Viscoelastic and adhesion properties of EVA/tackifier/wax ternary blend systems as hot-melt adhesives

Two types of wax were added to a ethylene vinyl acetate (EVA) copolymer/aromatic hydrocarbon resin (tackifier) blend in the molten state and the miscibility, viscoelastic and adhesion properties of ternary blends as hot-melt adhesives (HMAs) were investigated. Miscibility and viscoelastic properties were studied using differential scanning calorimetry (DSC), Brookfield viscometry and dynamic mechanical thermal analysis (DMTA), and their adhesion strength was determined in terms of single lap shear strength. DSC thermograms of both types of waxes showed their melting peaks in a similar region to that of EVA/tackfier blend. It was difficult to evaluate the miscibility of ternary blends using DSC because the melting peaks of the waxes overlapped with those of the EVA/tackifier blend, although the glass transition temperature (T _g) of the ternary blend systems slightly increased with increasing wax concentration. However, their storage modulus (E′) increased slightly and loss tangent (tan δ) showed different peaks when two types of wax were added to the EVA/tackifier blend. Therefore, the miscibility of EVA/tackifier blend altered with addition of waxes. In addition, their melt viscosity decreased with increasing wax concentration. Furthermore, the adhesion strength of the ternary blends decreased with increasing wax concentration, despite the increment of storage modulus. These results suggested that the ternary blends of EVA/tackifier/wax were heterogeneous.     

A study on the lap shear strength of a co-cured single lap joint

In this paper, the lap shear strength of a co-cured single lap joint subjected to a tensile load was investigated by experimental analysis. Co-cured joint specimens with several different bonding parameters such as bond length, surface roughness, and stacking sequence of the composite laminate were fabricated and tested. The dependence of the lap shear strength of the co-cured joint on the bonding parameters was investigated from the experimental results. The failure mechanism of the co-cured single lap joint was partially cohesive failure. The lap shear strength of the co-cured single lap joint was significantly affected by the bond length and the stacking sequence of the composite laminate. However, the effect of surface roughness on the lap shear strength of the co-cured single lap joint was not so significant.     

Effect of phenolic resin structure on the bonding properties of nitrile rubber-based adhesives

Three phenolic resins were used to study the effect of resin structure and its percentage content on the bonding properties of nitrile rubber-based adhesives. The phenolic resins studied are derived from phenol, resorcinol and para-t-butyl phenol, and are of novalac type. These resins were characterized by infra-red and thermal studies. Several formulations were prepared by varying the phenolic resin/nitrile rubber ratio and these formulations were tested for viscosity and bonding properties. At a given resin-to-rubber ratio, the viscosity for resorcinol-formaldehyde resin was higher than phenol-formaldehyde resin followed by para-t-butyl phenol-formaldehyde resin. The peel strength of nitrile rubber-based adhesive prepared from resorcinol-formaldehyde resin was higher than adhesives that from para-t-butyl phenol-formaldehyde resin followed by phenol-formaldehyde resin. The lap shear strength of nitrile rubber-based adhesive containing para-t-butyl phenol-formaldehyde resin was higher than of adhesives containing the other two resins. The trend observed in peel strength could be explained on the basis of hydrogen bonding between hydroxyl groups of phenolic resin (adhesive) and hydroxyl groups of the starch-coated canvas cloth (adherend), whereas the trend observed in lap shear strength could be explained on the basis of extent of linearity in the resin structure.     

Indirect estimation of fiber/polymer bond strength and interfacial friction from maximum load values recorded in the microbond and pull-out tests. Part I: local bond strength

The techniques aimed at adhesion strength measurement between reinforcing fibers and polymer matrices (the pull-out and microbond tests) involve the measurement of the force, F _max, required to pull out a fiber whose end is embedded in the matrix. Then, this maximum force value is used to calculate such interfacial parameters as the apparent bond strength, τ_app, and the local interfacial shear strength (IFSS), τ_d. However, it has been demonstrated that the F _max value is influenced by interfacial friction in already debonded regions, and, therefore, these parameters are not purely 'adhesional' but depend, in an intricate way, on interfacial adhesion and friction. In the last few years, several techniques for separate determination of adhesion and friction in micromechanical tests have been developed, but their experimental realization is rather complicated, because they require an accurate value of the external load at the moment of crack initiation. We have developed a new technique which uses the relationship between the maximum force and the embedded length ('scale factor') to separately measure fiber-matrix interfacial adhesion and friction. Using the equation for the current crack length as a function of the applied load, based on a stress criterion of interfacial debonding, we modeled the pull-out and microbond experiments and obtained the maximum force value versus the embedded length. By varying τ_d and interfacial friction, τ_f, to fit experimental plots, both interfacial parameters were estimated. The micromechanical tests were modeled for three types of specimen geometries (cylindrical specimens, spherical droplets, and matrix hemispheres in the pull-out test) with different levels of residual thermal stresses and interfacial friction. The effect of all these factors on the experimental results is discussed, and the importance of specimen geometry is demonstrated. One of the most interesting results is that the 'ultimate' IFSS (the limiting τ_app as the embedded length tends to zero) is not always equal to the 'local' bond strength.     

Influence of the vinyl acetate content and the tackifier nature on the rheological,thermal, and adhesion properties of EVA adhesives

Three ethylene vinyl acetate (EVA) copolymers with different vinyl acetate (VA) contents (28-40 wt%) were mixed with rosin ester and polyterpene resin tackifiers in a 1 : 1 (weight/weight) ratio. The rheological and thermal properties of the tackifiers were determined and the use of rheological measurements as a precise way to measure the softening point of the tackifiers is proposed. The glass transition temperature of the tackifiers was obtained from the second heating run, after the thermal history of the tackifiers was removed. The addition of the rosin ester to EVA produced a compatible mixture, whereas for the terpene resin a less compatible mixture was obtained. The increase in the VAamount decreased the crystallinity of EVAand both the storage and the loss moduli also decreased, but the peel strength and the immediate adhesion were increased. The immediate adhesion of EVA/tackifier blends was affected by both the compatibility and the rheological properties of the blends. In fact, a relationship between the mechanical storage modulus (E^t′) - obtained from DMTA experiments - of the adhesives and the immediate adhesion to thin rubber substrates was obtained. The adhesives containing the T tackifier showed higher moduli than those containing the G tackifier, and therefore higher peel strength values were obtained. An increase in the VA content increased the flexibility of the adhesives and thus a decrease in peel strength was obtained.     

Effects of atmospheric pressure helium/air plasma treatment on adhesion and mechanical properties of aramid fibers

In order to investigate the effect of atmospheric pressure plasmas on adhesion between aramid fibers and epoxy, aramid fibers were treated with atmospheric pressure helium/air for 15, 30 and 60 s on a capacitively-coupled device at a frequency of 5.0 kHz and He outlet pressure of 3.43 kPa. SEM analysis at 10 000× magnification showed no significant surface morphological change resulted from the plasma treatments. XPS analysis showed a decrease in carbon content and an increase in oxygen content. Deconvolution analysis of C1s, N1s and O1s peaks showed an increase in surface hydroxyl groups that can interact with epoxy resin. The microbond test showed that the plasma treatment for 60 s increased interfacial shear strength by 109% over that of the control (untreated). The atmospheric pressure plasma increased single fiber tensile strength by 16-26%.     

Indirect estimation of fiber/polymer bond strength and interfacial friction from maximum load values recorded in the microbond and pull-out tests. Part II: Critical energy release rate

A new approach to experimental data treatment in the pull-out and microbond tests has been developed. It uses the relationship between the maximum force recorded in these tests and the embedded length ('scale factor') to separately determine adhesional interfacial parameters (critical energy release rate, local bond strength) and interfacial friction in debonded regions. The new method does not require the measurement of the debond force, which corresponds to interfacial crack initiation, and is, therefore, much more convenient and simpler than 'direct' techniques involving continuous monitoring of crack growth. Using the equation for the current crack length as a function of the load applied to the fiber, based on a fracture mechanics analysis of interfacial debonding, we modeled the pull-out and microbond experiments and obtained the maximum force versus the embedded length. By varying the critical energy release rate and interfacial frictional stress to fit experimental plots, both interfacial parameters were determined for several fiber-polymer pairs. Effects of specimen geometry, residual thermal stresses, and interfacial friction on the measured values are discussed. The results are compared with those obtained with our similar stress-based approach. The energy criterion works when the embedded length is not very short, and in this range of embedded length it is better than the stress criterion. Both criteria can be complementarily used for interface characterization.     

Thermal conductivity and lap shear strength of GNP/epoxy nanocomposites adhesives

The addition of graphene nanoplatelets (GNPs) into the epoxy adhesives has been studied in order to increase their thermal conductivity. Thermally conductive adhesives are often used as thermal interface materials (TIMs). The incorporation of 8 and 10 wt% GNPs reinforcement caused a thermal conductivity enhancement of ~206 and ~306%, respectively. The wettability seems to decrease with low GNPs content (2–3 wt%) in comparison with the neat epoxy adhesive but the contact angle remains constant for higher GNPs contents. Lap shear strength remains constant for neat adhesives and resins doped with GNPs. The lack of enhancement of adhesive properties of doped resins is due to a weak interface reinforcement-matrix. In fact, the joint failure is in the adhesive except for high GNPs content (10 wt%) where a cohesive failure mode is observed.     

Initial tack and viscoelastic properties of MF/PVAc hybrid resins used as adhesives for composite flooring materials

The initial tack and viscoelastic properties of blends of melamine–formaldehyde (MF) resin and poly(vinyl acetate) (PVAc) emulsion on decorative veneer and plywood surfaces were investigated using a texture analyzer and dynamic mechanical thermal analysis (DMTA) at room temperature with respect to the 'open time', the time delay between applying an adhesive to a surface and contacting that surface with the other material. We determined and compared the effects of PVAc content, at 0, 30, 50, 70 and 100 wt%, in blends with MF resin. As PVAc is curable at room temperature, PVAc markedly affected the initial tack, as well as DMTA results. The degree of 'tack' was determined quantitatively based on the probe tack data. As the adhesion in an engineered flooring should be achieved in 2–3 min, the acceptable tack range is between 100 and 200 g. From the DMTA results, i.e., the tan δ _max values, the maximum loss modulus (E&Prime) and the rigidity (ΔE) of MF/PVAc blends at room temperature, it was found that tan δ and loss modulus (E&Prime) increased with increasing MF resin content. Moreover, the rigidities of the 70:30 and 50:50 MF/PVAc blends were higher than those of the other blends, especially in comparison with the pure 100% PVAc and 100% MF. We conclude that the initial tack correlates with the MF/PVAc blend ratio during the adhesion process at room temperature.     

The effect of silica (SiO2) nanoparticles and ammonia/ethylene plasma treatment on the interfacial and mechanical properties of carbon-fiber-reinforced epoxy composites

A nanoparticle dispersion is known to enhance the mechanical properties of a variety of polymers and resins. In this work, the effects of silica (SiO₂) nanoparticle loading (0–2 wt%) and ammonia/ethylene plasma-treated fibers on the interfacial and mechanical properties of carbon fiber–epoxy composites were characterized. Single fiber composite (SFC) tests were performed to determine the fiber/resin interfacial shear strength (IFSS). Tensile tests on pure epoxy resin specimens were also performed to quantify mechanical property changes with silica content. The results indicated that up to 2% SiO₂ nanoparticle loading had only a little effect on the mechanical properties. For untreated fibers, the IFSS was comparable for all epoxy resins. With ethylene/ammonia plasma treated fibers, specimens exhibited a substantial increase in IFSS by 2 to 3 times, independent of SiO₂ loading. The highest IFSS value obtained was 146 MPa for plasma-treated fibers. Interaction between the fiber sizing and plasma treatment may be a critical factor in this IFSS increase. The results suggest that the fiber/epoxy interface is not affected by the incorporation of up to 2% SiO₂ nanoparticles. Furthermore, the fiber surface modification through plasma treatment is an effective method to improve and control adhesion between fiber and resin.     

Miscibility and adhesive properties of ethylene vinyl acetate copolymer (EVA)‐based hot‐melt adhesives. I. Adhesive tensile strength

A series of ethylene vinyl acetate copolymers (EVA) were blended with some tackifier resins that are made from wood extracts, and possible relations between their miscibility and properties as hot‐melt adhesives (HMA) were investigated. From our previous report on miscibility of various EVA‐based HMAs, we chose some blends that represent some of typical miscibility types and measured their adhesive tensile strengths. When the blends were miscible at testing temperatures, the temperature at which the maximum value of adhesive tensile strength was recorded tended to move toward higher temperature as tackifier content of blends increased. This result corresponds to the glass transition temperature (T_g) of the blends that became higher as tackifier content of blends increased when blend components were miscible. In terms of HMA performances, we suggest that factors other than miscibility affect absolute values of adhesive tensile strength more directly than miscibility; this idea has to be investigated further in a future study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 719–725, 2002