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     

Effects of compatibility between tackifier and polymer on adhesion property and phase structure: Tackifier‐added polystyrene‐based triblock/diblock copolymer blend system

The effects of compatibility of tackifier with polymer matrix and mixing weight ratio of triblock/diblock copolymers as the matrix on the adhesion property and phase structure of tackifier‐added polystryrene triblock/diblock copolymer blends were investigated. For this purpose, polystyrene‐block‐polyisoprene‐block‐polystyrene triblock and polystyrene‐block‐polyisoprene diblock copolymers were used and the diblock weight ratio in the blend was varied from 0 to 1. Spherical polystyrene domains with a mean size of about 20 nm were dispersed in the polyisoprene (PI) continuous phase. In the case of the hydrogenated cycloaliphatic resin as tackifier having a good compatibility with PI and a poor compatibility with polystyrene, the peel strength increased with an increase of the tackifier content, and the degree of increase became significant above 40 wt % of tackifier. It was found that the nanometer‐sized agglomerates of tackifier in the PI matrix were formed and the distance between the nearest neighbors of agglomerates was about 15 nm from SAXS measurement. The peel strength increased with an increase of the nanometer‐sized agglomerates of tackifier from TEM observation. On the other hand, in the case of the rosin phenolic resin as tackifier having a good compatibility with both polystyrene and PI, the peel strength increased effectively at the lower tackifier content, while no significant increase at higher tackifier content was observed. The agglomerates of tackifier were never confirmed in this system. The higher peel strength was obtained at the diblock weight ratio in the blend of 0.5–0.7 for both tackifier‐added systems. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

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.     

Effects of miscibility on probe tack of natural-rubber-based pressure-sensitive adhesives

Natural rubber (NR) was blended in various ratios with 29 kinds of tackifier resins, which were prepared from rosin, terpenes, and petroleum. Miscibilities of all the blend systems were illustrated as phase diagrams in our previous articles. From these blend systems, we selected 7 systems having typical phase diagrams [completely miscible, completely immiscible, and lower critical solution temperature (LCST) types] and carried out measurements of probe tack. Probe tack values were measured at various rates of separation and temperatures to obtain master curves. In the case of miscible pressure sensitive adhesives (PSAs) at the condition of measurement, the peak position in the master curve of probe tack shifted to the lower velocity (higher temperature) as the tackifier content increased. On the contrary, immiscible PSAs had much smaller probe tack values than miscible ones and did not give manifest shift of peaks. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 771–776, 1998     

Miscibility and shear creep resistance of acrylic pressure-sensitive adhesives: Acrylic copolymer and tackifier resin systems

The miscibility between an acrylic copolymer and a tackifier resin was investigated in terms of phase diagrams, glass transition temperatures (T_g's), and dynamic mechanical properties of blends. Shear creep resistance (holding power, t_b) of the blends was measured as a function of both temperature and stress (σ₀) in order to obtain the master curves. It was found that the shear creep resistance of the pressure-sensitive adhesives (PSAs) was closely related to the miscibility between the components and viscoelastic properties of the blends. The master curve of the miscible blends shifts toward a longer time scale as the amount of tackifier resin in the blend is increased as a result of the modification of the bulk properties, and their behavior greatly depends on the glass transition temperature (T_g) and storage modulus (G′) of the blends. However, the master curve of immiscible blends where two phases exist in the system does not shift greatly toward a longer time scale, because T_g and the storage modulus of the blend do not change greatly. © 1995 John Wiley & Sons, Inc.     

Adhesion properties of pressure-sensitive adhesives prepared from SMR 10/ENR 25, SMR 10/ENR 50, and ENR 25/ENR 50 blends

The adhesion properties, i.e. viscosity, tack, and peel strength of pressure-sensitive adhesives prepared from natural rubber/epoxidized natural rubber blends were investigated using coumarone-indene resin and toluene as the tackifier and solvent respectively. One grade of natural rubber (SMR 10) and two grades of epoxidized natural rubbers (ENR 25 and ENR 50) were used to prepare the rubber blends with blend ratio ranging from 0 to 100%. Coumarone-indene resin content was fixed at 40 parts per hundred parts of rubber (phr) in the adhesive formulation. The viscosity of adhesive was measured by a HAAKE Rotary Viscometer whereas loop tack and peel strength was determined using a Lloyd Adhesion Tester operating at 30 cm/min. Results show that the viscosity of the adhesive passes through a minimum value at 20% blend ratio. For loop tack and peel strength, it indicates a maximum at 60% blend ratio for SMR 10/ENR 25 and SMR 10/ENR 50 systems. However, for ENR 25/ENR 50 blend, maximum value is observed at 80% blend ratio. SMR 10/ENR 25 blend consistently exhibits the best adhesion property in this study, an observation which is attributed to the optimum compatibility between rubbers and wettability of adhesive on the substrate. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of the compatibility of a polyacrylic block copolymer/tackifier blend on the phase structure and tack of a pressure‐sensitive adhesive

Adhesion and viscoelastic properties and morphology of a polyacrylic block copolymer/tackifier blend were investigated. Special rosin ester resins with different weight average molecular weights of 650, 710, 890, and 2160 were used as the tackifier and blended with a polyacrylic block copolymer consisting of poly(methyl methacrylate) and poly(n‐butyl acrylate) blocks at tackifier content levels of 10, 30, and 50 wt %. The compatibility decreased with an increase in molecular weight. From TEM observation, the number of formed agglomerates of the tackifier with sizes on the order of several tens of nanometers increased with increasing tackifier content and molecular weight of the tackifier in the range from 650 to 890. For the tackifier with a molecular weight of 2160, micrometer‐sized agglomerates were observed. The storage modulus at low temperature and the glass transition temperature of adhesive measured by a dynamic mechanical analysis increased dependent on the number of formed nanometer sized agglomerates. Tack was measured using a rolling cylinder tack tester over wide temperature and rolling rate ranges, and master curves were prepared in accordance with the time‐temperature superposition law. Tack and peel strength were optimum at a blend combination of intermediate compatibility, i.e., the molecular weight of 890. These optimum properties were correlated to maximal values of the storage modulus at room temperature and the glass transition temperature. Therefore, it was found that these features of blend properties are strongly affected by the nanometer sized agglomerates of tackifier. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal and mechanical characterization of partially miscible blends of poly(ether ether ketone) and polyethersulfone

The miscibility behavior of poly(ether ether ketone) (PEEK) and polyethersulfone was studied by differential scanning calorimetry (glass transition temperature) and tensile properties: Young's modulus and ultimate tensile strength. A single glass transition temperature was observed over the entire composition range. The glass transition temperature of blends, however, did not follow any of the theoretical equations. Utracki and Jukes equation was used with K = 11 to fit the experimental data that indicate partial miscibility. Up to 30 wt % PEEK, the blends showed amorphous behavior with the glass transition temperature very close to that of polyethersulfone. Because of partial miscibility, blends showed mechanical compatibility. Both the modulus and strength increased significantly with an increasing concentration of PEEK in the blends, reaching a maximum around 40%. Electron microscopic results revealed phase separation but strong adhesion between the phases.     

Influence of diblock addition on tack in a polyacrylic triblock copolymer/tackifier system measured using a probe tack test

The influence of diblock copolymer addition on the tack properties of a polyacrylic triblock copolymer/tackifier system was investigated. For this purpose, poly(methyl methacrylate)‐block‐poly(n‐butyl acrylate)‐block‐poly(methyl methacrylate) triblock copolymer (MAM) and a 1/1 blend with a diblock copolymer consisting of the same components (MA) were used as base polymers, and a tackifier was added in amounts ranging from 10 to 30 wt %. The temperature dependence of tack was measured by a probe tack test. The tack of MAM/MA at room temperature was significantly higher than that of MAM, and the improvement of MAM/MA upon the addition of the tackifier was higher than that of MAM. The peeling process at the probe/adhesive interface during the probe tack test was observed using a high‐speed microscope. It was found that for MAM/MA, cavitation was caused in the entire adhesive layer, and peeling initiation was delayed by the absorption of strain energy due to deformation of the adhesive layer. In contrast, for MAM, peeling progressed linearly from the edge to the center of the probe. The greater flexibility of the soft block chain in the diblock copolymer resulted in improved interfacial adhesion. ¹H pulse nuclear magnetic resonance analysis showed that the addition of the tackifier improved the cohesive strength of the adhesive. Adhesion strength is affected by two factors: the development of interfacial adhesion and cohesive strength. In the MAM/MA/tackifier system, the presence of MA and the tackifier improved the interfacial adhesion and cohesive strength, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

Compatibility behavior in thermoplastic polymer blends containing poly(t-butylstyrene-co-acrylonitrile)

The phase behavior of a series of binary component polymer blends of poly(ε-caprolactone) (PCL) and poly(t-butylstyrene-co-acrylonitrile) (TBSAN) containing varying contents of acrylonitrile (AN) was examined to determine the influence of copolymer composition and PCL content on blend miscibility or immiscibility. Thermal measurements were extensively used to determine phase behavior, i.e., a single compositionally dependent glass transition temperature implies blend miscibility. Otherwise, immiscibility is assumed to dominant blend behavior. It was determined that TBSAN and PCL form miscible blends over a broad range of AN content, i.e., spanning from below 43.2 mol % (19.8 wt %) to about 66.4 mol % (39.6 wt %), a range considerably different from that found in poly(styrene-co-acrylonitrile) copolymers. TBSAN-containing blends were found to be immiscible when the AN content is less than about 43 mol % or greater than about 67 mol %. Small-angle light-scattering and polarized light microscopy was used to probe the substantial morphological changes in the miscible blends. Little change was observed in the immiscible blends. These results clarify the phase separation observed in these blend systems. © 1993 John Wiley & Sons, Inc.     

Miscibility and Probe Tack of Acrylic Pressure Sensitive Adhesives—Acrylic Copolymer/Tackifier Resin Systems

Miscibility between acrylic copolymers and tackifier resins are investigated in terms of phase diagrams, and the probe tack of the blends are measured as a function of both temperature and rate of separation in order to obtain the master curves. It is found that the probe tack of the pressure sensitive adhesives are closely related to the miscibility between the components. The master curves of the miscible blends shift along the X(rate)-axis according to the change of T_g of the bulk materials with a gradual variation of the peak heights. However, those of the immiscible blends will not shift along the X(rate)-axis, but the magnitude will decrease with increase of a dispersed phase.     

Ultimate properties of polycarbonate blends: Effects of inclusion plastic deformation and of matrix phase continuity

Tensile energy to break (TEB) of polycarbonate (PC) blends has been increased by exploiting (i) the plastic deformation of dispersed or co-continuous brittle polymer(s) and (ii) higher matrix phase continuity in ternary blends with two dispersed minority components. Monotonic dependence of yield strength on blend composition and micrographs of drawn specimens concurrently evidence a strong interfacial adhesion sufficient for transmission of yield and/or break stress. Good adhesion at created interfaces, was achieved through partial miscibility of PC with other components, i.e., poly(styrene-co-acrylonitrile) (PSAN) and poly(styrene-co-methyl methacrylate) (PSMMA), which was evaluated from the shifts of the glass transition temperatures of conjugate phases. Binary and ternary blends with PC contents higher than 35% show extensive plastic deformation after yielding. TEB and strain-at-break of ternary blends with 50% or 40% PC pass through a maximum at compositions with equal fractions of PSAN and PSMMA, which is in qualitative accord with model calculations of the matrix phase continuity. Thus, the blend PC/PSAN/PSMMA = 40/30/30 preserves 70% of TEB of neat PC.     

Calorimetric and dielectric study on poly(trimethylene terephthalate)/polycarbonate blends

Poly(trimethylene terephthalate) (PTT)/polycarbonate (PC) blends with different compositions were prepared by melt blending. The miscibility and phase behavior of melt-quenched and cold-crystallized blends were studied using differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy. The blends of all compositions display only one glass transition (T _g ) in both states. The melting temperature and the crystallinity of PTT in the blend decrease with increasing PC content. The dielectric results for the melt-quenched blends, for PC content up to 60 wt.%, exhibited two merged relaxation peaks during the heating scan; the lower temperature relaxation peak represent the normal glass-transition (α) relaxation of the mixed amorphous phase and the higher temperature relaxation due to the new-constrained mixed amorphous phase after crystallization. Cold-crystallized blends displayed only one glass transition α-relaxation whose temperatures varied with composition in manner similar to that observed by DSC. The dielectric α-relaxation of cold crystallized blends has been analyzed. Parameters relating to relaxation broadening, dielectric relaxation strength, and activation energy were quantified and were found to be composition dependent. The PTT/PC blends could be considered as two-phase system, a crystalline PTT phase and a mixed amorphous phase consisting of a miscible mixture of the two polymers. However, the crystallinity was only detected for blends containing greater than 40 wt.% PTT.     

Study of compatibilizers for glass fibre reinforced nylon 6/polypropylene blends

The efficiency of a synthesized interfacial modifier agent, acrylic acid grafted polypropylene (AAgPP) in glass fibre reinforced nylon 6/polypropylene (GFRN6/PP) blends has been studied. Scanning electron microscopy clearly shows that the dispersed phase particle size decreases when AAgPP content increases (12‐fold decrease in diameter) resulting in a more stable morphology. The established emulsification curve for this system emphasizes the efficiency of the synthesised AAgPP as a potential interfacial modifier for GFRN6/PP blends. AAgPP at 7.5 wt% is to be considered as the critical concentration for our blend; such a concentration corresponds to maximum interaction between the matrix and the dispersed phase. Strong interactions between the blend components have been observed. The effect of increasing the compatibility agent content on Izod impact, tensile strength, tensile modulus and elongation at yield has also been investigated, and a bell‐shaped trend observed with a maximum at 7.5 wt% AAgPP content. A 25 % increase in impact strength for the unnotched specimen, a twofold increase in tensile strength and a fourfold increase in tensile modulus are obtained. At 7.5 wt% AAgPP, a tough–brittle fracture transition is observed with a 2.5 µm particle size diameter. © 2000 Society of Chemical Industry.     

Miscibility between natural rubber and tackifiers. I. Phase diagrams of the blends of natural rubber with rosin and terpene resins

Natural rubber (NR) was blended in various ratios with 17 kinds of tackifiers, which were prepared from rosin and terpenes. The blends were heated to various temperatures (20–120°C) in order to investigate their miscibility. The blends were visually observed for transparency or opacity at each temperature and further observed under an optical microscope for any existence of phase-separated structure. Miscibility of the blends is illustrated as phase diagrams in this article. Phase diagrams of all blends investigated in this study were classified into four types: completely miscible, lower critical solution temperature, upper critical solution temperature, and completely immiscible. The miscible range of a blend system tends to become smaller as the molecular weight of a tackifier increases. The data also indicate that the esters of hydrogenated rosin and of disproportionated rosin show comparatively good miscibility with NR whereas polymerized rosin and its esters have poor compatibility with NR in most cases. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2191–2197, 1997     

Temperature dependence of tack and pulse NMR analysis of polystyrene block copolymer/tackifier system

The influence of tackifier structure on the temperature dependence of tack for a polystyrene block copolymer/tackifier system was investigated. A blend of polystyrene-block-polyisoprene-block- polystyrene triblock and polystyrene-block-polyisoprene diblock copolymers was used as the base polymer. Four different tackifiers were used: special rosin ester resin (RE), rosin phenolic resin (RP), hydrogenated cyclo-aliphatic resin (HC), and aliphatic petroleum resin (C5). Tack at 20?°C increased with the tackifier content for both RE and HC tackifier systems. Tack is affected by two factors: the work of adhesion at the adherend interface and the viscoelastic properties of the adhesive. The good balance of these two factors brought high tack. The adhesive with 10 wt.% tackifier exhibited the highest tack at 20?°C, whereas those with 30 and 50 wt.% tackifier were lower than those systems with 10 wt.% of the RP or C5 tackifiers. The adhesive with overly high hardness lowered the work of adhesion and the tack was not improved with more than 30 wt.%. A compatibility test in toluene solution and in solid state showed that tackifier RE has good compatibility with both polyisoprene and polystyrene, whereas tackifier RP has lower compatibility. Tackifiers HC and C5 had good compatibility with polyisoprene, but poor compatibility with polystyrene, and that of C5 was poorer. Pulse nuclear magnetic resonance (NMR) analyses indicated that tackifiers RE and HC effectively restrict the molecular mobility of polyisoprene phase.     

Polyester–Polycarbonate blends. IV. Poly(ε-caprolactone)

Polycarbonate blends with poly(ε-caprolactone) were prepared by both melt-blending and solution-blending techniques, and the properties of these blends were studied by thermal analytical and dynamic mechanical testing methods. Each blend composition was found to have a single glass transition temperature, and the temperature location of this transition was found to be a function only of blend composition and to be independent of the blending technique employed. This behavior led to the conclusions that these two polymers form blends containing a single amorphous phase comprised of the two materials and that this miscible phase results primarily from physical rather than chemical interactions between the two polymers. A reversible liquid-liquid-type phase separation was found to occur when the blend system was heated to high melt temperatures. The temperature required for phase separation, the lower critical solution temperature, was found to vary with blend composition and component molecular weight in the manner expected from thermodynamic considerations. The level of crystallinity of poly(ε-caprolactone) was affected by the presence of the polycarbonate. The polycarbonate also crystallized to an appreciable extent in many of the blends.     

New miscible blends composed of polysulfone and poly(1-vinylpyrrolidone-co-acrylonitrile) copolymers and their phase behavior

The miscibility of polysulfone, PSf, blend with poly(1-vinylpyrrolidone), PVP, and that of PSf blend with poly(1-vinylpyrrolidone-co-acrylonitrile) copolymers, P(VP-AN), containing various amount of VP were explored. Even though PSf did not formed miscible blends with PVP when both components had high molecular weight, it formed miscible blend with PVP by decreasing molecular weight of PVP. PSf also formed homogeneous mixtures with P(VP-AN) containing AN from 2 to 16 wt%. These miscible blends underwent phase separation on heating caused by LCST-type (lower critical solution temperature-type) phase behavior. The phase separation temperature of miscible blends first increases with AN content, goes through a maximum centered at about 8 wt% AN. Interaction energies of binary pairs involved in blends were evaluated from the observed phase boundaries using the lattice-fluid theory. The decline of the contact angle between water and blend film by increasing P(VP-AN) content in blend indicated that the hydrophobic properties of PSf could be improved by blending with P(VP-AN) copolymers.