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     

Characterization and control of interfaces in emulsified incompatible polymer blends

Information on the interfacial region in incompatible polymer mixtures can be gathered using various techniques including electron microscopy, thermal transition analysis, and more sophisticated methods such as nonradiative energy transfer (NRET). Selected examples are reported here to illustrate the exciting potentialities offered by diblock copolymer emulsifiers in controlling interfacial adhesion and devising high performance polymer blends.     

Compatibility of poly(ϵ-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) blends. I. Blends containing SAN with 24 wt% acrylonitrile

Polymer blends of poly(?-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN), containing 24 wt % acrylonitrile (AN), were prepared, and their transition behavior was examined by thermal analysis and dynamic mechanical testing. The blends were judged to be compatible on the basis of the presence of a single, compositionally dependent glass transition. The results of thermal treatment upon blends glass transition behavior and the dependence of thermal history upon the crystallization of semicrystalline PCL were also studied. The crystallization of PCL from SAN/PCL blends was found to be retarded by the presence of SAN, and crystalline PCL was found to exist only in blends containing a high PCL concentration. Blends which do not contain crystalline PCL were transparent, and their glass transition behavior can be correlated by the Gordon–Taylor equation. Phase separation, which was characterized by lower critical solution temperature (LCST) behavior, was found to occur when blends were heated to elevated temperatures.     

On the analysis of positron annihilation lifetime spectroscopy data in semicrystalline miscible polymer blend systems

A free volume probing technique, positron annihilation lifetime spectroscopy (PALS) is used to characterize miscible blends of amorphous polycarbonate with a semicrystalline copolyester at room temperature. The paper describes the analysis required to use the PALS technique to probe the amorphous regions in which the miscibility of the blends occurs. Analysis of the raw PALS data in this system involves taking account of the influence of crystallinity on the PALS results. The results demonstrate that the PALS technique is able to discriminate between free volume in the amorphous regions of as-molded and annealed samples. This difference in free volume between samples of differing thermal history is assigned to the influence of polymer crystals on the stress state of the miscible amorphous regions. © 1994 John Wiley & Sons, Inc.     

Poly(styrene-g-ethylene oxide) copolymers as interfacial agents in immiscible polymer blends

A poly(styrene-g-ethylene oxide) copolymer with an average of 100 styrene units between the graft points is studied with respect to its interfacial activity in binary incompatible mixtures of polymers having different degrees of miscibility toward the graft copolymer components. The interfacial properties were studied by scanning electron microscopy, dynamic mechanical spectroscopy, and differential scanning calorimetry. The data obtained are compared with previously published data from a graft copolymer with the same composition but with shorter PEO branches and only 20 styrene units between them. In spite of their structure, the two graft copolymers could reduce the size of the dispersed phase in the case of athermal mixing. With a negative heat of mixing between only one graft component and the blend, the short branch graft had no effect, while the longer branch graft caused a reduction of the size of the dispersed phase. With a negative heat of mixing for the graft branches as well as for the backbone a strong compatibilizing effect was found for both types of graft copolymers. The results show that even very short parts of the backbone of a graft copolymer can contribute to compatibilization in a polymer blend, especially when the backbone has a negative heat of mixing with one of the blend components.     

Compatibility of poly(ϵ-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) blends. II. The influence of the AN content in SAN copolymer upon blend compatibility

The compatibility of polymer blends of poly(?-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) containing various acrylonitrile (AN) contents was studied to evaluate the influences of copolymer composition and PCL concentration upon blend compatibility. Blend compatibility was characterized by the occurence of a single glass transition intermediate between the transitions of the respective pure components. The glass transitions were determined by differential scanning calorimetry (DSC) and dynamic mechanical measurement (Rheovibron). It was found that SAN and PCL form compatible blends when the AN content of SAN ranges from 8% to 28% by weight. These blends are compatible in all proportions except for SAN 28 (AN wt % = 28) and PCL blends containing 70 or 85 wt % PCL. Blends of PCL and SAN were found to be incompatible when the AN content in SAN is greater than 30 wt % or less than 6 wt %. Lower critical solution temperature (LCST) behavior, which can be attributed to phase separation, was found to occur when these blends were heated to elevated temperatures. The cloud point, or phase separation, was found to vary with AN content in SAN and the concentration of SAN in the blend.     

Effect of acrylonitrile content of styrene-co-acrylonitrile (SAN) on morphology and electrooptical properties of polymer/liquid crystal composite films

Effects of copolymer composition on morphology and electrooptical properties of polymer/liquid crystal (LC) (40/60 w/w) composite films were studied with styrene-co-acrylonitrile (SAN) of varying acrylonitrile (AN) content (6.3–35 wt %) and a cyanobiphenyl-type liquid crystal (E8). The dimension of the LC domain in the composite film decreased with increase of AN content of SAN up to 30 and increased at 35 wt %. The contact angle of the film with an LC drop showed a similar trend; however, its minimum was obtained at 24% AN. Threshold voltage (V_th) and rise time (τ_R) increased, and decay time (τ_D) decreased with AN content up to 30%, and the tendency is reversed at 35%. The results were interpreted in terms of, possibly, a solubility parameter matching between SAN and LC. © 1993 John Wiley & Sons, Inc.     

Polypropylene/elastomer/poly(styrene-co-acrylonitrile) blends: Manifestation of the critical volume fraction of SAN in dynamic mechanical, tensile and impact properties

The effect of the critical volume fraction v_cr of poly(styrene-co-acrylonitrile) (SAN) on the mechanical properties of its blends with rubber-toughened polypropylene (RTPP) containing about 12% grafted ethylene-propylene copolymer was studied. To encompass a wide spectrum of mechanical properties, blend components were selected which are characterized with rather different viscoelastic, tensile and ultimate properties. The SAN volume fraction in blends covers the interval 0∼0.30; concentration dependencies of measured mechanical properties indicate v_cr = 0.13. Experimental data on storage modulus E_b′, loss modulus E_b″, tensile modulus E_b, yield S_yb and tensile S_ub strength are in plausible accord with their simultaneous prediction based on a predictive scheme which operates with a two-parameter equivalent box model and the data on the phase continuity of components obtained from modified equations of the percolation theory. Strain at break, tensile energy to break and total impact energy of blends show a conspicuous drop in the interval 0∼15 % of SAN where SAN forms a discontinuous component; further growth of the SAN fraction accounts for a reduction of the blend ultimate properties to the values typical of brittle polymers.     

Dielectric spectroscopy using dielectric probes: a new approach to study glass transition dynamics in immiscible apolar polymer blends

Dielectric relaxation spectroscopy using dielectric probes was applied to study the (glass transition) dynamics in binary blends of isotactic PP, PS and LDPE. The blends were prepared by melt-mixing and doped with 0.5% of the dielectric probe 4,4′-(N,N-dibutylamino)-(E)-nitrostilbene (DBANS) (van den Berg O, Sengers WGF, Jager WF, Picken SJ, Wübbenhorst M. Macromolecules 2004;37:2460. [17]). Due to the selective amplification of the dielectric relaxation processes related to the dynamic glass transition of the polymers, accurate relaxation data were obtained, even for the minor phases. No substantial influence of the blend composition and the blend morphology on the glass transition dynamics was found, indicating that both blend constituents behave like homogeneous bulk materials. The normalised relaxation strength of glass transition processes remained constant, regardless of the blend type and blend composition. This indicates that the probe molecule, DBANS, was equally distributed over the two blend components in all three polymer combinations PE-PP, PE-PS and PP-PS.     

Polypropylene based polymer blends: Fields of application and new trends

The new industrial strategy in the polymer field requires the transformation of plastic “commodities” into “specialties”. From this point of view, polypropylene (PP) plays an important role both for its intrinsic properties such as high melting temperature, low density, high chemical inertness and for its capability to be produced with different morphological and molecular structures, to be modified with the addition of other polymers or mineral fillers and to be grafted with functional groups. The present range of special and reinforced polypropylene grades includes: elastomer-modified PP, elastomer-modified filled PP, glass fiber-reinforced PP, filled PP, esthetic filled PP, flame-retardant PP, and thermoplastic elastomers. New trends for significantly improving this family of polymers involve impact resistance, processability, durability, dimensional stability, elasticity, and surface properties. A positive answer to this complex emerging demand will put, as indicated, in this work, “special and reinforced polypropylene grades” in a position to successfully compete with technopolymers in some important, rapidly growing application sectors.     

Physical aging in poly(methyl methacrylate)poly(styrene-co-acrylonitrile) blends. Part II: Enthalpy relaxation

An investigation of the effect of physical aging on excess enthalpy of compatible polymer blends was carried out. Poly(methyl methacrylate) (PMMA) and poly(styrene-co-acrylonitrile) (SAN) were chosen for this study. Blends of different ratios of PMMA and SAN were physically aged at different times and temperatures below their glass transition (T_g) and then subjected to enthalpy relaxation measurement in a differential scanning calorimeter (DSC). An improved procedure was developed and, employed to analyze the data. The error associated with the calculation of the normalized deviation in enthalpy, known as the “Φ” function, was below 4%. The relaxation was observed to proceed faster at higher aging temperature. It was also found that at higher aging temperatures of T_g – 20 and T_g– 35°C, enthalpy relaxation in SAN-rich blends proceeds faster than in PMMA rich blends, while at the low aging temperature of T_g– 50°C the rate of relaxation becomes independent of the composition.     

Probing the structure of polymer blends by vibrational spectroscopy: the case of poly(ethylene oxide) and poly(methyl methacrylate) blends

The blends of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) are prepared in the form of thin films from solution casting. The Fourier transform infrared spectra of the blends are recorded in the spectral range 400–4000 cm^?1. The spectra are analysed using various recent techniques of vibrational spectroscopy. It is concluded that upon blending PEO takes preferentially a planar zig-zag structure. Furthermore the intermolecular interactions between the molecules of PEO and PMMA in blends are very weak and their compatibility as blends is more ‘physical’ than ‘chemical’. Further, on the basis of the atomic charges transferred from model molecules it is seen that the blending is preferred with isotactic PMMA when compared to syndiotactic PMMA.     

Gas permeation of polymer blends. II. Poly(vinyl chloride)/acrylonitrile–butadiene copolymer (NBR) blends

The transport behavior of He, O₂, N₂, and CO₂ in a series of PVC/NBR polymer blends with varying acrylonitrile (AN) content in the NBR component has been studied at 25° and 50°C. In addition, measurements of density, crystallinity, and thermal expansion coefficients were carried out. The transport behavior of these blends is similar to previous result for PVC/EVA.¹. With increasing AN content in NBR, the permeability (P) and diffusivity (D) of the permeants decreased while the activation energy for diffusion (E_D) increased. For the polymer blends, better additivity of permeability and diffusivity was observed with increasing AN content in the NBR component. The polymer blends also showed increasing volume contraction with increasing AN content in the NBR component. These effects have been discussed as due mainly to increased polymer–polymer interaction causing reduced segmental mobility and increased compatibility of the two polymers. The sorption values calculated from P/D ratios were largely irregular and fluctuated with the blend composition. They were less reproducible than other transport parameters, i.e., P and D measured separately. Several reasons for the irregular sorption behavior were proposed.     

Dielectric behavior of polymer blends based on poly(vinylidene fluoride)

Dielectric properties of polymer blends based on PVDF and two amorphous polymers, i.e. poly(vinyl acetate) and poly(methyl methacrylate), have been studied at different frequencies in the temperature range between –150 and +150°C. The novelty of this work lies in the way of planning the polymer blends compositions, which have been prepared according to a statistical design proposed by Scheffé. The purpose is to obtain an empirical equation capable of reproducing the behavior of these systems. From the results obtained after applying the model to the values of the glass transition temperature of PVDF in these polymer blends, it is possible to draw conclusions about their compatibility.     

Crosslinkable coupling agents: Synthesis and use for modification of interfaces in polymer blends

A novel coupling agent containing 2-oxazoline and 2-oxazinone as well as hydrosilane moieties has been prepared by hydrosilylation of the corresponding allyl ether containing precursor with a methylhydrosiloxane-dimethylsiloxane copolymer. This hydrosiloxane containing coupling agent, termed as SCA, was characterized by ¹H NMR and its crosslinkability was proven by DSC. SCA was used for the modification of the interfaces in heterogeneous polymer blends. In a model blend system based on mono-carboxylic acid terminated polystyrene (PS-COOH) and mono-amino terminated poly(methyl methacrylate) (PMMA-NH₂) the 2-oxazoline and 2-oxazinone units of SCA can selectively react with the carboxylic groups or amino groups, respectively. The remaining hydrosilane units partially crosslink under the used mixing conditions.The morphology of the three-component blends prepared by melt mixing was evaluated. SCA is immiscible with the polymers and forms its own phase. The expected location of the SCA at the interface between the polymers was proven only in an annealed, strongly phase separated blend. Overall the effect of the compatibilizer on the morphology is very small. Neither the domain size nor the composition for phase inversion are significantly affected in this blend system by the presence of SCA.     

Free volume changes in mechanically milled PS and PC studied by positron annihilation lifetime spectroscopy (PALS)

The effect of mechanical milling on free volume was studied by means of positron annihilation lifetime spectroscopy (PALS) in polystyrene (PS) as a typical brittle polymer and in polycarbonate (PC) as a tough representative. Long‐time milling increases the free volume, while a decrease is observed for short milling times. The changes are mostly irreversible in PS. The irreversible fraction is much smaller for PC. Gel permeation chromatography (GPC) measurements show a decrease of the molecular weight, which is much more pronounced in PS. The milling‐induced irreversible changes in free volume are attributed to chain‐end defects resulting from chain scission. In PC, other deformation‐induced defects that anneal upon heat treatment above the glass transition temperature dominate. Polym. Eng. Sci. 44:1351–1359, 2004. © 2004 Society of Plastics Engineers.     

Gas permeation of polymer blends. III. Poly(vinyl chloride) (PVC)/chlorinated polyethylene (CPE)

The permeability P, diffusivity D, and activation energy for diffusion, E_D, of He, O₂, N₂, and CO₂ were determined for blends of PVC/chlorinated polyethylene (CPE), where the chlorine content of the CPE components varied: 36 wt-% for CPE-1, 42 wt-% for CPE-2, and 48 wt-% for CPE-3. The difference in thermal expansion coefficients Δα above and below the glass transition temperature T_g of the polymers and the fractional free volume V_g of the polymers at their T_g were determined. Density and crystallinity measurements for the blends were also carried out as in the earlier work (Shur and Rånby, J. Appl. Polym. Sci., 19 , 1337 (1975)). Dynamic mechanical measurements of the blends were made using a torsion pendulum at about 1 Hz. P and D decreased, but E_D increased with increasing CI content of CPE in the blends. P and D for the blends showed no additivity. The permeability indicated phase inversion for blend compositions at about 10% of CPE-1 and CPD-2 by weight. The experimental and the calculated densities were largely the same for PVC/CPE-1 blends; but for PVC/CPE-2 and PVC/CPE-3 blends, the experimental values were higher than the calculated ones. The Δα and V_g values for PVC and the three CPE samples decreased with increasing CI content in the polymers. Dynamic mechanical measurements indicate that PVC/CPE-1 and PVC/CPE-2 blends form largely incompatible blends, while PVC/CPE-3 blends are compatible to some extent. There is some weak interaction between PVC and CPE-3 giving a low level of compatibility. The solubility of gases obtained from time-lag measurements of diffusion for 50/50 blends decreased for He, O₂, and N₂, but increased for CO₂ with increasing Cl content in CPE. The solubility of He, O₂ and N₂ shows a positive correlation with the Lennard-Jones force constant ?/k. However, a deviation from the linear relation between ?/k and In S was observed for CO₂ and the deviation became larger with increasing Cl content in CPE. The abnormally high solubility of CO₂ is probably due to the high polarizability of this gas. The heat of solution ΔH_s indicates that for He the sorption process may be a molecular slip process (endothermic), but for other gases the sorption may proceed by a dissolution process (exothermic). There is a large difference between the calculated solubility for the blends assuming incompatibility and the experimental values from time-lag measurements. This may partly be due to the uncertainty of sorption values obtained from the time-lag method and/or partly to changes of sorption modes by interaction between PVC and CPE in the blends. The resulting transport behavior of the blends is discussed on the basis of the free volume concept and of phase–phase interaction in the blends.     

Effect of dehydrochlorination of PVC on miscibility and phase separation of binary and ternary blends of poly(vinyl chloride), poly(ethylene-co-vinyl acetate) and poly(styrene-co-acrylonitrile)

The enhancement of miscibility at the lower critical solution temperature (LCST) of the blends poly(vinyl chloride)/poly(ethylene-co-vinyl acetate) (PVC/EVA), poly(vinyl chloride)/poly(styrene-co-acrylonitrile) (PVC/SAN) and poly(vinyl chloride)/poly(ethylene-co-vinyl acetate)/poly(styrene-co-acrylonitrile) (PVC/EVA/SAN) was observed at the micron level. Such miscibility is attributed to the dehydrochlorination and formation of hydrogen bonds between blend components. However, macrolevel immiscibility of these blends heated to the LCST was observed. Such microdomain compatibility of these blends gives a synergistic character. Brittle-type failure observed for LCST samples testifies to the synergism in treated blends. ©1997 SCI     

Phase separation of poly (methyl methacrylate) / poly (styrene-co-acrylonitrile) blends in the presence of silica nanoparticles

The effects of silica nanoparticles on the phase separation of poly (methyl methacrylate)/poly (styrene-co-acrylonitrile) (PMMA/SAN) blends are studied by the rheological method. The binodal temperatures of near-critical compositions were obtained by the gel-like behavior during spinodal decomposition, which is a character of polymer blends with co-continuous morphology. The shifted Cole–Cole plot method was introduced to determine the binodal temperatures of off-critical compositions based on the appearance of shoulder-like transition in the terminal regime of blends with droplet morphology. Such method is found also applicable in nanoparticle filled polymer blends. Moreover, a new method to determine the spinodal temperature from Fredrickson-Larson mean field theory was suggested, where the concentration fluctuation's contribution to the storage modulus is used instead of the whole dynamic moduli. This method was also successfully extended to nanoparticle filled polymer blend. The influences of the concentration and the average diameter of silica particles on the phase separation temperature were studied. It was found that the small amount of the silica nanoparticles in PMMA/SAN blends will significantly change the phase diagram, which is related to the selective location of silica in PMMA. The comparisons with thermodynamic theory of particle-filled polymer blends are also discussed.     

Characterization of cathodes for rechargeable lithium batteries based on new vanadium oxides and PEO/PPz polymer blends

Three new vanadium oxides were synthesized and characterized using an X-ray. Once incorporated into different polymer systems containing either poly(ethylene oxide) or a poly(ethylene oxide)–polyphosphazene (PPz), together with carbon black (CB) as an electronic crosslinker, kinetic isothermal and nonisothermal crystallization studies were conducted, as well as an electrical characterization study through complex impedance spectroscopy for the purpose of examining, on the one hand, the effects exerted by the different vanadium compounds on the microstructure of the systems into which they are incorporated, and, on the other hand, of determining which of the synthesized vanadium compounds possesses the best conducting properties. © 1996 John Wiley & Sons, Inc.