. However, the high modulus fibre could not be characterized due to considerable scatter in the experimental results. It is suggested that the source of this phenomenon is the existence of surface energy gradients which leads to hysteresis effects.     

Unit Cell Evolution in Structurally Damageable Particulate-Filled Elastomeric Composites under Simple Extension

A special form of the unit cell is offered for investigation of matrix separation in particulate composites. The threshold tear strength of the matrix is used as a basis for the strength-of-cell estimations. Numerical experiments have been performed within the bounds of large deformation theory.

A weak dependence of the ultimate strength on the filler content as well as the extensive plateaus on tensile elongation have been revealed. The latter are due to the slow and stable character of matrix detachment from filler particles.

These results have proved to be in a good agreement with the available experience.     

EVALUATION OF CONDUCTIVE HEAT TRANSFER MECHANISMS BETWEEN AN IMMERSED SURFACE AND THE ADJACENT LAYER OF PARTICLES IN BUBBLING FLUIDIZED BEDS

The evaluation of the heat transfer coefficient h_wp between a heat exchanging surface immersed in a gas fluidized bed and the adjacent layer of dense phase particles is analyzed in this contribution. Gas convective and radiant effects are not included in the present analysis.

The inclusion of h_wp, or an equivalent formation, in mechanistic models describing heat transfer has been necessary because the sudden voidage variation close to the immersed wall restrains significantly the heat transfer rate. However, there is not at present a widely accepted expression to evaluate h_wp.

A precise formulation for h_wp accounting for transient conduction inside spherical particles, the Smoluchowski effect, the concentration of particles in the adjacent layer (N_p) and an effective separation gap (l₀) is developed here.

Although N_p can be estimated, in principle, from experimental evidence in packed beds, and it is reasonably expected that l₀ = 0, the analysis of experimental heat transfer rates in moving beds, packed beds, and bubbling fluidized beds indicate that values of h_wp are, in general, smaller than expected from these assumptions. Appropriate values of l₀ and N_p are then stimated by fitting the experimental data.

The probable effect of surface asperities is also discussed by analyzing a simplified geometrical model. It is concluded that the parameter l₀ can be also effective to account for particle roughness, independently of thermal properties.     

Mechanical and Dynamic Mechanical Properties of Photocrosslinked Norbornene-Thiol Copolymer Films

A number of novel organic norbornene and norbornene siloxane polymer precursors have been synthesized as part of an on-going research project to produce a non-acrylate, UV-curable adhesive system. These precursors (monomers or oligomers) are di-, tri- and tetra-functional. The crosslinking agent is a multifunctional thiol.

The organic norbornene systems, formulated to stoichiometry, have been characterized using thermal, static and dynamic mechanical analysis. We have found that norbornene ester systems have a range of physical properties, with tensile moduli ranging from 820-2300 MPa (118-350 kpsi), tensile strengths of 17-61 MPa (2.5-8.8 kpsi) and elongations of 4-100%. Glass transition temperatures range from 30-71°C for samples cured at room temperature with a dose of 620 mJ/cm².

Norbornene siloxanes crosslinked with thiol siloxanes have been formulated with increasing levels of a high surface area reinforcing agent. Tensile properties of filled films show that filler loading to 30 wt% significantly increases peak stress and elongation to break above that of 25 wt% filler. The addition of filler did not appear to increase the T_g of the films in this series monotonically. Increased levels of filler were found to produce films with a broadened cold crystallization range and an increased melting temperature.     

Hygrothermal Properties of Epoxy Film Adhesives

The hygrothermal response of high performance epoxy film adhesives, in their bulk state, has been characterized over a wide range of temperatures, following exposure to a combination of humidity (95% R.H.) and heat (50°C).

Experimental results have indicated that the testing temperature has a pronounced effect on both tensile modulus and strength of the adhesives, while the effect of moisture content varies with respect to the adhesive type. The moduli of the film adhesives, which have a wide range of glass transition temperatures (T_g), have been related to both moisture level in the adhesive and testing temperature. This has been accomplished by employing a dimensionless temperature, which incorporates the wet and dry T_g and the testing, as well as a reference, temperature. The strength properties have shown a higher degree of scatter using the abovementioned dimensionless temperature.

Scanning electron microscopy of the fracture surfaces have shown a good agreement between the effects of moisture and the mechanical properties. Adhesives which exhibited good moisture resistance, as manifested by the stability in their tensile properties, showed minor changes in their fracture surfaces regardless of moisture conditioning. Distinctively, the effect on strength properties has been correlated with typical moisture-induced fracture mechanisms.     

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

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

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

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

The Role of the Interface in Carbon Fibre-Epoxy Composites

The final performance of a composite material depends strongly on the quality of the fibre-matrix interface. The interactions developed at the interface were studied using the acid-base or acceptor-donor concept.

The surface characteristics of the carbon fibres and the epoxy matrix were studied using a tensiometric method and the inverse gas chromatography technique. Acid-base surface characters could be determined allowing the interactions at the interface to be described by a specific interaction parameter.

It was shown that the shear strength of the interface, as measured by a fragmentation test, is strongly correlated to this specific interaction parameter, demonstrating the importance of acid-base interactions in the fibre-matrix adhesion.     

Thermodynamic Criteria for the Maximum and Minimum Strength of Fibre-Reinforced Composite Materials

The overall performance and reliability of composite materials are, in most cases, dependent upon the behaviour of the reinforcement-matrix interface, particularly upon its ability to transfer stress.

A theory for predicting thermodynamic conditions for the maximum and zero-adhesion at the reinforcement-matrix interface is tested in this paper, based on experimental data. Proposed is a model of the relationship between mechanical properties of composite materials (tensile strength, flexural strength, Young's modulus and impact resistance) and energetic properties of matrix and reinforcement expressed by the energy ratio a = γ_l/γ₂.     

Wilhelmy Technique and Solidification Front Technique to Study the Wettability of Fibres

The strength of fibre-reinforced materials depends heavily on the adhesion between the fibre and the resin. To predict the bond strength of the adhesion, it is desirable for the surface tension of the fibre to be known. Two independent methods, the Wilhelmy balance method and the solidification front method, were investigated. The fibres used for this investigation included a carbon fibre, Thornel 300®, and an aromatic poiyamide fibre, Kevlar.

In the Wilhelmy experiments three liquids, ethylene glycol, glycerol and distilled water were employed to measure the surface tensions of the test fibres. They were found to be 42.4 mJ/m² and 43.7 mJ/m² for the carbon fibre and Kevlar, respectively. These values agreed very well with the results obtained from the solidification front method, from which the carbon fibre was found to have a surface tension value of 41.8 mJ/m² while that for Kevlar was 46.4 mJ/m². Furthermore, error analysis has shown that the error limits of the experiments are within 5% of the resulting values. The reproducibility and accuracy of these two techniques indicate that they are viable for determining the surface tension of small diameter fibres.     

SIMULTANEOUS MEASUREMENT OF INTERFACIAL AREA AND MASS TRANSFER COEFFICIENT FOR RISING BUBBLES BY Na2S03—o2ABSORPTION METHOD WITH C2H4 DESORPTION TECHNIQUE

A new system of sulfite oxidation accompanied by C ₂H₄ desorption was proposed to determine interfacial area and liquid side physical mass transfer coefficient in bubble column. The method ensures that K ₁, and a are measured under identical hydrodynamic conditions.

The interfacial areas determined from the new system and from geometrical calculation show reasonable consistency. The values of physical mass transfer coefficient kc₂H₄comparable and they agree well with Danckwerts surface renewal model     

Polymer—Aluminium Adhesion IV. Kinetic Aspect of the Effect of a Liquid Environment

The effect of a liquid in the failure of an assembly depends strongly on the ability of the liquid to follow the fracture front. Thus, the existence of a critical rate of separation above which the liquid has no effect on the strength of the assembly, has been clearly demonstrated.

From a crack model, parameters determining the penetration rate of the liquid in the growing fracture have been established and are:

—the viscosity of the liquid

—its surface energy

—and the solid/liquid interactions.

This analysis also shows that the dimension of the crack opening is of the order of a micron.     

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.     

Bonding of Titanium Alloys

Surface pretreatments affect joint strength, some improve it, e.g. etching in aqueous hydrofluoric acid or oxidation in alkaline hydrogen peroxide; while others decrease the strength e.g. etching in acids containing high concentrations of oxidising agents.

For Ti-6A1-4V alloy, best results are obtained by either etching in aqueous hydrofluoric acid or oxidation in alkaline hydrogen peroxide for about two hours.

The results indicate that a pretreatment which leaves a coherent TiO₂-rutile layer, on a rough surface, form the strongest joints. Surface roughness is shown to enhance bond strength.     

The Effect of Sodium Ions on the Stability of the Interphase Region of Glass Fibre Reinforced Composites

The single embedded filament fragmentation and the short beam shear strength tests together with angle-resolved X-ray Photoelectron Spectroscopy (XPS) have been used to investigate the interfacial region of vinyl ester composites reinforced with sized AR-glass fibres, with and without amino and vinyl functional adhesion promoters.

The 7-aminopropyltriethoxysilane (APS) deposit on AR-glass is susceptible to a thermal degradation during post-cure, which has been attributed to a base catalysed equilibration of the siloxane bonds. The functional groups of APS required for resin compatibility were buried beneath the surface layers, contributing to a low bond strength, furthermore, mobile sodium ions existed within the interfacial region. Aqueous extraction prior to fabrication enhanced the composite bond strength by removing the soluble silane oligomers, the sodium ions, and exposing the organo-functional groups for co-reaction with the matrix.

The silane deposit on AR-glass is made hygroscopic by the presence of sodium ions. This increased the equilibrium moisture content of AR-glass composites, and diminished their retained short beam shear strength in contrast to the E-glass control which retained its properties after redrying.     

Preadhesion Laser Treatment of Aluminum Surfaces

An excimer laser may be used for preadhesion treatment of aluminum alloys. This method presents an alternative to the use of ecologically unfriendly chemicals involved in conventional anodizing pretreatments.

Experimental results indicate that preadhesion laser surface treatment significantly improved the shear strength of modified-epoxy bonded aluminum specimens compared with untreated and anodized substrates. The best results were obtained with laser energy of about 0.2 J/Pulse/cm² where single lap shear strength was improved by 600-700% compared with that of untreated Al alloy, and by 40% compared with chromic acid anodizing pretreatment.

The mode of failure changed from adhesive to cohesive as the number of laser pulses increased during treatment. The latter phenomenon has been correlated with morphology changes as revealed by electron microscopy, and chemical modification as indicated by Auger and infrared spectroscopy.

It can be concluded that the excimer laser has potential as a precise, clean and simple preadhesion treatment of Al alloys.     

The Interfacial Bond Strength in Glass Fibre-Polyester Resin Composite Systems

The interfacial bond strength in glass fibre-polyester resin composites has been investigated using various experimental techniques. These included blocks of resin containing fibre (in which, depending on the geometry of the specimen, failure occurs in either a shear or tensile mode) the pullout of a fibre from a disc of resin and a short beam shear test for interlaminar shear strength determination.

Low power optical microscopy and optical retardation measurements of stress induced birefringence were used to detect the difference between intact and debonded fibre resin interfaces. The shear modulus and shear strength of the resin were obtained from torsion tests on cylindrical rods of the resin.

The single fibre shear debonding specimen and the short beam shear test are shown to be the most viable test methods but interpretation of the results is complicated by the various modes of failure possible and by the different stress states which exist in the area of the specimen where debonding starts. Stress concentration factors obtained by finite element analysis and photoelastic analysis have been applied to the results from these tests and the corrected interfacial bond strengths are in close agreement.

The real interfacial bond strengths of well bonded glass-fibre polyester resin systems is shown to be of the order of 70 MN m^-2.     

Effect of Xylene Formaldehyde Resins on Epoxy Resin Adhesive

The effect of some types of xylene formaldehyde on epoxy resin adhesive is studied. Xylene formaldehyde resin or modified xylene formaldehyde resins are mixed into liquid epoxy resin and curing properties of the blends, their adhesive properties and the dispersion state of xylene formaldehyde resin in cured adhesive film are examined. The results obtained are as follows.

1) Generally, by the addition of xylene formaldehyde resins, the degree of curing of blends are decreased, but pot life is prolonged, and tensile shear strength of steel bonds is increased.

2) It is observed that effects of the amount of xylene formaldehyde resins and curing condition on tensile shear strength vary with the kind of xylene formaldehyde resin, because of the difference in chemical structure of xylene formaldehyde resins and their reactivity to epoxy resin.

3) It is found that a limited region of compatibility, between 80 and 100 phr, exists for 100% xylene formaldehyde resin in epoxy resin. It is also found that joint strength is reduced with higher viscosity and molecular weight of 100% xylene formaldehyde resin in the case of 80 phr blends, and that these results have some relation to the dispersion state of xylene formaldehyde resin in epoxy resin, judging from the cured adhesive film observed under a phase contrast microscope.     

SURFACE TENSION EFFECTS IN THE SEDIMENTATION OF COAL PARTICLES IN VARIOUS LIQUID MIXTURES

The sedimentation volume, V_sed, of coal particles in mixtures of pairs of non-polar and more polar organic liquid combinations as well as in aqueous solutions was determined at 20°C.

The liquid combinations were chosen such that the surface tension, γ_SV, of the coal particles fell between the surface tensions, γ_LV, of the two liquids. A constant mass of a given coal sample was suspended in constant volumes of liquid mixtures of different concentrations.

It was found that the sedimentation volume changed with varying composition of the liquid mixtures, as did the surface tension. A maximum or a minimum occurred in V_sed when the surface tension of the suspending liquid was equal to that of the coal particles, i.e. when γ_LV = γ_SV. Maxima occurred in more polar and minima in the non-polar or less polar liquid mixtures. The position of the extrema, and hence the surface tension, γ_sv, of the particles, was found to change with particle size, in agreement with findings from other independent techniques.

It was found that the surface tension of coal, γ_sv, depends on the surrounding liquid, i.e. coal is hydrophobic in organic and hydrophilic in aqueous media, again in agreement with the results from other techniques.