Effect of mixing protocol on compatibilized polymer blend morphology

We investigated the effect of mixing protocol on the morphology of compatibilized polymer blends made with premade compatibilizer and reactively formed in‐situ compatibilizer in a custom‐built miniature mixer Alberta Polymer Asymmetric Minimixer (APAM). The compatibilized blends show a finer morphology than uncompatibilized blends if the polymers are mixed together in the dry state and then fed into the mixer. It is found that premelting one polymer, and premixing polymers and compatibilizer, both greatly affect the compatibilized blends' morphology. The effects are complex since the dispersed phase particle size and distribution of the compatibilized blends may be smaller or larger when compared with the uncompatibilized system, depending on the material's physical and chemical properties; for example, diblock molecular weight or the preference of copolymer to migrate to a particular phase can change the final morphology. Good mobility of the copolymer to reach the interface is crucial to obtain a finer morphology. Micelles are observed when a high molecular weight diblock copolymer P(S‐b‐MMA) is used for a PS/PMMA blend. Because of its enhanced mobility, no micelles are found for a low molecular weight diblock copolymer P(S‐b‐MMA) in a PS/PMMA blend. For PS/PE/P(S‐b‐E) blends, finer morphology is obtained when P(S‐b‐E) is first precompounded with PS. Because the block copolymer prefers the PE phase, if the P(S‐b‐E) block copolymer is compounded with PE first, some remains inside the PE phase and does not compatibilize the interface. In the case of reactive blend PSOX/PEMA, premelting and holding the polymers at high temperature for 5 min decreases final dispersed phase particle size; however, premelting and holding for 10 min coarsens the morphology. POLYM. ENG. SCI. 46:691–702, 2006. © 2006 Society of Plastics Engineers.     

Compatibility studies of polystyrene–polybutadiene blends by thermal analysis

In order to examine the behavior of incompatible blends of polystyrene and polybutadiene, the glass transition temperature, the melting point, and the specific heat increment at the glass transition temperature for atactic polystyrene (a-PS), isotactic polystyrene (i-PS), polybutadiene (PBD), and blends of a-PS/PBD and i-PS/PBD were determined by use of a differential scanning calorimeter. Blends were prepared by solution casting, freeze-drying, and milling. Weight fractions of polystyrene in the blends ranged from 0.95 to 0.05. The glass transition temperature of polystyrene changed with weight fraction in the blends, and with blending preparation methods; the glass transition temperature of polybutadiene remained essentially unchanged. The specific heat increment at the glass transition temperature of PBD decreases linearly with increasing proportions of PS in the PS/PBD blend for the broad and narrow molecular weight distribution polybutadience polymers, whereas the specific heat increment for PS did not decrease with increasing proportions of PBD in the PS/PBD blend. These results suggest that the polybutadiene dissolves more in the polystyrene phase than does the polystyrene in the polybutadiene phase.     

Effect of γ‐irradiation on the physical properties and dyeability of poly(vinyl butyral) blends with polystyrene and poly(ethylene glycol)

Cast films of polymer blends essentially based on poly(vinyl butyral) (PVB) and equal ratios of polystyrene (PS) and poly(ethylene glycol) (PEG) were prepared from benzene and butyl alcohol solutions of the individual polymers. The effect of γ‐irradiation on the thermal decomposition and tensile mechanical properties was investigated. Moreover, the effect of γ‐irradiation on the dye affinity of PVB/PS and PVB/PEG for basic and acid dyestuffs was studied. The thermogravimetric analysis (TGA) study showed that the unirradiated PVB polymer films prepared in benzene displayed higher thermal stability than the same polymer films prepared in butanol. However, in all cases the thermal stability was found to increase with increasing γ‐irradiation dose. On the other hand, PVB/PS blend possesses higher thermal stability than PVB/PEG, as shown from the determination of the weight loss (%) at different heating temperatures, the temperatures of the maximum rate of reaction and the activation energy. While, pure PS films showed the stress‐strain behavior of brittle polymers, PVB/PS films showed the behavior of tough polymers with yielding properties. The results of dyeing clearly showed that the solvent type, blend composition, and irradiation dose are determining factors for the dye affinity for basic or acid dyes. For example, unirradiated PVB films prepared from butanol displayed a higher affinity for the basic and acid dyes than the same polymer prepared from the same benzene. However, PVB prepared from butanol showed higher affinity to the dyes than PS prepared from the same solvent. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Efficient mixing of polymer blends of extreme viscosity ratio: Elimination of phase inversion via solid‐state shear pulverization

A novel, continuous process, solid‐state shear pulverization (S³P), efficiently mixes blends with different component viscosities. Melt mixing immiscible polymers or like polymers of different molecular weight often requires long processing times. With a batch, intensive melt mixer, a polyethylene (PE)/polystyrene (PS) blend with a viscosity ratio (low to high) of 0.019 required up to 35 min to undergo phase inversion. Phase inversion is associated with a morphological change in which the majority component, the high‐viscosity material in these blends, transforms from the dispersed to the matrix phase, and may be quantified by a change from low to high mixing torque. In contrast, such blends subjected to short‐residence‐time (～3 min) S³P yielded a morphology with a PS matrix and a PE dispersed phase with phase diameters ≤ 1 μm. Thus, S³P directly produces matrix and dispersed phases like those obtained after phase inversion during a melt‐mixing process. This assertion is supported by the similarity in the near‐plateaus in torque obtained in the melt mixer at short times with the pulverized blend and at long times with the non‐pulverized blend. The utility of S³P to overcome problems associated with melt mixing like polymers of extreme viscosity ratio is also shown.     

PC-SAFT Equation: A Predictive Tool to Determine Experimental Conditions for Polymer Blend Demixing

Abstract

The perturbed-chain statistical associating fluid theory equation of state (PC-SAFT) was applied to predict the phase behavior of polymer solutions in order to determine the pressure – temperature region for the high molecular weight polymer blend separation by using n-alkanes at high pressure and high temperature. The polymer blends selected were physical blends of polyethylene (PE)/polystyrene (PS), and polypropylene (PP)/PS. The miscibility and immiscibility region of each polymer in different alkanes (n-pentane, n-hexane, and n-heptane) was studied and from this analysis, the experimental conditions of the polymer blend demixing were predetermined. The results obtained were validated with experimental data indicating that the PC-SAFT equation is a good tool to predict experimental conditions for the processing windows of polymer blend separation.     

Molecular weight effects on the phase morphology of PS/P4VP blend films on homogeneous SAM and heterogeneous SAM/Au substrates

The effects of the molecular weight of polystyrene (PS) component on the phase separation of PS/poly(4-vinylpyridine) (PS/P4VP) blend films on homogeneous alkanethiol self-assembled monolayer (SAM) and heterogeneous SAM/Au substrates have been investigated by means of atomic force microscopy (AFM). For the PS (22.4k)/P4VP (60k) system, owing to the molecular weight of PS component is relatively small, the well-aligned PS and P4VP stripes with good thermal stability are directed by the patterned SAM/Au surfaces. With the increase of the molecular weight of PS component (for the PS (582k)/P4VP (60k) system), the diffusion of P4VP is hindered by the high viscosity of PS during the fast spin-coating process. The phase separation behavior of PS/P4VP on the SAM/Au patterned substrates is similar to that on the homogeneous SAM and cannot be easily directed by the patterned SAM surfaces even though the characteristic length of the lateral domain morphology is commensurate with the stripe width. This indicates that the relative viscosity of the PS is one of the dominant factors in obtaining well-aligned pattern by the phase separation of polymer blends.     

Thermal degradation and combustion of polymeric blends

The thermal stability of polymer blends was investigated by means of gas chromatography–mass spectroscopy (GC/MS) and thermal analysis. Evaluated changes in thermal stability can be attributed to blending. On the other hand, we were interested in whether blending may provide a method to control thermal stability and combustibility of polymeric materials. A new scheme of thermal degradation for polystyrene‐polydimethylsiloxane (PDMS) blend was suggested. In the case of polystyrene (PS) as a part of the blend, the products of degradation of PS diffuse through the phase boundary, which cause interaction with PDMS polymers. Apparently, PDMS acts as an inert component, slowing down the termination reaction by dilution of macroradicals formed in random scission degradation process of the PS component. On the other hand, it stabilizes the PS by means of interpolymer recombination, which leads to cross products of thermal degradation. Two of the degradation products: 2‐phenyl‐4(1′,3′,3′,5′,5′‐pentamethylcyclotrisiloxane)‐butane and 2‐phenyl‐4(1′,3′,3′,5′,5′,7′,7′‐heptamethylcyclotrisiloxane)‐butane were assigned to the products of cross‐interpolymer recombination which can accelerate the process of PDMS depolymerization by means of radical initiation of PS* fragments. The connection between a polymer thermal oxidative degradation and its combustion under diffusion flames condition was shown by using composition of polypropylene‐polypropylene‐co‐polyethylene (PP/PP‐co‐PE). In general, the solid‐phase polymer reaction can play a very important role in the reduction of polymer combustibility. It was shown that the composition of PP/PP‐co‐PE (62 : 38) has the highest induction period of autooxidation, which correlates with its combustibility. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3300–3311, 2002     

Elongational viscosity for miscible and immiscible polymer blends. II. Blends with a small amount of UHMW polymer

The effect of miscibility on elongational viscosity of polymer blends was investigated in homogeneous, miscible, and immiscible states by the blend of 1.5 wt % of ultrahigh‐molecular‐weight (UHMW) polymer. The matrix polymer was either poly(methyl methacrylate) (PMMA), or poly(acrylonitrile‐co‐styrene) (AS) that has a comparable elongational viscosity value. The homogeneous blend consisted of 98.5 wt % of PMMA and 1.5 wt % of UHMW–PMMA. The miscible blend was composed of AS and UHMW–PMMA at the same ratio. The immiscible blend was a combination of AS and UHMW–polystyrene (PS) at the same ratio. The strain‐hardening behavior of the different blends were compared with that of pure PMMA. It was demonstrated that 1.5 wt % of UHMW induces a strong strain‐hardening property in the homogeneous and miscible blends but was hardly changed in the immiscible blend. The optical microscope observation of the immiscible blend suggested that the UHMW domains were stretched, but that the degree of domain deformation was less than a given elongational strain. It was concluded that the strain‐hardening property is strongly affected by the miscibility of UHMW chain and matrix. The strong strain‐hardening property is caused by the deformation of the UHMW polymer. UHMW chains are stretched when they are entangled with surrounding polymers. However, UHMW chains in an immiscible state are not so deformed because of viscosity difference and no entanglements between domain and matrix. A smaller degree of UHMW chain deformation in immiscible state results in weaker strain‐hardening property. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 961–969, 1999     

Blend composition dependence of the compatibilizing efficiency of graft copolymers for immiscible polymer blends

This work is concerned with the dependence of the compatibilizing efficiency of graft copolymers on the composition of immiscible polymer blends. A series of graft copolymers of polystyrene (PS) and polyamide 6 (PA6), denoted as PS‐g‐PA6, with different molecular structures were used as compatibilizers. The PS‐g‐PA6 was more efficient for the PS/PA6 (80/20) blend than for the PS/PA6 (20/80) one, indicating that a graft copolymer whose backbone and grafts match the matrix and the disperse phase polymers, respectively, has higher compatibilizing efficiency. This is in disagreement with the literature. Moreover, whatever the blend composition, for PS‐g‐PA6 graft copolymers with the same backbone and the same number of grafts per backbone, the longer the grafts, the higher their compatibilizing and stabilizing efficiency; for a given backbone/graft mass ratio, the longer the grafts and concomitantly the smaller the number of grafts per backbone, the higher the compatibilizing and stabilizing efficiency of the graft copolymer. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Application of phase dispersion–crosslinking synergism on recycling commingled plastic wastes

A tetra‐component blend, consisting of low‐density polyethylene (LDPE), polyvinyl chloride (PVC), polypropylene (PP), and polystyrene (PS), was studied as a model system of commingled plastic wastes (LDPE/PVC/PP/PS, mass ratio: 70/10/10/10). Effects of chlorinated polyethylene (CPE), ethylene–propylene–diene monomer (EPDM), styrene–butadiene–styrene (SBS), and their mixture (CPE/EPDM/SBS, mass ratio: 2/2/2) on the mechanical properties and morphology of the system were investigated. With addition of several elastomers and their mixture, the tensile strength of the blends decreased slightly, although both the elongation at break and the impact strength increased. Among these elastomers, EPDM exhibited the most significant impact modification effect for the tetra‐component blends. SBS and the mixture have a good phase‐dispersion effect for the tetra‐component blend. By adding a crosslinking agent [dicumyl peroxide (DCP)], the mechanical properties of the tetra‐component blends also increased. When either SBS or the mixture was added to the blend together with DCP, the probability that the crosslinking agent (DCP) would be at the interface improved because of the phase‐dispersion effect of SBS. Therefore, more co‐crosslinked products will form between LDPE and other components. Accordingly, remarkable improvement of the interfacial adhesion and hence the mechanical properties of the tetra‐component blends occurred. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2947–2952, 2001     

Compatibilizers for recycling of the plastic mixture wastes. II. The effect of a compatibilizer for binary blends on the properties of ternary blends

In this article, we discuss the effect of a compatibilizer for binary blends on the properties of ternary blends composed of high‐density polyethylene (HDPE), polypropylene (PP), or polystyrene (PS) and poly(vinyl chloride) (PVC) virgin polymers with a simulated waste plastics fraction. Chlorinated polyethylene (CPE), ethylene–propylene rubber (EPR), and their 1/1 (w/w) mixture were tested as compatibilizers for the HDPE/PP/PVC ternary blend. CPE, styrene‐ethylene‐propylene block copolymer (SEP), or their 1/1 (w/w) mixture were tested as compatibilizers for the HDPE/PS/PVC ternary blend. The composition of the ternary blends were fixed at 8/1/1 by weight ratio. The amount of the compatibilizer was 3 phr. Rheological, mechanical, and thermal properties were measured. For the 8/1/1 HDPE/PP/PVC ternary blends, the tensile strength was slightly decreased, but the impact strength was significantly increased by adding EPR, CPE, or their mixture. EPR exhibited the most significant impact modification effect for the ternary blends. In a similar way, for 8/1/1 HDPE/PS/PVC ternary blends, on adding SEP, CPE, or their mixture, the tensile strength was slightly decreased, but the impact strength was noticeably increased. It was found that the SEP worked much better as an impact modifier for the ternary blends than CPE or the SEP/CPE mixture did. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1048–1053, 2000     

An effective method of processing immiscible polymer blends into strong fiber

A unique methodology employing a “nearly co‐continuous morphology” for processing immiscible polymers into strong fiber is presented, and an immiscible polypropylene/polystyrene (PP/PS) blend is used as a model system to demonstrate the effectiveness of this methodology. The “nearly co‐continuous morphology” is easier to obtain than the fully co‐continuous structure, and yet, it provides an engineering solution to the production of strong fiber from an immiscible polymer blend. In addition, a process different from traditional melt spinning is used to prepare fiber with good mechanical properties. Traditional melt spinning involves large jet stretch and therefore introduces large interfacial orientation but little molecular orientation in polymer blends. To address this issue, the PP/PS blend is spun with nearly zero jet stretch and after solidification undergoes hot drawing at temperature close to the glass transition temperature of PS. This process sequence imparts a large degree of molecular orientation to the PP phase and produces a strong fiber. The proposed methodology can be extended to other blend systems and provides a potential route for directly recycling commingled polymer waste without preseparation or compatibilization. POLYM. ENG. SCI., 59:2052–2061, 2019. © 2019 Society of Plastics Engineers     

Microheterogeneity in PPO/PS blends

Proton spin magnetization relaxation in the rotating frame is a simple exponential for poly(2,6-dimethylphenyleneether) (PPO) (23K)/polystyrene (PS) (9K) blends of various compositions; these blends are truly homogeneous at the spin-diffusion distance scale of a few nanometers. Blends of PPO with high molecular weight PS exhibit nonexponential decays for the PS component but exponential decays for the PPO component, indicating compositional fluctuation for PS. In some blends, the relaxations are nonexponential for both components. Three factors have been identified to promote microheterogeneity of nanometer dimensions: high polymer molecular weight, increase of temperature, and preparation of blend using solvent that induces crystallization of PPO such as toluene.     

Dissolution mechanism of polymers in high pressure–high temperature n‐alkanes—Application to blends separation

The use of a high temperature–high pressure near critical solvent is an interesting alternative to dissolve high‐molecular‐weight polyolefins with alkanes. This characteristic allows their separation from the blends with other polymers. In the present work, the polymer dissolution of commercial polypropylene (PP) and polystyrene (PS) in n‐alkanes at high pressure and high temperature is analyzed. The comprehension of the different polymer dissolution behaviors and solvent affinities clarifies the understanding of the mechanism of PP/PS physical blend separation under these conditions. The PP dissolution in n‐pentane and n‐heptane was interpreted in terms of chain disentanglement and solvent diffusion. A mathematical model is proposed to predict the experimental results and to calculate mass transfer coefficients in order to quantify the PS barrier effects. It is possible to assess the effect of the temperature on the pure PP solubilization using these coefficients. In blends separation, it was demonstrated that the PS, insoluble at the same conditions, hinders the PP diffusion. As the PS blend content increases, the separation efficiency decreases. Particularly, mass transfer coefficient increases with PP content while PS is the matrix (PS barrier decreases). Afterwards, PP has no ulterior barriers and mass coefficient remains constant. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Dispersion of fillers and the electrical conductivity of polymer blends filled with carbon black

Dispersion state of carbon black(CB) was studied in polymer blends which are incompatible with each other. It was found that CB distributes unevenly in each component of the polymer blend. There are two types of distribution. (1) One is almost predominantly distributed in one phase of the blend matrix, and in this phase fillers are relatively homogeneously distributed in the same manner as a single polymer composite. (2) In the second, the filler distribution concentrates at interface of two polymers. As long as the viscosities of two polymers are comparable, interfacial energy is the main factor determining uneven distribution of fillers in polymer blend matrices. This heterogeneous dispersion of conductive fillers has much effect on the electrical conductivity of CB filled polymer blends. The electrical conductivity of CB filled polymer blends is determined by two factors. One is concentration of CB in the filler rich phase and the other is phase continuity of this phase. These double percolations affect conductivity of conductive particle filled polymer blends.     

Molecular Weight Polydispersity Effects on Diffusion at Polymer/Polymer Interfaces

The effect of molecular weight distribution (MWD) on diffusion at symmetric polymer/polymer interfaces is investigated by rheological tools. A new model allowing the determination of a self‐diffusion coefficient of polydisperse polymer systems is presented. The model is based on the double reptation theory and Doi and Edwards' molecular dynamics applied to A/A polymers brought into intimate contact in the molten state. The material parameters for the model are obtained from linear oscillatory shear experiments, in which the dynamic shear modulus is measured in parallel plate geometry under a small amplitude of deformation as a function of time and frequency for a sandwich‐like assembly. The experiments were conducted on polystyrene (PS) blends with constant weight average molecular weight (M_w) but with variable number average molecular weights (M_n). The measured self‐diffusion coefficients showed that the presence of short molecules in the blend increases the mean value of the self‐diffusion coefficient and the magnitude of such increase can be quantitatively evaluated by the proposed model.     

Charge storage of ternary polymer blends based on poly(phenylene ether)

BACKGROUND: Charge storage capability is a fundamental property of polymers used in electromechanical transducer applications. In this work, the charge retention of ternary blends of poly(phenylene ether) and polystyrene modified with poly(styrene‐co‐acrylonitrile), polystyrene‐block‐poly(ethylene‐co‐butylene)‐block‐polystyrene or polystyrene‐block‐polyisobutylene‐block‐polystyrene (SIBS) triblock copolymers was correlated with the blend composition, final morphology and the chemical structure of the components. RESULTS: It was determined that the charge storage capability is favoured by a finely dispersed and non‐interconnected phase and can be reduced by high polarity or low molecular weight of the blend components. Additionally, the molecular weight and the amount of styrene of the copolymers also determined the phase morphology, which in turn affected the charge retention. The use of SIBS for the ternary blends, especially in small quantities, significantly improved the charge storage. As such, 100 µm films with a surface potential of about 400 V were able to retain up to 240 V (60%) after 24 h at 130 °C. CONCLUSION: The electret behaviour of the polymer blends was influenced by a complex relationship between chemical structure, molecular weight and phase morphology. Copyright © 2009 Society of Chemical Industry     

Morphological effects on glass transition behavior in selected immiscible blends of amorphous and semicrystalline polymers

The effects uncompatibilized immiscible polymer blend compositions on the T_g of the amorphous polymer were studied in the systems polystyrene/polypropylene (PS/PP), polystyrene/high density polyethylene (PS/PE) and polycarbonate/high density polyethylene (PC/PE). In the two similar systems of PS/PP and PS/PE, the T_g of PS increased with decreasing PS percentage in the blends. This variation in glass transition is attributed to the polymer domain interactions resulting from the different morphologies of various blend compositions. Experiments were conducted to study these effects by preparing blends with various polymers that varied the relationship between the T_g of the amorphous polymer and the crystallization behavior of the semicrystalline polymer. Results show that the variation in amorphous component T_g with composition depends strongly on the physical state of the semicrystalline domains. Whereas the T_g of PS in PS/PE blends changed with composition, the T_g of PC in the PC/PE blend did not change with composition.     

Comparative study on phase and properties between rPET/PS and LCP/PS in situ microfibrillar-reinforced composites

Microfibrillar-reinforced composites based on two dispersed phases, liquid crystalline polymer (LCP) and recycled poly(ethylene terephthalate) (rPET), and polystyrene (PS) were prepared using extrusion process. The rheological behavior, morphology, and thermal stability of LCP/PS and rPET/PS blends containing various dispersed phase contents were investigated. All blends and LCP exhibited shear thinning behavior, whereas Newtonian fluid behavior was observed for rPET. The incorporation of both LCP and rPET into PS significantly improved the processability. The potential of rPET as a processing lubricant by bringing down the melt viscosity of the blend system was as good as LCP. The elongated LCP domains were clearly observed in as-extruded strand. Although the viscosity ratio of rPET/PS system was lower than that of LCP/PS system, most rPET domains appeared as small droplets. An addition of LCP and rPET into PS matrix improved the thermal resistance in air significantly. The obtained results suggested the high potential of rPET as a processing aid and thermally stable reinforcing-material similar to LCP. The mechanical properties of the LCP-containing blends were mostly higher than those of the corresponding rPET-containing blends when compared at the same blend composition.     

Polystyrene and polyester polyurethane elastomer blends compatibilized by SMA

Blends of polystyrene (PS) with polyester polyurethane elastomer (PU‐es) were compatibilized by addition of poly(styrene‐co‐maleic anhydride) (SMA) containing 7 wt % of maleic anhydride. Binary nonreactive (PS/PU‐es) blends, binary reactive (SMA/PU‐es) blends, and ternary reactive blends (PS/SMA/PU‐es) were prepared with 10 and 20 wt % of PU‐es. The maleic anhydride content in the ternary reactive blends was varied through addition of different SMA amounts from 0.5 to 5 wt %. Polyurethane in the blends was crosslinked by using dicumyl peroxide or sulfur to improve its mechanical properties. The experimental processing conditions, such as temperature and rotor speed in an internal mixer, were analyzed before blend preparation by processing the individual polymers, PS and SMA, and the PS/PU‐es nonreactive blend (90/10), to prevent the degradation of the polymer during melt mixing and to assure macroscopic homogeneity. The torque behavior during the mixture indicated a grafting copolymerization, which was responsible for the significant drop of the PU‐es domain size in the glassy matrix, as observed by scanning electronic microscopy (SEM). The miscibility of the glassy matrix, which was shown to be dependent on the composition and the phase behavior of ternary blends, became very complex as the SMA concentration increased, as concluded from dynamical–mechanical analysis. Blends containing 20 wt % of PU‐es presented an increase up to a factor of 2 in the deflection at break in relation to PS. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2297–2304, 2004