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.     

Miscibility and pressure‐sensitive adhesive performances of acrylic copolymer and hydrogenated rosin systems

Relationship between the miscibility of pressure‐sensitive adhesives (PSAs) acrylic copolymer/hydrogenated rosin systems and their performance (180° peel strength, probe tack, and holding power), which was measured over a wide range of time and temperature, were investigated. The miscible range of the blend system tended to become smaller as the molecular weight of the tackifier increased. In the case of miscible blend systems, the viscoelastic properties (such as the storage modulus and the loss modulus) shifted toward higher temperature or toward lower frequency and, at the same time, the pressure‐sensitive adhesive performance shifted toward the lower rate side as the T_g of the blend increased. In the case of acrylic copolymer/hydrogenated rosin acid systems, a somewhat unusual trend was observed in the relationship among the phase diagram, T_g, and the pressure‐sensitive adhesive performance. T_g of the blend was higher than that expected from T_gs of the pure components. This trend can be due to the presence of free carboxyl group in the tackifier resin. However, the phase diagram depended on the molecular weight of the tackifier. The pressure‐sensitive adhesive performance depended on the viscoelastic properties of the bulk phase. A few systems where a single T_g could be measured, despite the fact that two phases were observed microscopically, were found. The curve of the probe tack of this system shifted toward a lower rate side as the T_g increases. However, both the curve of the peel strength and the holding power of such system did not shift along the rate axis. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 651–663, 1999     

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     

Miscibility and fracture energy of probe tack for acrylic pressure-sensitive adhesives: acrylic copolymer/tackifier resin systems

The relationship between the miscibility of acrylic pressure-sensitive adhesive (PSA) and the fracture energy (W) (Jm⁻²) of the probe tack was investigated, wherein the master curve of W was compared with that of the maximum force (σ_max) (gf) of the probe tack. It was ascertained that W of acrylic PSA was closely related to the miscibility between the components (acrylic copolymer and tackifier resin). In the case of the miscible blend system, the master curve of W shifted toward the lower rate side and, at the same time, the magnitude decreased as the tackifier resin content increased. The degree of the shift of W was extremely smaller than that of σ_max. In the case of the immiscible blend system, the master curve of W remarkably decreased as the tackifier resin content increased, which suggests the fact that W of the PSA depended on the dynamic mechanical properties of the matrix phase and that the resin-rich phase acted as a kind of filler, thus reducing the practical performance. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 581–587, 1998     

Phase behavior and mechanical properties of blends of poly(butylene terephthalate) and poly(amino–ether) resin

The structure, thermal and mechanical properties of blends of poly(butylene terephthalate) (PBT) and a poly(amino–ether) (PAE) barrier resin obtained by direct injection molding are reported. The slight shift of the glass transition temperatures (T_g) of the pure components when blended is attributed to partial miscibility rather than interchange reactions. Both the small strain and the break properties of the blends were close or even above those predicted by the direct rule of mixtures. The specific volume of the blends appeared to be the main reason for the modulus behavior. The linear values of the elongation at break indicated that the blends were compatible, and were attributed to a combination of good adhesion between the two phases of the blends and the small size of the dispersed phases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 132–139, 2004     

Compatibility and viscoelastic properties of brominated isobutylene‐co‐p‐methylstyrene rubber/tackifier blends

Brominated isobutylene‐co‐p‐methylstyrene (BIMS) rubber has been blended with hydrocarbon resin tackifier and alkyl phenol formaldehyde resin tackifier, and the compatibility between the blend components has been systematically evaluated. Dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) studies show that BIMS rubber and hydrocarbon resin tackifier blends are compatible at all blend proportions studied. However, BIMS rubber and phenol formaldehyde resin blends exhibit very limited compatibility with each other and phase separation even at very low phenolic tackifier concentration. Morphological studies of the rubber–resin blends by scanning electron microscopy (SEM) corroborate well with the DMA and DSC results. From the DMA frequency sweep and temperature sweep studies, it is shown that the hydrocarbon resin tackifier acts as a diluent and causes a decrease in the storage modulus values (by reducing the entanglement and network density) in the rubbery plateau region. On the other hand, phenol formaldehyde resin behaves in the way similar to that of the reinforcing filler by increasing the storage modulus values (by increasing the entanglement and network density) in the rubbery plateau zone. The relaxation time estimated from the different zones of frequency sweep master curves provides information about the influence of the two tackifiers on the viscoelastic properties of the BIMS rubber in the respective zones. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of novolac type phenolic resin blended with poly(dimethylsiloxane adipamide)

Phenolic resin/poly(dimethylsiloxane adipamide) (PDMSA) blends, which have been prepared, show miscibility due to intermolecular H‐bonding existing between phenolic resin and the PDMSA. The specific H‐bonding of novolac type phenolic/PDMSA blends was characterized by means of glass transition temperature behavior and Fourier Transform Infrared Spectroscopy (FTIR). The strength of intermolecular H‐bonding within the phenolic blend is a function of the H‐bonded group of the PDMSA modifier and corresponds to the deviation glass transition temperature (ΔT_g). Phenolic/PDMSA blends were completely miscible, as confirmed by the T_g study. The FTIR result is in good agreement with the inference from T_g behavior. The char yield of phenolic/PDMSA corresponds to the phenolic resin content. The molecular mobility of phenolic/PDMSA blends increases with PDMSA content in the phenolic‐rich region. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 984–992, 2002     

Miscibility,crystallization behavior and specific intermolecular interactions in thermosetting polymer blends of novolac epoxy resin and polyethylene glycol

Thermosetting polymer blends of novolac epoxy resin (EPN) and polyethylene glycol (PEG) were studied. The miscibility and crystallization behavior of the blends before curing reaction were investigated by polarized optical microscopy and differential scanning calorimetry (DSC). Overall uncured blend compositions were homogeneous in amorphous state. Single composition‐dependent glass‐transition temperature (T_g) for each blend could be observed, and the experimental T_g's of blends with EPN content ≥40 wt% could be explained well by the Gordon–Taylor equation. Thermal properties of blends cured with 4,4′‐diaminodiphenylmethane were also determined by DSC. The capability of PEG to crystallize in cured blends was different from that in uncured ones because of the topological effect of highly crosslinking structure. On the basis of Fourier transform infrared spectroscopy results, it was judged that there were intermolecular hydrogen‐bonding interactions between EPN and PEG in both cured and uncured blends. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Miscibility and adhesive properties of EVA‐based hot‐melt adhesives. II. Peel strength

A series of ethylene vinyl acetate copolymers (EVA) were blended with some tackifier resins that were 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 the typical miscibility types and investigated their peel strengths. When the blends were miscible at testing temperatures, the temperature at which the maximum value of peel strength was recorded tended to move toward higher temperature as tackifier content of blends increased. This result corresponds to the storage modulus of the blends whose curves tended to move toward higher temperature as tackifier content of blends increased when blend components were miscible as well as their maximum values of tan δ, or glass transition temperatures. It was characteristic for peel strength that there existed second peaks on peel strengths curves at ～ 100°C, which adhesive tensile strengths for the blends did not have. In terms of relationship between miscibility and HMA performances, we suggest that there are several factors other than miscibility that affect absolute values of peel strength more directly than miscibility; this idea has to be investigated further in the a future study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 726–735, 2002     

Miscibility evolution of polycarbonate/polystyrene blends during compounding

The miscibility evolution of polycarbonate/polystyrene (PC/PS) blends during the compounding process in three blending methods of industrial relevance, namely melt blending, remelt blending in a twin‐screw extruder and third melt blending in an injection molding machine, was investigated by measuring their glass transition temperatures (T_g) and their specific heat increment (ΔC_p). Differential scanning calorimetry (DSC) was used to examine nine blend compositions. Shifts in glass transition temperature (T_g) of the two phases in melt‐mixed PC/PS blends suggest partial miscibility of one polymer in the other. The observed solubility strongly depends on blend composition and blending method. The T_g measurements showed maximum mutual solubility around 50/50 composition. The miscibility of PC/PS blended after the third stage (melt injection molding) was higher than that after the first stages (melt extrusion) and the second stages (remelt extrusion).     

Studies on morphology and thermomechanical performance of ABS/PC/organoclay hybrids

In the present research, poly(acrylonitrile‐butadiene‐styrene)/polycarbonate (ABS/PC) blends were prepared in a twin screw extruder. An attempt to reinforce and promote compatibility of the above systems was made by the incorporation of organically modified montmorillonite (OMMT, Cloisite 30B), as well as by the addition of compatibilizer (ABS grafted with maleic anhydride, ABS‐g‐MAH), and the effect of those treatments on the morphology, thermal transitions, rheological, and mechanical properties of the above blends was evaluated. The addition of compatibilizer in ABS/PC blends does not significantly affect the glass transition temperature (T_g) of SAN and PC phases, whereas the incorporation of Cloisite 30B decreases slightly the T_g values of SAN and, more significantly, that of PC in compatibilized and uncompatibilized blends. The T_g of PB phase remains almost unaffected in all the examined systems. The obtained results suggest partial dissolution of the polymeric components of the blend and, therefore, a modified Fox equation was used to assess the amount of PC dissolved in the SAN phase of ABS and vice versa.Reinforcing with OMMT enhances the miscibility of ABS and PC phases in ABS/PC blends and gives the best performance in terms of tensile strength, modulus of elasticity, and storage modulus, especially in 50/50 (w/w) ABS/PC blends. The addition of ABS‐g‐MAH compatibilizer, despite the improvement of intercalation process in organoclay/ABS/PC nanocomposites, did not seem to have any substantial effect on the mechanical properties of the examined blends. POLYM. COMPOS., 35:1395–1407, 2014. © 2013 Society of Plastics Engineers     

Blends of poly(p-oxybenzoate-co-p-phenylene isophthalate) and polycarbonate: Miscibility and free volume behaviors

Blends of a thermotropic liquid crystalline polymer [poly(p-oxybenzoate-co-p-phenylene isophthalate)] (HIQ45) and a polycarbonate (PC) are studied with regard to their miscibility and free volume behavior. The glass transition temperatures (T_gs) of the blends are found to be uncharacteristically higher than those of the pure components, even increasing with the addition of the low-T_g component, HIQ45. Based on the non-appearance of the T_g of HIQ45 in the tanδ spectra of the blends and the observed homogeneous morphology of the blend, mixtures of HIQ45 and PC are concluded to be a miscible blend system. The free volume properties determined by positron annihilation lifetime spectroscopy show that close packing does not occur in these miscible blends as indicated by positive deviations in size and number concentration of free volume cavities from average values as a function of blend composition. The increase in free volume is attributed to the loss of liquid crystalline alignment of HIQ45 and disturbed packing of PC molecules due to intimate miscibility between different molecules. The free volume fraction index of the blend correlates well with measured blend density.     

Probing the viscoelastic properties of brominated isobutylene‐co‐p‐methylstyrene rubber/tackifier blends using a rubber process analyzer

The viscoelastic behavior of brominated isobutylene‐co‐p‐methylstyrene (BIMS) rubber/hydrocarbon resin blends and BIMS/phenol formaldehyde resin blends was studied with the use of a rubber process analyzer. Dynamic mechanical analysis and scanning electron microscopy were used to evaluate the compatibility between the BIMS/tackifier blends. Strain sweep tests at temperature below the softening point of the tackifiers showed the formation of resin–resin networks in the incompatible BIMS/phenolic resin blends. However, resin–resin network was not prominent in the case of the compatible BIMS/hydrocarbon resin blends. Frequency sweep tests were performed at the strain amplitude within the linear region at several temperatures and the variations of shear storage modulus, G′ and complex viscosity, η* against frequency were recorded. The tackifying resins modified the viscoelastic properties of the BIMS rubber by reducing the storage modulus at lower frequency and by increasing the storage modulus at higher frequencies. However, this action was found to be highly dependent on (a) rubber‐tackifier compatibility, (b) blend proportions, and (c) test temperature. Furthermore, stress relaxation measurements of the BIMS/tackifier blends at temperature below the softening point of the tackifiers showed longer period of relaxation for the incompatible BIMS/phenolic resin blends. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Mechanical and thermal properties of (acrylonitrile‐styrene‐acrylic)/(α‐methylstyrene‐acrylonitrile) binary blends

In this work, (acrylonitrile‐styrene‐acrylic)/(α‐methylstyrene‐acrylonitrile) copolymer (ASA/α‐MSAN) binary alloy was prepared with different composition ratios via melt blending. This work mainly focused on improving the heat resistance of ASA. According to the results of dynamic mechanical thermal analysis, the binary blends exhibited three glass transition temperatures (T_gs) and the shift of the T_gs indicated the partial miscibility of binary blends. This partial miscibility maintained the high T_g of α‐MSAN, which led to the outstanding heat resistance of binary blends. Furthermore, heat distortion temperature also showed that the heat resistance of binary blends was significantly enhanced with the addition of α‐MSAN. However, the introduction of this highly rigid polymer also brought with it the sharp decrease of the impact strength and elongation at break, which is reflected in the morphologies of the blend system obtained via scanning electron microscopy. In addition, the incorporation of α‐MSAN increased the tensile strength, flexural strength, and modulus. There were no new groups observed from Fourier‐transform infrared spectra, which means no strong specific intermolecular interactions existed between ASA and α‐MSAN. Moreover, the processibility of the blend system was obviously improved from the results of melt flow rate. J. VINYL ADDIT. TECHNOL., 22:156–162, 2016. © 2014 Society of Plastics Engineers     

The phase behavior,mechanical, and rheological characteristics of blends containing nitrile polymers and poly(ethylene-co-maleic anhydride)

The phase behavior of binary blends of acrylonitrile/methyl acrylate/butadiene terpolymer (B210) and poly(ethylene-co-maleic anhydride) (PEMA) was examined based on thermal analysis and optical microscopy. Miscibility of these polymer blends was recognized over a wide range of compositions. The appearance of phase separation during subsequent heatings above the glass transition temperature (T_g) of these blends was associated with a lower critical solution temperature (LCST) behavior. Rheological characteristics such as shear storage modulus (G′), loss modulus (G″) and complex viscosity have been shown to depend on the amount of PEMA in the blend. Mechanical properties including the tensile strength and flexural modulus also were found to be related to the composition of the blend. © 1993 John Wiley & Sons, Inc.     

Dynamic mechanical analysis of fiber-reinforced phenolics

Dynamic mechanical analysis (DMA) was used to investigate the thermomechanical behavior and the effects of postcuring on a range of glass-reinforced phenolics. The materials examined were a pure resol (reinforced with S- and E-glass), a pure novolac (reinforced with S-glass), and three derivatives of the resol and/or novolac: a resol/novolac blend, a phenolic–furan graft copolymer, and a rubber-modified resol (all reinforced with S-glass). The blend and copolymer were prepared to obtain phenolic resins with improved impact strength, without degeneration of their high-temperature performance. They have a more loosely crosslinked structure compared to the pure resol or novolac. The rubber-modified resol was prepared with the intention of reducing the brittleness of the resin structure by incorporating an elastomeric phase within the resol resin matrix. It was found that the stiffness and glass transition temperature (T_g) of the materials could be increased by postcuring, which also produced a decrease in their damping capacity. Knowing that the postcure process is a function of time and temperature, a master curve was constructed that allowed prediction of the T_g of the resol/novolac blend over a broad range of postcure times and temperatures. The effect of frequency on the storage modulus of the pure resol (S-glass), copolymer, and blend was also studied from 0.01 to 100 Hz. Master curves were constructed by time–temperature superpositioning that allowed prediction of the storage modulus at times and temperatures that are not experimentally accessible. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 649–658, 1999     

Thermal,morphological, and physicomechanical properties of (chlorinated polyethylene rubber)/(chloroprene rubber) blends

The effect of the blend ratio on the thermal, morphological, and physicomechanical properties of (chlorinated polyethylene rubber)/(chloroprene rubber) (CPE/CR) blends was studied. Two distinct glass transition temperatures (T_g) of all blends were observed in differential scanning calorimetry curves, falling between the T_g of the two pure rubbers. Analysis of the blends by scanning electron microscopy showed both dispersed and continuous phase morphology that depended on the blend composition. Thermogravimetric analysis showed that all the compounds underwent two stages of thermal degradation. The Mooney viscosity and optimum cure times increased with the increase in CPE contents, whereas the scorch times decreased. The tensile strength and elongation at break decreased, whereas the 100% modulus, hardness, and compression set increased with the increase of CPE content; the tear strength had the lowest value for the 50/50 CPE/CR blend because of the poor miscibility. The results from thermal aging and oil resistance tests showed that pure CPE possessed better thermal aging property and oil resistance than those of pure CR. Thus, considerable improvement in oil resistance of the blend compounds was achieved with the increase of CPE content. J. VINYL ADDIT. TECHNOL., 21:18–23, 2015. © 2014 Society of Plastics Engineers     

Miscibility and melting behavior of poly(ethylene terephthalate)/poly(trimethylene terephthalate) blends

The miscibility and melting behavior of binary crystalline blends of poly(ethylene terephthalate) (PET)/poly(trimethylene terephthalate) (PTT) have been investigated with differential scanning calorimetry and scanning electron microscope. The blends exhibit a single composition‐dependent glass transition temperature (T_g) and the measured T_g fit well with the predicted T_g value by the Fox equation and Gordon‐Taylor equation. In addition to that, a single composition‐dependent cold crystallization temperature (T_cc) value can be observed and it decreases nearly linearly with the low T_g component, PTT, which can also be taken as a valid supportive evidence for miscibility. The SEM graphs showed complete homogeneity in the fractured surfaces of the quenched PET/PTT blends, which provided morphology evidence of a total miscibility of PET/PTT blend in amorphous state at all compositions. The polymer–polymer interaction parameter, χ₁₂, calculated from equilibrium melting temperature depression of the PET component was ?0.1634, revealing miscibility of PET/PTT blends in the melting state. The melting crystallization temperature (T_mc) of the blends decreased with an increase of the minor component and the 50/50 sample showed the lowest T_mc value, which is also related to its miscible nature in the melting state. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of carbon nanotubes with different functional groups on the morphology and properties of PPO/PA6 blends

Carbon nanotubes with different functional groups were prepared and then incorporated into the poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 (PPO/PA6) blend via melt blending. The influence of different carbon nanotubes on the morphology and properties of the blend was studied. The results show that addition of pristine CNTs, CNTs‐OH, CNTs‐NH₂ leads to the evolution of the phase structure of PPO/PA6 (mass ratio: 60/40) blend from sea‐island to cocontinuous, whereas incorporation of CNTs‐COOH does not change the blend morphology due to serious aggregation of the carbon nanotubes. Incorporating different CNTs into PPO/PA6 blend increases the tensile modulus and storage modulus of the blends, whereas decreases slightly the tensile strength. At the same time, the glass transition temperatures (T_g) of PA6 and PPO are enhanced. ΔT_g, the gap between the T_g of PA6 and PPO, decreases with the addition of carbon nanotubes due to the stronger interaction of carbon nanotubes with PA6 than PPO. A similar tendency was found in the storage modulus (G′) and complex viscosity (η*) of the composites. The dispersion state of different carbon nanotubes and their interaction with polymer components are different, which causes the different confinement effect to the macromolecular chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dynamic mechanical properties of extruded nylon–wood composites

Dynamic mechanical properties determine the potential end use of a newly developed extruded nylon–wood composite in under‐the‐hood automobile applications. In this article, the dynamic mechanical properties of extruded nylon–wood composites were characterized using a dynamic mechanical thermal analyzer (DMTA) to determine storage modulus, glass transition temperature (T_g), physical aging effects, long‐term performance prediction, and comparisons to similar products. The storage modulus of the nylon–wood composite was found to be more temperature stable than pure nylon 66. The T_g range of the nylon–wood composite was found to be between 23 and 56°C, based on the decrease in storage modulus. A master curve was constructed based on the creep curves at various temperatures from 30 to 80°C. The results show that the relationship between shift factors and temperature follows Arrhenius behavior. Nylon–wood composites have good temperature‐dependent properties. Wood fillers reduced the physical aging effects on nylon in the wood composites. The comparison of the nylon–wood composite with other similar products shows that nylon–wood composites are a promising low cost material for industrial applications. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers