Poly(ethylene oxide)/poly(methyl methacrylate) blends: Influence of tacticity of PMMA on the radial growth rate of PEO spherulites

Cimmino, Sossio; Pace, Emilia Di; Martuscelli, E.; Silvestre, Clara

doi:10.1002/marc.1988.030090412

Cited by 20 publications

(7 citation statements)

References 7 publications

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“…Solid polymer electrolytes (SPEs) (the solvent‐free polymer electrolytes) based on poly(ethylene oxide) (PEO) as a polymer host have been extensively studied, due to its high solvating capability of wide variety of metallic salts such as lithium sulfate (Li 2 SO 4 ), lithium iodide (LiI), lithium triflate (LiCF 3 SO 3 ), lithium bis(fluorosulfonyl)imide (LiFSI), lithium perchlorate (LiClO 4 ) and lithium tetrafluoroborate (LiBF 4 ) . However, the binary systems of PEO and salt display low conductivity ( σ DC ∼10 −6 –10 −8 S cm −1 ) and show higher conductivity ( σ DC ∼10 −4 S cm −1 ) above its melting temperature at around 65 °C and hence, they are not suitable for the commercial application at ambient temperature. This is due to the high crystallinity (up to 70%) for high molar‐mass SPEs .…”

Section: Introductionmentioning

confidence: 99%

Thermal Properties and Morphology of Poly(ethylene oxide)/Poly(n‐butyl methacrylate) Blends

Ramli

Chan

Ali

2018

Macromolecular Symposia

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From the thermodynamic point of view, most of the high molar‐mass binary polymer blends are immiscible due to the entropic contribution to the free energy of mixing is relatively small. The miscibility of the systems on the molecular scale can be assessed by the thermal properties such as quantities of glass transition temperature (Tg) and change in heat capacity (ΔCp) of the polymers. For a semi‐crystalline polymer such as poly(ethylene oxide) (PEO), the crystallinity (X*) and the melting temperature (Tm) can also give some hints on the miscibility. Apart from the thermal properties, additional scientific findings such as morphology of the blends are needed as supplementary evidences to support the results. We focus on the PEO as the polymer host, blends with poly(n‐butyl methacrylate) (PnBMA) which were prepared using solution casting technique. Thermal properties of PEO/PnBMA polymer blends were investigated by modulated differential scanning calorimeter (MDSC) on the isothermal crystallized samples at 25 °C. Tg of PEO in the blends do not show significant variation with addition of PnBMA for entire composition range while for Tg of PnBMA in the blends, it is challenging to be estimated under the experimental condition due to the overlapping of the Tg of PnBMA and melting endotherm of PEO. Constancy of quantity Tg of PEO and ΔCp of PEO corresponding to the content of PEO in the blends suggest that PEO and PnBMA are immiscible for entire blend composition. X* and Tm of PEO in the blends show insignificant variation in PEO/PnBMA blends, when PEO as major component. This implies that these blends are immiscible under the experimental conditions as agreed with results of Tg and ΔCp. Spherulitic morphologies of PEO in the blends were studied by polarized optical microscopy (POM). PnBMA phase disperses randomly in PEO matrix when PEO in excess. The absence of significant change for the fibrillar spherulitic structures of PEO spherulites with addition of PnBMA (when PEO is the major component) suggests that immiscibility of PEO and PnBMA. Besides, the crystalline structure of PEO in PEO/PnBMA blends using X‐ray diffraction (XRD) reveals that the crystalline structure of PEO is not disturbed with the addition of PnBMA when PEO is in excess as the two distinct peaks of PEO do not shift as compared to neat PEO. Impedance spectroscopy (IS) studies show that the ionic conductivities (σDC) of the polymer blends at room temperature slightly increase with increasing of PEO with the order of magnitude of 10−11–10−10 S cm−1. This system serves as a potential polymer host as solid polymer electrolytes when added with inorganic salt.

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Section: Introductionmentioning

confidence: 99%

Thermal Properties and Morphology of Poly(ethylene oxide)/Poly(n‐butyl methacrylate) Blends

Ramli

Chan

Ali

2018

Macromolecular Symposia

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“…Furthermore such systems offer an opportunity to learn more about the occurrence of nonequilibrium phenomena in mixtures containing crystallizable components. The freezing in of intermediate states during the 16.04.03 approach of equilibria is well documented for polymer blends of semi-crystalline and amorphous components in general [1][2][3][4][5][6][7][8][9][10][11][12][13] and with PEO as one component in particular [14][15][16][17][18][19] . Analogous investigations for the considerably less viscous solutions of such polymers (which should therefore be less prone to non-equilibria phenomena) are to our knowledge lacking.…”

Section: Introductionmentioning

confidence: 99%

PEO/CHCl₃. Crystallinity of the Polymer and Vapor Pressure of the Solvent. Equilibrium and Nonequilibrium Phenomena

Khasanova

Wolf

2003

Macromolecules

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Vapor pressures were measured for the system CHCl 3 /PEO 1000 (PEO stands for polyethylene oxide and 1000 for M w in kg/mol) at 25 °C as a function of the weight fraction w of the polymer by means of a combination of head space sampling and gas chromatography. The establishment of thermodynamic equilibria was assisted by employing thin polymer films. The degrees of crystallinity α of the pure PEO and of the solid polymer contained in the mixtures were determined via DSC. An analogous degree of polymer insolubility β was calculated from the vapor pressures measured in this composition range. The experiments demonstrate that both quantities and their concentration dependence are markedly affected by the particular mode of film preparation. These non-equilibrium phenomena are discussed in terms of frozen local and temporal equilibria, where differences between α and β are attributed to the occlusion of amorphous material within crystalline domains. Equilibrium information was obtained from two sources, namely from the vapor pressures in the absence of crystalline material (gas/liquid) and from the saturation concentration PEO (liquid/solid). The thermodynamic consistency of these data is demonstrated using a new approach that enables the modeling of composition dependent interaction parameters by means of two adjustable parameters only.

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“…Mobility of ions, in some cases, is related to segmental motion of polymer chains in the amorphous phase of the systems. [14][15][16][17] PEO with lithium salt systems posses low conductivity ($10 À6 À 10 À8 S cm À1 ) at room temperature [17][18][19][20] and show higher ionic conductivity (10 À4 S cm À1 ) above its melting temperature at around 65 C. [21][22] Many approaches have been used for enhancement of conductivity of SPEs, e.g.…”

Section: Introductionmentioning

confidence: 99%

Thermal, Conductivity and Molecular Interaction Studies of Poly(ethylene oxide)/Poly(methyl acrylate) Solid Polymer Electrolytes

Halim

Chan

Winie

2017

Macromolecular Symposia

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Summary Solid polymer electrolytes of poly(ethylene oxide) (PEO) and poly(methyl acrylate) (PMA) with addition of lithium perchlorate (LiClO4) were studied. Samples were prepared by solution casting method. An existence of single and compositional‐dependant glass transition temperature (Tg) of PEO/PMA systems [studied by Differential scanning calorimetry (DSC)] shows miscibility of the binary PEO/PMA blends as well as when added with small of amount of LiClO4 in the molten state and amorphous phase. The systems are miscible in molten state and amorphous phase at high salt content with PEO content in the blends is in excess. In this case, the Tgs of the PEO/PMA blends increase slightly with increasing salt concentration suggesting the molecular interaction of salt with the polymers. Impedance spectroscopy (IS) studies reveal that PEO/PMA 80/20 blend (w/w) added with 0.12 of LiClO4 (YS) shows the highest conductivity (σDC = 1.43 × 10−5 S cm−1) as compared to PEO/LiClO4 system at the same salt concentration (σDC = 6.43 ×10−6 S cm−1). Results of Tg using DSC and molecular interaction from Fourier‐transform infrared (FTIR) spectra suggest that blend with PEO in excess, Li+ ions coordinate with ether oxygen of PEO instead of carbonyl oxygen of PMA. Hence, the percolation pathway for these SPEs is lying in the amorphous region of the PEO phase.

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Poly(ethylene oxide)/poly(methyl methacrylate) blends: Influence of tacticity of PMMA on the radial growth rate of PEO spherulites

Cited by 20 publications

References 7 publications

Thermal Properties and Morphology of Poly(ethylene oxide)/Poly(n‐butyl methacrylate) Blends

Thermal Properties and Morphology of Poly(ethylene oxide)/Poly(n‐butyl methacrylate) Blends

PEO/CHCl₃. Crystallinity of the Polymer and Vapor Pressure of the Solvent. Equilibrium and Nonequilibrium Phenomena

Thermal, Conductivity and Molecular Interaction Studies of Poly(ethylene oxide)/Poly(methyl acrylate) Solid Polymer Electrolytes

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Poly(ethylene oxide)/poly(methyl methacrylate) blends: Influence of tacticity of PMMA on the radial growth rate of PEO spherulites

Cited by 20 publications

References 7 publications

Thermal Properties and Morphology of Poly(ethylene oxide)/Poly(n‐butyl methacrylate) Blends

Thermal Properties and Morphology of Poly(ethylene oxide)/Poly(n‐butyl methacrylate) Blends

PEO/CHCl3. Crystallinity of the Polymer and Vapor Pressure of the Solvent. Equilibrium and Nonequilibrium Phenomena

Thermal, Conductivity and Molecular Interaction Studies of Poly(ethylene oxide)/Poly(methyl acrylate) Solid Polymer Electrolytes

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PEO/CHCl₃. Crystallinity of the Polymer and Vapor Pressure of the Solvent. Equilibrium and Nonequilibrium Phenomena