Sequential Structure,Crystallization, and Properties of Biodegradable Poly(ethylene Terephthalate-Co-Ethylene Oxide-Co-Lactide) Copolyester

The sequential structure, isothermal crystallization, tensile property, and degradation behavior of poly(ethylene terephthalate-co-ethylene oxide-co-lactide) (ETOLA) copolyester based on melt transesterification of poly(ethylene terephthalate) with poly(ethylene oxide) and oligo(lactic acid) was investigated. The degree of randomness was calculated to be 0.38, showing the incorporation of poly(ethylene oxide) (PEO) blocks into the homogeneous sequences of ethylene terephthalate (ET) and lactide (LA) units. The isothermal crystallization kinetics results revealed that the crystallization activation energy of the copolyester calculated using the Arrhenius’ equation was lower than that reported for poly(ethylene terephthalate) (PET), indicating that the addition of PEO and LA units into PET retarded the crystallization of PET. The copolyester exhibited the same crystal structure at different crystallization temperatures, similar to that of PET homopolymer, based on wide angle X-ray diffraction results. The size of the spherulites of ETOLA increased with crystallization temperature. The increase of crystallization temperature reduced the elongation at break of the copolyesters, as well as the enzymatic degradation.     

Influence of NaY on the morphology and conductivity characteristics of poly(ethylene oxide)-LiClO4 electrolyte with plasticizer EC

A novel solid-state composite polymer electrolyte (CPE), based on a polymer, poly(ethylene oxide) (PEO), alkali metal salts, and NaY molecular sieve powders with a small amount of low molecular weight plasticizer, ethylene carbonate (EC) is investigated. (PEO)₁₆LiClO₄ polymer metal salt complexes with 5 wt% EC, and different content of NaY are prepared by the solution casting technology. The crystallization characteristic, surface morphology, and ionic conductivity of the CPE systems are studied using X-ray diffractometer (XRD) analysis, scanning electron microscopy (SEM), energy dispersive spectrometer, and impedance spectroscopy. It is found that NaY incorporation has a beneficial effect on the enhancement of ionic conductivity, increasing two orders of magnitude. XRD spectra show that the NaY has a major influence on the crystallization process of polymer matrix. By incorporating NaY, the crystallinity degree of PEO matrix obviously decreases. SEM images show a dramatic modification of surface morphology, the surface spherulites of polymer matrix disappear, and ultra-branched and cross-linked framework structure forms, which play an important role in ion transport and enhancing the tensile strength (TS). The TS is achieved 2.12 MPa with the content of 35 wt% NaY, far higher than the 0.17 MPa with (PEO)₁₆LiClO₄–5 wt% EC. In addition, it is demonstrated for the first time that EC affects the network structure of the molecular sieve and leads to exhibit enhanced ionic conductivity of electrolyte maintaining for a long time.     

TIME-RESOLVED SAXS/WAXS STUDY OF PHASE BEHAVIOR AND CRYSTALLIZATION IN POLYMER BLENDS

Real-time SAXS and WAXS patterns have been simultaneously obtained during isothermal melt-crystallization of blends of low-molecular-weight poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA). The analysis of results shows that the originally homogeneous, single-phase polymer blend separates into two phases. The PMMA molecules diffuse from the blend and form completely segregated regions while PEO starts to crystallize. The first and dominating effect at the beginning of crystallization is the formation of unstable lamellae of nonintegrally folded chains (NIF). The real-time crystallinity and density of the PEO crystalline phase in absolute units were obtained from the time-resolved SAXS/WAXS results. The structure development proceeds in two steps. A very fast evolution of PEO crystals from the melt starts to crystallize in disordered NIF lamellae with thick amorphous interlayers and with a lower density of crystalline phase. The steep growth of crystallinity and crystalline density mean quick thickening of crystalline part of lamellae and improvement of their crystalline structure. In the second step, the structure of the crystalline phase gradually improves and crystallinity grows very slowly. The recrystallization of NIF lamellae into extended chain lamellae (EC) and lamellae with once folded chains (1F) proceeds during both stages of crystallization.     

Crystallization Behavior of PEO in Nano‐Structured PEO‐b‐PS/PPO Blends

Blends of poly (ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymer and poly (2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) homopolymer were obtained by solution blending, and the morphologies of PEO dispersed nanoparticles in PPO/PS matrix were observed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The isothermal crystallization kinetics was studied using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Nonisothermal crystallization kinetics was studied using DSC. The results showed that PEO segments were easier to crystallize in the blend than in the copolymer probably due to the interfaces of PPO acting as nucleation sites to promote the crystallization of PEO. The crystallization of PEO blocks destroyed the pre‐existing microdomain structure even though the glass transition temperature of the matrix was much higher than the crystallization temperature.     

Influence of Shearing on Crystallization Behavior of Polyoxymethylene/Poly(Ethylene Oxide) Crystalline/Crystalline Blends

The effect of shearing on crystallization behavior of a crystalline/crystalline blend, polyoxymethylene [POM]/poly(ethylene oxide) [PEO], was investigated using polarized light microscopy connected with a CSS450 shearing hot-stage, scanning electron microscopy, differential scanning calorimetry [DSC], and x-ray diffraction [XRD]. The experimental results indicated that the shearing made POM and PEO disperse more evenly and increased the inclusion and entanglement effects between the molecular chains of POM and PEO and therefore enhanced the influence of PEO on the crystallization of POM. As a result, the blend sheared at a shear rate of 20 s^?1 for 10 min at 160°C formed shish–kebab crystals and produced more interlamellar structures compared with the formation of perforated spherulites in the unsheared blend. Moreover, a more obvious shoulder melting peak of POM appeared in the DSC heating trace and a new diffraction peak occurred at 2θ = 31.7° in the XRD pattern for the sheared POM/PEO [50/50] blend.     

Single-molecule single crystals of poly(ethylene oxide)

Single-molecule single crystals were prepared from two fractions of poly(ethylene oxide) (PEO) with narrow molar mass distribution and an equimolar mixture of the two fractions. It was proven that the molar mass distribution of the single-molecule single crystals from the mixed sample corresponds to an addition of those of the pure fractions. Well-shaped crystals were obtained after isothermal crystallization or on annealing. A variety of morphologies typical for multimolecule single crystals of PEO were found and are described on the basis of the various known modes of twinning. The results are in agreement with the known unit cell of PEO.     

Preparation and Characterization of Poly(ethylene oxide)/Graphene Nanocomposites from an Aqueous Medium

The nanocomposite films of a functionalized graphene sheet (FGS) and poly(ethylene oxide) (PEO) were cast from the physical blend of an aqueous FGS dispersion assisted by sodium dodecyl sulfate and an aqueous PEO solution. The thermal properties observed by differential scanning calorimetry suggested that FGS had a nucleating effect on the PEO crystallization. However, we found FGS actually hindered the growth of PEO crystals. The dynamic mechanical properties indicated that FGS effectively reinforced the matrix PEO. The FGS also efficiently improved the electric conductivity of PEO. With the addition of 2 parts of FGS per 100 parts of PEO, the conductivity was increased by more than 10³-fold from that of pristine PEO.     

A novel PEO-based composite polymer electrolyte with NaAlOSiO molecular sieves powders

Ion-conducting thin film polymer electrolytes based on poly(ethylene oxide) (PEO) complexes with NaAlOSiO molecular sieves powders has been prepared by solution casting technique. X-ray diffraction, scanning electron microscopy, differential scanning calorimeter, and alternating current impedance techniques are employed to investigate the effect of NaAlOSiO molecular sieves on the crystallization mechanism of PEO in composite polymer electrolyte. The experimental results show that NaAlOSiO powders have great influence on the growth stage of PEO spherulites. PEO crystallization decrease and the amorphous region that the lithium-ion transport is expanded by adding appropriate NaAlOSiO, which leads to drastic enhancement in the ionic conductivity of the (PEO)₁₆LiClO₄ electrolyte. The ionic conductivity of (PEO)₁₆LiClO₄-12 wt.% NaAlOSiO achieves (2.370 ± 0.082) × 10⁻⁴ S · cm⁻¹ at room temperature (18 °C). Without NaAlOSiO, the ionic conductivity has only (8.382 ± 0.927) × 10⁻⁶ S · cm⁻¹, enhancing 2 orders of magnitude. Compared with inorganic oxide as filler, the addition of NaAlOSiO molecular sieves powders can disperse homogeneously in the electrolyte matrix without forming any crystal phase and the growth stage of PEO spherulites can be hindered more effectively.     

Influence of Blend Composition on Crystallization of Poly(L-Lactic Acid)/Poly (Ethylene Oxide) Crystalline/Crystalline Blends

The effect of blend composition on crystallization morphology and behavior of a crystalline/crystalline blend, poly(l-lactic acid) (PLLA)/poly(ethylene oxide) (PEO), during slow, non-isothermal crystallization was studied by polarized light microscopy (PLM) connected with a hot-stage and differential scanning calorimetry (DSC). The results showed that all of the PLLA/PEO blends produced spherulites which gradually became bigger and looser, as well as coarser, with the increment of the PEO content, indicating that the PEO crystals was resided in the interlamellar or interfibrillar (between clusters of commonly oriented lamellae) regions of the PLLA spherulites. In the (25/75) and (10/90) blends, the nucleation and growth processes of the PEO spherulites could be clearly observed in the pre-existing PLLA spherulites. The onset crystallization temperature and the melting point of one component decreased with increasing the content of the other one owing to the good miscibility of the two components in the non-crystalline state and the interaction between their macromolecules, indicating that the crystallization of each component was influenced by the other one.     

Kinetics of Isothermal and Nonisothermal Crystallization of Poly(ethylene oxide) (PEO) in PEO/Fatty Acid Blends

In this work, isothermal and nonisothermal crystallization kinetics of poly(ethylene oxide) (PEO) and PEO in PEO/fatty acid (lauric and stearic acid) blends, that are used as thermal energy storage materials, was studied using differential scanning calorimetry (DSC) data. The Avrami equation was adopted to describe isothermal crystallization of PEO and nonisothermal crystallization was analyzed using both the modified Avrami approach and Ozawa method. Avrami exponent (n) for PEO crystallization was in the range 1.08–1.32 (10–90% relative crystallinity), despite of spherulites formation, while for PEO in PEO/fatty acid blends n was between 1.61 and 2.13. Hoffman and Lauritzen theory was applied to calculate the activation energy of nucleation (K_g) – the lowest value of K_g was observed for pure PEO, despite of heterogeneous nucleation of fatty acid crystals in PEO/fatty acid blends. For nonisothermal crystallization of PEO in PEO/lauric acid (1:1 w/w) and PEO/stearic acid (1:3 w/w) blends, secondary crystallization occurred and values of the Avrami exponent were 2.8 and 2.0, respectively. The crystallization activation energies of PEO were determined to be ?260 kJ/mol for pure PEO, ?538 kJ/mol for PEO/lauric acid blend, and ?387 kJ/mol for PEO/stearic acid blend for isothermal crystallization and ?135,6 kJ/mol, ?114,5 kJ/mol, and ?92,8 kJ/mol, respectively, for nonisothermal crystallization.     

Phase Behavior of Poly(Ethylene Oxide) Studied by Modulated‐Temperature DSC—Influence of the Molecular Weight

Abstract

Melting and crystallization behavior of poly(ethylene oxide) (PEO) with different molecular weight was investigated by modulated‐temperature differential scanning calorimetry (MT‐DSC)—step‐scan alternating DSC. It was found that by separating the reversing and nonreversing components of the (total) heat flow, PEO 10000, which exhibits the highest degree of crystallinity, shows the smallest nonreversing signal during crystallization. This effect can be attributed to the favorable structural features associated with spacial alignment. On the other hand, the crystallization process of PEO with molecular weight of 3400 is hindered by a relatively high content of end groups that may cause defects in the crystal lattice. For PEO 35000, low segmental mobility and chain entanglements lower the rate of crystallization. The area of the reversing component of PEO melting for different molecular weight fractions confirms that for PEO 10000, recrystallization is less intensive than for both the lower and higher molecular weight analogues.     

Maleic Acid–alt–Styrene Copolymer as Compatibilizer for Poly(Ethylene Oxide)-Poly(Styrene)Blends

Maleic acid-alt-styrene (MAaS) copolymer with number-average molecular weight [Mbar] _n = 2500 was used as a compatibilizer in blends of poly(ethylene oxide) (PEO) and poly(styrene) (PS). PEO with weight-average molecular weight [Mbar] _w = 10⁵ (PEO₁₀₀) and two PS samples with [Mbar] _w = 9 × 10⁴ and 4 × 10⁵, respectively (PS₉₀ and PS₄₀₀, respectively) were used. A depression of the melting temperature T _m of PEO in blends containing MAaS relative to pure PEO and PEO/PS blends was observed. The melting enthalpy ΔH _m for the PEO/PS blends containing MAaS was lower than those of pure PEO and PEO/PS blends without compatibilizer. The crystallization kinetics of PEO and the blends were studied by differential scanning calorimetry (DSC) at different crystallization temperatures T _c. Flory-Huggins interaction parameters χ₁₂ for the blends were estimated. Their values are in good agreement with those obtained for similar systems and suggest that the free energy of mixing ΔG _mix should be negative. Polarized optical microscopy shows differences in the macroscopic homogeneity of the blends containing compatibilizer that could be attributed to a compatibilization process.     

Nanostructured Thermosetting Blends of Phenolic Thermosets and Poly(ethylene oxide)‐block‐poly(propylene oxide)‐block‐poly(ethylene oxide) Triblock Copolymer

The amphiphilic triblock copolymer, poly(ethylene oxide)‐block‐poly(propylene oxide)‐block‐poly(ethylene oxide) (PEO‐b‐PPO‐b‐PEO) was incorporated into novolac resin to prepare thermosetting blends. The morphology of the thermosetting blends was investigated by means of atomic force microscopy (AFM) and small‐angle x‐ray scattering (SAXS) and the nanostructures were obtained. It was identified that the reaction‐induced phase separation occurred in the blends of phenolic thermosets with the model poly(propylene oxide) (PPO), whereas poly(ethylene oxide) (PEO) was miscible with novolac resin after and before the curing reaction. In terms of miscibility and phase behavior of the subchains of the triblock copolymer with novolac resin, it was demonstrated that the formation of nanostructures in the thermosets followed a mechanism of reaction‐induced microphase separation.     

Effect of melt compounding temperature on dielectric relaxation and ionic conduction in PEO–NaClO<Subscript>4</Subscript>–MMT nanocomposite electrolytes

Polymer nanocomposite electrolytes (PNCEs) of poly(ethylene oxide) and sodium perchlorate monohydrate complexes with montmorillonite (MMT) clay up to 20 wt.% MMT concentration of poly(ethylene oxide) (PEO) are synthesized by melt compounding technique at melting temperature of PEO (∼70 °C) and NaClO₄ monohydrate (∼140 °C). Complex dielectric function, electric modulus, alternating current (ac) electrical conductivity, and impedance properties of these PNCEs films are investigated in the frequency range 20 Hz to 1 MHz at ambient temperature. The direct current conductivity of these materials was determined by fitting the frequency-dependent ac conductivity spectra to the Jonscher power law. The PNCEs films synthesized at melting temperature of NaClO₄ monohydrate have conductivity values lower than that of synthesized at PEO melting temperature. The complex impedance plane plots of these PNCEs films have a semicircular arc in upper frequency region corresponding to the bulk material properties and are followed by a spike in the lower frequency range owing to the electrode polarization phenomena. Relaxation times of electrode polarization and ionic conduction relaxation processes are determined from the frequency values corresponding to peaks in loss tangent and electric modulus loss spectra, respectively. A correlation is observed between the ionic conductivity and dielectric relaxation processes in the investigated PNCEs materials of varying MMT clay concentration. The scaled ac conductivity spectra of these PNCEs materials also obey the ac universality law.     

Stimuli-responsive poly(ethylene oxide)-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) triblock copolymers and complexation with poly(acrylic acid) at low pH

The self-organization of the double hydrophilic triblock copolymer poly(ethylene oxide)-b-poly(2-vinylpyridine)-b-poly(ethylene oxide), PEO-b-P2VP-b-PEO, was investigated in dilute aqueous solution under several experimental conditions using turbidimetry, as well as static and dynamic light scattering. As a result of the temperature-sensitive properties of the end PEO blocks and the p H-responsive properties of the middle P2VP block, the formation of large star-like micellar nanostructures is observed at high p H, while at low p H, but in the presence of salt and at high temperature, flower-like micelles are formed. Moreover, the viscosimetric and dynamic light scattering studies at low p H revealed that micelle-like nanostructures are formed upon mixing the triblock copolymer with poly(acrylic acid), PAA, due to hydrogen bonding interpolymer complexation.     

Conductivity studies of poly(ethylene oxide)(PEO)/poly(vinyl alcohol) (PVA) blend gel polymer electrolytes for dye-sensitized solar cells

Poly(ethylene oxide)(PEO)–poly(vinyl alcohol) (PVA) blend-based gel polymer electrolytes (GPEs) have been prepared by blending equal weights of PEO and PVA in ethylene carbonate (EC), dimethyl sulfoxide (DMSO), tetrabutylammonium iodide (TBAI), and iodine crystals (I₂). The conductivity, diffusion coefficient, number density, and ion mobility of the electrolytes have been calculated from the impedance data obtained from electrochemical impedance spectroscopy (EIS) measurements. The GPE with the composition of 7.02 wt%, PVA, 7.02 wt% PEO, 30.11 wt% ethylene carbonate (EC), 30.11 wt% DMSO, 24.08 wt% TBAI and 1.66 wt% I₂ exhibits the highest conductivity of 5.5 mS cm^?1 at room temperature. Dye-sensitized solar cells (DSSCs) with configuration fluorine tin oxide (FTO)/titanium dioxide/N3-dye/GPE/platinum/FTO have been fabricated and tested under the white light of intensity 100 mW cm^?2. The DSSC containing the highest conducting GPE exhibits the highest power conversion efficiency, η of 5.36 %.     

Crystallization of Poly(Ethylene Oxide) in Thin Films

Crystallization of poly(ethylene oxide) (PEO) in thin films was studied using hot-stage polarized optical microscopy. Isothermal linear crystal growth rates were measured for various film thicknesses at various degrees of undercooling. At a given crystallization temperature, the linear crystal growth rate decreased exponentially with decreasing film thickness below a film thickness of 80 nm. Films showed similar spherulitic morphology down to a film thickness of 30 nm. Control experiments on hydrophilic and hydrophobic surfaces showed that surface chemistry affects stability of the polymer films and causes a competition between crystallization and dewetting.     

WAXS studies on crystalline behavior of polymethyl methacrylate-polyethylene oxide graft copolymers and their ionic complexes

A graphical multiple-peak resolution method for wide-angle x-ray scattering (WAXS) patterns is described and used to estimate the apparent crystallinities relative to the entire sample (Xca) in polymethyl methacrylate-polyethylene oxide graft copolymers (PMMA-g-PEO) and their ionic complexes with LiClO₄, KSCN and FeCl₂. The crystallinities (Xcg) and crystallite sizes (L ₁₂₀) in the PEO graft component, alone, were estimated at the same time. A concept of “reduced degree of crystallinity (Rc)” and “critical PEO content” is proposed and applied as a yardstick of the effects of PMMA backbone chains and salts on the crystalline behavior of the PEO graft chains. Xca and Xcg increase with both the content and molecular weight of the PEO graft chains. The critical PEO content, below which PEO crystallinity is not seen, is about 23.7%. PMMA backbone chains can reduce the crystallization of the PEO graft chains at any given PEO content. Xca and Xcg diminish after complexing with the salts and the order of reducing crystallinity is: LiClO4 > KSCN > FeCl₂; salts have two inverse effects, reduction and promotion, on the crystallization of the PEO graft chains. The salt effects depend on the salt concentrations and coordination of the cations. The crystallite sizes in the PEO graft chains are smaller than those in the PEO homopolymers but increase after complexing with salts. The PEO crystallite sizes are not noticeably affected by the content and molecular weight of the PEO graft chains but are noticeably affected by salt concentration.     

Infrared and conductivity studies on blends of PMMA/PEO based polymer electrolytes

Poly(methylmetacrylate)/poly(ethylene oxide) (PMMA/PEO) based polymer electrolytes were synthesized using the solution cast technique. Four systems of PMMA/PEO blends based polymer electrolytes films were investigated:

1. PMMA/PEO system,
2. PMMA/PEO + ethylene carbonate (EC) system,
3. PMMA/PEO + lithium hexafluorophosphate (LiPF₆) system and
4. PMMA/PEO + EC + LiPF₆ system.

The polymer electrolytes films were characterized by Impedance Spectroscopy and Fourier Transform Infrared Spectroscopy (FTIR). The FTIR spectra show the complexation occurring between the polymers, plasticizer and lithium salt. The FTIR results give further insight in the conductivity enhancement of PMMA/PEO blends based polymer electrolytes.     

Crowding-Induced Crystallization of Poly(Ethylene Terephthalate)

Samples of poly(ethylene terephthalate) (PET) extracted from three-component systems with different ratios among PET, phenol, and poly(ethylene glycol) (PEG) were prepared. As a crowding agent, PEG can greatly increase PET crystallinity. The crystal and thermal behaviors were characterized by wide-angle x-ray scattering and differential scanning calorimetry. There were two endothermic maxima of the crowding-induced crystallization process as molecular weight and concentration of PEG increased. The theory of crowding can interpret the phenomena well.