Molecular dynamics simulation studies of the miscibility and thermal properties of PMMA/PS polymer blend

This investigation is an attempt to improve our understanding of the thermal properties of PMMA (Polymethyl methacrylate) by using PS(Polystyrene); the miscibility of PMMA/PS polymer blend is studied. Our work aims to study the impact of the percentage of PMMA/PS polymer blend on the simulated values of the glass transition temperature (Tg) using the dilatometric method. Compass was chosen as the force field (second category force field). The results reveal a single value of the glass transition temperature Tg that is found for all the curves of the PMMA/PS blend system (molar ratio: (50:50, 60:40, 54:46 and 80:20)); this could be a good criterion for predicting the miscibility. Additionally, the solubility parameters of PMMA and PS are calculated and used to obtain the Flory–Huggins parameter, and the morphology of our polymer blend is simulated using the dissipative particle dynamics method (DPD). Our results exhibit an increase in the Tg of PMMA whenever PS is added; hence, we can confirm the miscibility of the PMMA/PS polymer system.     

Calorimetric study of blend miscibility of polymers confined in ultra-thin films

Miscibility in blends of polystyrene and poly(phenylene oxide) (PS/PPO) confined in thin films (down to 6 nm) was investigated using a recently developed sensitive differential alternating current (AC) chip calorimeter. Comparison of composition dependence of glass transition in thin films with common models should provide information on miscibility. This study focuses on the blend system polystyrene and poly(phenylene oxide) (PS/PPO) because it is thought as a miscible model system in the whole composition range. Furthermore, its local dynamic heterogeneity is already identified by dynamic mechanic thermal analysis (DMTA) and solid state NMR techniques. For this blend, we find that even for the thinnest films (6 nm, corresponding to about half of PPO’s radius of gyration R _g) only one glass transition is observed. The composition dependence of T _g is well described by the Fox, Couchman or Gordon-Taylor mixing law that are used for the miscible bulk blends. Although there is a contradicting result on whether T _g decreases with decreasing film thickness between our calorimetric measurements and Kim’s elipsometric measurements on the same blend (Kim et al. Macromolecules 2002, 35, 311–313), the conclusion that the good miscibility between PS and PPO remains in ultrathin films holds for both studies. Finally, we show that our chip calorimeter is also sensitive enough to study the inter-layer diffusion in ultrathin films. PS chain in a thin PS/PPO double layer that is prepared by spin coating PPO and PS thin film in tandem will gradually diffuse into the PPO layer when heated above T _g of PS, forming a PS_xPPO_100−x blend. However, above the PS_xPPO_100−x blend, there exists an intractable pure PS like layer (∼30  nm in our case) that does not diffuse into the blend beneath even staying at its liquid state over 10 hours.     

Morphology and Crystallization in Polystyrene/polyamide 6 Blends: Influence of a Reactive Compatibilizer and Nano-TiO2

A polystyrene (PS)/polyamide 6 (PA6) (70/30, weight ratio) blend in the presence of terminal malic anhydride functionalized PS (FPS) and nano-TiO₂ were prepared using a meltmixing technique. The morphology of the blend was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The crystallization behavior of the PA6 phase in the blend was studied using DSC techniques. The results showed that by adding 7.5 phr nano-TiO₂, the size of the dispersed PA6 domains was dramatically decreased; An additional 1.5 phr FPS to the PS/PA6/TiO₂ blend, for reactive blending, caused the size of the dispersed PA6 domain to become even smaller and more uniform, and a weak, broad crystallization exotherm of PA6 was observed. However, the degree of crystallinity of PA6 in PS/PA6/TiO₂/FPS blend was sharply increased.     

Effect of Polydispersity on the Phase Behavior of Polystyrene (PS)/Poly (Vinyl Methyl Ether) (PVME)

The thermodynamics and kinetics of phase separation in partially miscible blends of poly (vinyl methyl ether) (PVME) and two kinds of polystyrene (PS) with the same weight average molecular weight but different polydispersity were studied. The miscibility of PS/PVME with the monodisperse PS was better than that of PS/PVME with the polydisperse PS. Different morphology was observed for the two kinds of PS/PVME (10/90) blends during the nonisothermal phase separation process. The blend with monodisperse PS presented a co-continuous structure while the blend with polydisperse PS presented a viscoelastic phase separated network structure at a quench depth of 29°C. With increase of the heating rate, the increase of cloud point of PS/PVME (30/70) with polydisperse PS was smaller than that of PS/PVME (30/70) with monodisperse PS. During the isothermal phase separation of the critical composition (20/80) of PS/PVME with a quench depth of 30°C, it was found that the phase morphology of the two kinds of blends was nearly the same at the early stage of phase separation. However, as the dispersed phase, an approximately spherical droplet structure was observed in the blend with monodisperse PS at the late stage of phase separation, which did not appear in the blend with polydisperse PS.     

The development of Li<Superscript>+</Superscript> conducting polymer electrolyte based on potato starch/graphene oxide blend

Solid polymer electrolytes based on potato starch (PS) and graphene oxide (GO) have been developed in this study. Blending GO with PS has improved the ionic conductivity and mechanical properties of the electrolytes. In this work, series of polymer blend consisting of PS and GO as co-host polymer were prepared using solution cast method. The most amorphous PS-GO blend was obtained using 80 wt% of PS and 20 wt% of GO as recorded by X-ray diffraction (XRD). Incorporation of 40 wt% lithium trifluoromethanesulfonate (LiCF₃SO₃) into the PS-GO blend increases the conductivity to (1.48 ± 0.35) × 10^?5 S cm^?1. Further enhancement of conductivity was made using 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]). The highest conductivity at room temperature is obtained for the electrolyte containing 30 wt% of [Bmim][Cl] with conductivity value of (4.8?0 ± 0.69) × 10^?4 S cm^?1. Analysis of the Fourier transform infrared spectroscopy (FTIR) spectra confirmed the interaction between LiCF₃SO₃, [Bmim][Cl], and PS-GO blend. The variation of the dielectric constant and modulus studies versus frequency indicates that system of PS-GO-LiCF₃SO₃-[Bmim][Cl] obeys non-Debye behavior.     

Effect of Nanoparticles on the Phase Behavior of Polystyrene/Poly(vinyl methyl ether) Blends with Different Polydispersities

Effects of two kinds of silica nanoparticles on the phase behavior of blends of poly (vinyl methyl ether) (PVME) and two kinds of polystyrene (PS), with the same number average molecular weight but different polydispersities, were studied by using optical microscopy. The addition of both the hydrophilic A200-SiO₂ and hydrophobic R974-SiO₂ nanoparticles made the miscibility become worse. The decrease in the phase separation temperatures of PS/PVME with polydisperse PS (pPS) was larger than that of PS/PVME with monodisperse PS (mPS) in the presence of A200-SiO₂; the shifts of the phase separation temperatures of mPS/PVME and pPS/PVME were comparable for the incorporation of R974-SiO₂. The addition of both kinds of silica accelerated the phase separation during the nonisothermal phase separation. The domain size changes of the phase morphology of mPS/PVME (50/50) and pPS/PVME (50/50) were almost the same during the nonisothermal phase separation in the presence of nanoparticles. During the isothermal phase separation, the introduction of silica slowed down the phase separation dynamics by hindering the phase structure transition. The morphology changes of pPS/PVME (50/50) were more evident than those of mPS/PVME (50/50) with the incorporation of SiO₂.     

Solution blends of polyacrylonitrile with segmented polyurethanes: Effect of soft segments

Solution blends of a modified polyacrylonitrile (PAN) with polyurethane (PU) obtained from 4, 4′-diphenylmethane diisocyanate (MDI) and two different types of polyols– i.e., ether-linked polytetramethylene ether glycol (PTEG) and ester-linked polytetramethylene adipate glycol (PTAG) – were prepared in N, N-dimethylformamide (DMF). The domains in the PTAG-PU blends were much finer than those in the PTEG-PU blends. Shift of the soft segment transition temperatures (T _gs) of PU toward lower temperature with increasing PAN was more significant for PTAG-PU blends. Miscibility was also examined through Fourier transform infrared spectra. These showed clear carbonyl peak shifts due to the different types of hydrogen bonding. The PTAG-PU/PAN (30/70) blend had the maximum draw ratio at failure, measured in 100°C water; it was over 2.5 times that of pure PAN.     

Study of Miscibility in Polymer Blends Obtained from Binary Inclusion Complexes of γ-Cyclodextrin and Polycarbonate/Poly(Ethylene Terephthalate)

In this work the synthesis and characterization of the nanostructure of polymer blends of polycarbonate (PC) and poly(ethylene terephthalate) (PET) obtained from their inclusion complexes with γ-cyclodextrin are reported. The blends prepared by this method present differences in their miscibility compared with those blends obtained by conventional methods like solution casting, coprecipitation, or melt blending. In order to understand the influence of molecular weight in the inclusion complex process, PCs of M_w = 64,000 and 28,000 g/mol were used. The analysis of the nanostructured blend by Fourier transform infrared (FTIR), ¹H-nuclear magnetic resonance (¹H-NMR), wide-angle X-ray diffraction (WAXD), differential scanning colorimetry (DSC), and thermogravimetric analysis (TGA) suggests the existence of specific intermolecular interactions between PC and PET that promote miscibility in this normally immiscible polymer blend. Studies by FTIR confirm that the miscibility found was not due to a transesterification reaction during DSC analysis. There were also differences in the morphology of the blends, observed by optical microscopy, obtaining a more homogeneous phase for blends formed in inclusion complexes. The results obtained strongly suggest an improvement in miscibility of the PC/PET blends.     

Modification of Wood Flour Surfaces by Esterification with Acid Chlorides: Use in HDPE/Wood Flour Composites

Modification of wood fiber/flour (WF) surfaces can improve their compatibility with hydrophobic plastic matrices and reduce composite water uptake. WF was esterified with octanoyl chloride and palmitoyl chloride. Modified WF was analyzed by FT-IR. More extensive esterification occurred in highly polar dimethylformamide (DMF) than in much less polar CHCl₃ or methyl tert-butyl ether (MTBE). DMF penetrates into the fiber far more than CHCl₃ or MTBE, making more –OH groups available for esterification. Increasing the acid chloride chain length from C₈ to C₁₆ decreased the mole fraction of esterification. Longer chains cover surface –OH groups, retarding reactions with nearby hydroxyls after esterification. Longer chain acid chlorides also have lower reactivity and penetrate into the hydrophilic wood fiber more slowly. Modified wood flour surfaces were covered by a hydrophobic layer of ester groups (SEM). Modified wood flour surfaces and WF/HDPE composite fracture surfaces were studied by SEM. C₈-modified wood flour (60 wt%)/HDPE composites exhibited far less water absorption after 24 h and 216 h immersions compared with unmodified WF (60 wt%)/HDPE composites. Water absorption continues over the 216 h period. Esterified WF/HDPE composites exhibited lower flexural strengths and moduli. In contrast to C₈-esterification, the addition of maleated polypropylene (MAPP) to WF/HDPE composites improved composite mechanical performance and gave similar water absorption properties to C₈-esterified WF composites.     

Electrospinning and Mechanical Properties of Polystyrene and Styrene-Isoprene-Styrene Block Copolymer Blend Nanofibres

Electrospinning of polystyrene (PS) and styrene–isoprene–styrene block copolymer (SIS) blends with different composition weight ratios was carried out with a mixed solvent, tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) (80/20, v/v). Electrospun PS/SIS blend fibers were characterized using scanning electron microscopy. The results indicated that the presence of DMF resulted in a beneficial effect on fiber formation and greater electrospinnability of as-spun fibers. Furthermore, the morphological structure and diameters of as-spun fibers from PS and SIS blends were affected by the composition weight ratio and the solution properties. The fibers from 10 wt% solution exhibited the best mechanical properties compared to the fibers from other concentrations for the same composition, and increasing the SIS content one observes a vanishing of PS-related properties, while SIS-related properties emerges.     

Investigation of microwave absorbing properties for magnetic nanofiber of polystyrene–polyvinylpyrrolidone

Aligned magnetic blend of polystyrene–polyvinylpyrrolidone (PS–PVP) nanofibers were prepared by this method. First, polystyrene–polyvinylpyrrolidone (PS–PVP) blend solution in THF was synthesized. Then magnetic of PS–PVP–Fe₃O₄–polyethylene glycol (PEG) was prepared by masking method. Finally, magnetic nanofiber of PS–PVP–Fe₃O₄–PEG was prepared by electrospinning method, too. An electric potential difference of 25 kV was applied between the collector and a syringe tip, and the distance between the collector and the tip was 13 cm. Fe₃O₄ is exhibit various magnetic properties of which the complex permeability and the permittivity, in particular, are important in determining their high frequency characteristics. The magnetic oxide particles and nanofiber of nanometer size were characterized by TEM and SEM respectively. The thermal properties of nanofibers were determined by TGA and DSC. The magnetic characterization of the fibers was also performed by VSM and AFM techniques. On the other hand, nanofiber with diameters ranging from 30 to 40 nm, showing at room temperature, coercive field values of around 25 kV and saturation magnetization was 1.1 emu/g. Microwave reflection loss of the sample was tested at 8–12 GHz microwave frequencies and the results showed that magnetic nanofiber possessed the microwave absorbing properties.     

Morphological Aspects of In-Situ Compatiblized Binary Polymer Blends With Variable Viscosity Ratios of Components

The in-situ compatiblized binary polymer blend polypropylene(PP)/polystyrene(PS)/ anhydrous aluminum chloride(AlCl₃) was selected as a model system of a reactive polymer blend to investigate the effect of viscosity ratio of components at a constant shear rate on the phase morphological behavior in in-situ compatibilized systems. The results showed that the well-known interfacial compatibilization effect was related to variations of viscosity ratios of components in the reactive PP/PS blends with different contents of AlCl₃ catalyst. The phase morphology evolution of the in-situ compatiblized reactive blend was determined by both the interfacial compatibilization and the variation of the viscosity ratio of components under the fixed mixing conditions, which showed characteristics obviously different from and much more complex than those in binary polymer blends generally compatiblized by added compatiblizers. The results implied that the variation of the viscosity ratio of components should be checked carefully and taken into account if necessary, when the phase morphology of binary polymer blends is investigated, especially in complex in-situ compatiblized reactive polymer blends.     

Effect of gamma-irradiation on the structural,optical and electrical properties of PEO/starch blend containing different concentrations of gold nanoparticles

ABSTRACT

Blend of polyethylene oxide (PEO)/starch (70/30 wt.%) filled with different amounts of gold nanoparticles (AuNPs) were prepared using the casting technique. X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) techniques were used to investigate the structure of polymeric samples before and after exposing to gamma irradiation at different times. XRD showed a gradual decrease in intensity of crystalline peaks with increasing the gamma dose denotes a decrease in the amount of crystalline phase in the films, while the FTIR measurement shows induced changes in chemical structure assigned to the AuNPs amount and irradiation times. The optical energy gap values (E_g) for unirradiated and irradiated samples were calculated and interpreted. The differential scanning calorimetry (DSC) which showed the miscibility between the two components of the blend. The electrical conductivity (σ) measurement was showed increased in electrical conductivity after exposure to the gamma dose. The gold nanoparticles were used as nano?ller to improve the structural and electrical properties of polymeric samples. The results showed the Gamma irradiation significantly effect on the structural and electrical properties of PEO/starch blend.     

Structure and Thermal Stability of Polystyrene/Layered Silicate Nanocomposites

Polystyrene/layered silicates nanocomposites were prepared by intercalation in solution method, using CHCl₃ and CCl₄ as solvents. The clay used was organically modified by hexadecyltrimethyl–ammonium bromide (CTAB) at various surfactant loadings. It was found that intercalated nanocomposite structure was obtained using CHCl₃ as solvent while exfoliated or partially exfoliated was the predominant form in the case of CCl₄. X-ray diffraction and thermogravimetric analysis were used to characterize the nanocomposite morphology and thermal stability, respectively. Enhancement in thermal stability was observed for PS-nanocomposites compared to that of pristine polymer as indicated by TGA measurements. This increment was more prevalent for exfoliated nanocomposites prepared with carbon tetrachloride as solvent.     

Preparation and characterization of Tb and Tb(sal)3·nH2O doped PC:PMMA blend

Tb doped polycarbonate:poly(methyl methacrylate) (Tb-PC:PMMA) blend was prepared with varying proportions of PC and PMMA. Thermal and spectroscopic properties of the doped polymer have been investigated employing Fourier Transform Infrared (FTIR) absorption and differential scanning calorimetric (DSC) techniques. PC:PMMA blend (with 10 wt% PC and 90 wt% PMMA) shows better miscibility. Optical properties of the dopant Tb³⁺ ions have been investigated using UV-vis absorption and fluorescence excited by 355 nm radiation. It is seen that luminescence intensity of Tb³⁺ ion depends on PC:PMMA ratio and on Tb³⁺ ion concentration. Concentration quenching is seen for TbCl₃·6H₂O concentration larger than 4 wt%. Addition of salicylic acid to the polymer blend increases the luminescence from Tb³⁺ ions. Luminescence decay curve analysis affirms the non-radiative energy transfer from salicylic acid to Tb³⁺ ions, which is identified as the reason behind this enhancement.     

COMPATIBILIZATION OF POLY(ETHYLENE OXIDE)/POLY(STYRENE) BLENDS: EFFECT OF THE MOLECULAR WEIGHT OF THE COMPATIBILIZER

The effect of the molecular weight and concentration of the compatibilizer maleic acid-alt-styrene copolymer (MAaS) on the compatibility behavior of incompatible poly(ethylene oxide)/poly(styrene) (PEO/PS) blends was studied by differential scanning calorimetry (DSC) and polarized light microscopy (PLM). PEO with [Mbar] _w = 100,000 (PEO₁₀₀) and PS with [Mbar] _w = 225,000 (PS₂₂₅) were used for this study. DSC measurements showed two T _g values that were shifted relative to those of the pure components. This result should be indicative that MAaS acts as a compatibilizer for the blend. Diminishing of the spherulitic growth rate G was observed as the content and molecular weight of MAaS increased in the blend. This result was confirmed by morphological analysis, by which it was possible to observe that the amorphous component diminished its droplike domains. Contact angle measurements suggest that the wettability of PEO drops on a PS/MAaS surface are larger in the system containing MAaS as the compatibilizer.     

Miscibility of Solution Blends of Unsaturated Polyester Resin with Polystyrene and Polycarbonate

Miscibility studies of unsaturated polyester resin (UPR) blends with two different thermoplastics—polystyrene (PS) and polycarbonate (PC), in a common solvent, chloroform, were carried out by viscosity, ultrasonic velocity, density, and refractive index methods. Two interaction parameters, μ and α were calculated using viscosity data for these blends. The positive interaction parameter values (μ and α > 0) obtained for the UPR/PS blend and the negative interaction parameter values (μ and α < 0) obtained for the UPR/PC blend indicate that the former is a miscible blend and the latter is an immiscible blend. These results were further confirmed by the ultrasonic velocity, density, and refractive index measurements.     

Electrical,structural, and morphological studies of honeycomb-like microporous zinc-ion conducting poly (vinyl chloride)/poly (ethyl methacrylate) blend-based polymer electrolytes

Solid polymer electrolytes (SPEs) based on poly (vinyl chloride)/poly (ethyl methacrylate) [PVC/PEMA] blend complexed with zinc triflate [Zn(CF₃SO₃)₂] salt have been prepared using solution casting technique. Thin film samples containing various blend ratios of PVC/PEMA with fixed composition of salt have been examined by means of complex impedance analysis, and as a consequence, the typical composition corresponding to PVC (30 wt%)/PEMA (70 wt%) has been identified as the optimized blend exhibiting the highest room temperature ionic conductivity of 10^?8 Scm^?1. The ionic conductivity of the optimized blend was further enhanced from 10^?8 to 10^?6 Scm^?1 by adding the chosen salt in different weight percentages at 301 K. The occurrence of complexation of the polymer blend and an evidence of interaction of cations, namely Zn²⁺ ions with the polymer blend, have been confirmed by Attenuated total reflectance-Fourier transformed infrared (ATR-FTIR) spectroscopy measurement studies. The efficacy of ion-polymer interactions was estimated by means of an evaluation of transport number data pertaining to Zn²⁺ ions which was found to be 0.56. The apparent changes resulting in the structural properties of these polymer electrolytes possessing a honeycomb-like microporous structure were identified using X-ray diffraction (XRD) and scanning electron microscopic (SEM) studies. Such promising features of the present polymer blend electrolyte system appear to suggest possible fabrication of new rechargeable zinc batteries involving improved device characteristics.     

Intermacromolecular complexation due to specific interactions. 6. Miscibility and complexation between Poly{Styrene-co-[p-(2-Hydroxypropan-2-yl)Styrene]}and poly[n-butyl Methacrylate-co-(4-vinylpyridine)]

In recent years, considerable attention has been focused on polymer miscibility and Complexation due to hydrogen bonding. Monodisperse, proton-donating polystyrene (PS), that is, poly{styrene-co-[p-(2-hydroxypropan-2-yl)styrene]} [PS(t-OH)], was synthesized via chemical modification of polystyrene. Poly[n-butyl methacrylate-co-(4-vinylpyridine)] (BVPy), as a proton acceptor, was prepared by free-radical copolymerization of the corresponding monomers at low conversion. In organic solutions of PS(t-OH)/BVPy blends, viscometry was employed to study the Complexation behavior. Solvents with different proton-accepting abilities were used and hence proved to exert distinctive effects on solution complexation. In very dilute solutions, the complex aggregate was observed by static and dynamic light scattering (LS). Differential scanning calorimetry (DSC) investigation proved that miscibility could be greatly enhanced when a small amount of hydrogen bonding was introduced into the originally immiscible PS/PBMA (polybutyl methacrylate) system. Although it was found that the T _g of the hydrogen-bonding polymer complexes occurred at higher temperatures with respect to linear weight-average value, DSC measurement alone could not accurately distinguish polymer complexes from ordinary miscible blends. Based on the data of miscibility from DSC and complexation from vis-cometry in 1,2-dichloroethane for a few tens of blends, which cover broad ranges of the contents of interaction sites, a map showing the immiscibility-miscibility-complexation transitions by strengthening the hydrogen bonding for the system of PS(t-OH)/BVPy was successfully constructed.     

The photostability and fluorescence properties of diphenylisobenzofuran

The photostability and fluorescence properties of 1,3-diphenylisobenzofuran (DPBF), a popular singlet oxygen (¹O₂ or ¹Δ_g) trapping-agent used in various solvents, are examined by UV-vis absorption, steady-state and time-resolved fluorescence techniques, as well as laser flash photolysis. DPBF is found to be easily photolyzed even if it is only exposed to the weak daylight in halogen-containing solvents in the absence of singlet oxygen. The photolysis is due to the addition of •CCl₃ (•CHCl₂) to DPBF in the absence of oxygen, or •OOCCl₃ (•OOCHCl₂) initiated chain polymerization of DPBF in the presence of oxygen. This result suggests that the reported singlet oxygen production in these solvents detected by DPBF was significantly higher than the true value. DPBF in DMF, DMSO, etc., on the other hand, is stable enough to enable fluorescence measurements. The fluorescence quantum yield of DPBF is very high in aprotic solvents and close to unity. The absorption, excitation and emission maxima are only slightly affected by the nature of solvents. The fluorescence lifetime is 5.0±0.3 ns.