Preparation and Rheological Characteristics of Ethylene‐Vinyl Acetate Copolymer/Organoclay Nanocomposites

Ethylene‐vinyl acetate copolymer (EVA) with 40 wt.% vinyl acetate content (EVA40)/organoclay nanocomposites were prepared using a melt intercalation method with several different clay concentrations (2.5, 5.0, 7.5, and 10.0 wt.%). X‐ray diffraction confirmed the formation of exfoliated nanocomposite in all cases with disappearance of the characteristic peak corresponding to the d‐spacing of the pristine organoclay. Transmission electron microscopy studies also showed an exfoliated morphology of the nanocomposites. Morphology and thermal properties of the nanocomposites were further examined by means of scanning electron microscopy (SEM) and thermo gravimetric analysis (TGA), respectively. Rheological properties of the EVA40/organoclay nanocomposites were investigated using a rotational rheometer with parallel‐plate geometry in both steady shear and dynamic modes, demonstrating remarkable differences with the clay contents in comparison to that of pure EVA40 copolymer.     

Effect of Temperature and Comonomer Content on Thermal Behavior and Crystallization Property of the Propylene–Ethylene Random Copolymers

The effects of ethylene units content and crystallization temperature on the conformations, and the thermal and crystallization behavior were investigated by a combination of Fourier transform infrared (FTIR) spectroscopy, wide angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). The characterization of FTIR spectroscopy proves that the longer helical conformation sequences of the propylene–ethylene random (PER) samples decrease, whereas the shorter helical conformation sequences increase with the increase in ethylene units content. The increase of the shorter helical conformation sequences is favorable for the formation of the γ-phase in the crystals. A group of broad endothermic peaks can be seen clearly in the DSC curves of PER copolymers, which may be associated with the melting of mixtures of the α- and γ-forms in the crystals. The melting point, crystallization temperature, and crystallinity degree of the PER copolymers decrease with the increase in ethylene units contents. Three typical melting peaks of the PER copolymers crystallized isothermally between 80°C and 130°C were observed. The two higher melting peaks result from melting of the α- and γ-phase in the crystals, whereas the materials crystallized on quenching give the lowest peak. The WAXD results confirm that the PER copolymers crystallize from the melt, as mixtures of α and γ forms, in a wide temperature range. The critical number ζ_lim of the crystallizable units for the α-form increases with the increase in crystallization temperature for PER copolymers, which is favorable for the formation of the γ phases. The amount of γ-form increases with the increase in crystallization temperature at the expense of its α component, then reaches a maximum value at the crystallization temperature of 115°C, and finally decreases with further increase in the crystallization temperature.     

Ethylene and ammonia traces measurements from the patients’ breath with renal failure via LPAS method

The application of laser photoacoustic spectroscopy (LPAS) for fast and precise measurements of breath biomarkers has opened up new promises for monitoring and diagnostics in recent years, especially because breath test is a non-invasive method, safe, rapid and acceptable to patients. Our study involved assessment of breath ethylene and breath ammonia levels in patients with renal failure receiving haemodialysis (HD) treatment. Breath samples from healthy subjects and from patients with renal failure were collected using chemically inert aluminized bags and were subsequently analyzed using the LPAS technique. We have found out that the composition of exhaled breath in patients with renal failure contains not only ethylene, but also ammonia and gives valuable information for determining efficacy and endpoint of HD.     

Dielectric Relaxations and Structures of Nanoclay in Solution Cast Poly(Ethylene Oxide)– Montmorillonite Clay Nanocomposites

The relative complex dielectric function, electric modulus and alternating current electrical conductivity spectra and complex impedance plane plots of aqueous solution cast poly(ethylene oxide)–montmorillonite clay (PEO–MMT) nanocomposite films were investigated over the frequency range 20 Hz to 1 MHz at ambient temperature. The intercalated and exfoliated structures of nanoclay dispersed in PEO matrix were recognized by the significant change in real part of dielectric function with clay concentration in the range 0%–20 wt%. The relaxation times corresponding to PEO chain segmental motion and ionic conduction relaxation processes were used to explore the interactions compatibility between PEO molecules and the dispersed MMT clay nanoplatelets and their effect on PEO chain dynamics. Real part of conductivity spectra of these nanocomposites over five decades of frequency has nonlinear behavior, which is influenced by the MMT clay concentration. The complex impedance plane plots confirm the bulk properties of these nanocomposites over the experimental frequency range.     

Rheology and Dispersion Behavior of Ethylene‐Vinyl Acetate Copolymers/TiO2 Masterbatches Prepared by Melt‐Compounding

The rheology and dispersion behavior of ethylene‐vinyl acetate (EVA) copolymer/TiO₂ masterbatches prepared by melt‐compounding were investigated. The pure EVA exhibits obviously pseudoplastic behavior and the apparent viscosity decreases remarkably at experimental temperatures, especially in the range of 100–500 s^?1. The EVA/TiO₂ masterbatches exhibit similar shear rheology behavior with pure EVA and the apparent viscosities are obviously higher than that of pure EVA when the TiO₂ content is above 10 wt.%. Field‐emission scanning electron microscopy (FE‐SEM) and energy dispersive x‐ray spectroscopy (EDX) show that relatively low TiO₂ loading and moderate shear rate are helpful for the improvement of dispersion behavior of TiO₂ nanoparticles; moreover, the dispersion behavior of TiO₂ greatly influences the melt viscosity. The extensional rheology of pure EVA decreases with increasing extension rate, especially at low melt temperatures. EVA/TiO₂ masterbatches have similar extensional rheology behavior as pure EVA and the TiO₂ loading has almost no influence on the extensional viscosity of materbatches.     

A Light and X‐Ray Scattering Study of Aqueous Micellar Solutions of a Diblock Copolymer of Propylene Oxide and Ethylene Oxide with Solubilized Alkylcyanobiphenyl Liquid Crystals

Abstract

The temperature and concentration dependences of the physicochemical properties of aqueous solutions of the diblock copolymer P₄₃E₃₁₂ (P = oxypropylene, E = oxyethylene) with solubilized liquid crystal (LC) have been studied using static and dynamic light scattering (SLS and DLS), small‐angle x‐ray scattering (SAXS), and ultraviolet (UV) spectroscopy. Relaxation time distributions from DLS obtained from inverse Laplace transformation of intensity correlation functions are multimodal, where the two fastest modes are attributed to diblock copolymer unimers and micelles, respectively. The remaining modes at longer decay times reflect the presence of free LC with hydrodynamic radii (R _h) of hundreds of nm. The R _h of both unimers and micelles were independent of temperature (T), while the hydrodynamic virial coefficient k _D and the second virial coefficient, A ₂, decreased with increasing T. The UV spectroscopy measurements showed that there is a reduction in the amount of solubilized LC per gram of copolymer (c _s) as the copolymer concentration (c _p) is increased. The SAXS results agree well with a model of a homogeneous system of polydisperse interacting hard spheres. In solution, both the effective micellar radius of interaction (R _eff) and the hard‐sphere micellar radius (R¯_s) increase in the presence of LC due to solubilization of the latter in the hydrophobic micellar core. Both SAXS and SLS results show that intermicellar interactions become important at c _p > 1% (w/w) at high temperatures [T > the critical micelle temperature (cmt)].     

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.     

Distorted Wave Effects of the 1b3g Orbital in Ethylene

We study the unexpected distorted wave effects of the 1b3g orbital in ethylene using a high resolution binary (e,2e) electron momentum spectrometer,at an impact energy of 800eV plus the binding energy (8-22eV) with symmetric non-coplanar kinematics.The experimental monentum profile of the 1b3g orbital is obtained and compared with the data previously measured at an impact energy of 1200 eV plus the binding energy.Also,the experimental momentum profiles of the 1b3g orbital are compared with the theoretical momentum distributions calculated by using Hartree-Fock and density functional theory methods.The experimental momentum profiles of the 1b3g orbital of ethylene at different impact energies show that the cross section of the orbital below the momentum p-1 a.u.is higher for lower impact energies.     

Effects of Poly(Propylene Oxide)–Poly(Ethylene Oxide)–Poly(Propylene Oxide) Triblock Copolymer on the Gelation of Poly(Ethylene Oxide)–Poly(Propylene Oxide)–Poly(Ethylene Oxide) Aqueous Solutions

Poly(ethylene oxide)-poly(propylene oxide)–poly(ethylene oxide) ((EO)_n–(PO)_m–(EO)_n) block copolymers, commercially available as Pluronics (BASF Corp.) and Poloxamers (ICI Corp.), have been widely applied in medicine, biochemistry, and other fields because of their ability to form reversible micelles and physical gels in aqueous solution. Generally, for PEO–PPO–PEO block copolymers with higher ethylene oxide concentration, the micellization and gelation in aqueous solution are easier. However, if we introduce the reverse block copolymer PPO–PEO–PPO into PEO–PPO–PEO aqueous solutions, the micellization and gelation of the system will be more complex. In this work, the reverse block copolymer PO₁₄–EO₂₄–PO₁₄ (17R4) was added to the Pluronics EO₂₀–PO₇₀–EO₂₀ (P123), EO₁₀₀–PO₆₅–EO₁₀₀ (F127), and EO₁₃₃–PO₅₀–EO₁₃₃ (F108) aqueous solutions with different molar ratios. The rheological properties of different mixtures were measured to study the additive effect on the gelation behavior. The sol–gel transition temperature of the P123, F127, and F108 solutions shifted to a higher temperature when 17R4 was added to the solutions. In addition, the existence of 17R4 greatly affected the stability of gels. These results help to better understand the gelation of Pluronic aqueous solutions.     

Infrared Spectra of Poly(Ethylene Terephthalate) γ-Irradiated in Organic Solvents

The infrared spectra of poly(ethylene terephthalate) γ-irradiated in presence of organic solvents were recorded over the spectral region 200–300 cm^?1. The analysis of these spectra showed that the combined effect of solvent and γ-irradiation results in appearance of two strong bands at 1550 and 1630 cm^?1, increase in the intensities of the gauche bands at 1450 and 1370 cm^?1 and decrease in the intensity of the trans-band at 1340 cm^?1. The aromatic ring C=C stretching band at 1410 cm^?1 was also affected. The profound spectral changes were observed only in samples irradiated in presence of solvents and were not observed in samples treated with solvents or only irradiated in atmosphere of air, these spectral changes were attributed to the changes in the intermolecular of intramolecular forces as a result of penetration of solvent molecules in the polymer and the ionizing effect of γ-iffadiation. It was found that the extent of the intensity variations depends on the nature of the solvent.     

Dual-beam laser heterodyne spectrometer: Ethylene absorption spectrum in the 10 μm range

A laser heterodyne spectrometer for the 10 m region has been built. A 5 MHz apparatus function is obtained. The improvement of this spectrometer using a dual-beam technique is described. The folding effects in heterodyne spectroscopy are discussed. The recorded lineshapes are explained. An ethylene spectrum is shown as an example.     

Polystyrene‐b‐Poly(Ethylene‐r‐butylene)‐b‐Polystyrene Triblock Copolymer/Organoclay Nanocomposites and Their Phase Characteristics

Abstract

Intercalated polymer/clay nanocomposites were prepared using a polystyrene‐b‐poly(ethylene‐r‐butylene)‐b‐polystyrene (SEBS) cylindrical triblock copolymer. Dynamic rheological measurements, x‐ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetry analysis (TGA) were conducted to investigate the internal structure and physical and phase characteristics of the nanocomposites. The XRD data confirmed that the interlayer distance between the anisotropic silicates increased due to the intercalation of SEBS into the clay interlayers. As the clay loading increased, the onset points of the order–disorder transition (ODT) and order–order transition (OOT) were found to decrease, whereas the thermal decomposition temperatures, monitored by TGA, increased with the clay loading.     

Ethylene adsorption on Co/Pt(110)(1 × 2) surfaces

Ethylene adsorption has been followed by TDS on Pt(110)(1 × 2) surfaces covered with various amounts of cobalt atoms, including the multilayer range. A peculiar behaviour is found below 2.10 × 10¹⁵ cobalt atoms/cm²: partial desorption of ethylene low temperature replaces decomposition. The behaviour of bulk polycristalline cobalt is found above this coverage.     

Specific Solvation of a 4-DASPI Dye in a Water–Ethylene Glycol Binary Solvent

Optics and Spectroscopy - The solvatochromic shifts of the maxima of the absorption spectra of a 4-DASPI dye (4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide) in a water–ethylene glycol...     

Variable Angle ATR–FTIR Study of the Surface Aminolysis of Poly(Ethylene Terephthalate) Films

Hydrophobic surfaces of poly(ethylene terephtalate) films were modified by using a mild wet chemical procedure with triethylenetetramine as a reagent. The chemical composition was determined by Fourier transform infrared (FTIR) spectroscopy. With the aim of obtaining the depth profile of the newly created species the variable angle attenuated total reflectance (ATR)–FTIR spectroscopy was used. The most important functionalities resulting from the aminolysis that we chose to monitor were amide groups. By varying the incidence angle of the infrared radiation, chemical changes were investigated from layers of different thicknesses. It was observed that the absorption bands attributed to amide moieties became weaker with increasing analyzed depth, with a pronounced heterogeneity near the surface. By assuming an exponential decay for the depth profile spectrally obtained, the surface concentration of amide groups and the decay constant were determined for the reaction times used.     

Crosslinking-Dependent Relaxation Dynamics in Ethylene–Propylene–Diene (EPDM) Terpolymer above the Glass Transition Temperature

Dynamic mechanical experiments performed on ethylene–propylene–diene (EPDM) terpolymer, cross linked to different extents, evidenced three relaxation processes. Besides the glass transition (T_g) and the melting of the ethylene crystals formed in the ethylene-based EPDM, a new transition appeared at a temperature higher than the glass transition temperature (so-called tan δ_gh) and decreased dramatically in amplitude with increase in the degree of cure. The new transition (tan δ_gh) was also above the melting point. The viscoelastic properties of the rubber with various crosslinking degrees are described. Based on the behavior of tan δ_gh and the curing properties of EPDM, the tan δ_gh peak is primarily attributed to the motion of non-elastic network chains loosely attached to the three-dimensional network, including free chains.     

Morphology of Poly(Ethylene Oxide)- b-Poly(ϵ-Caprolactone) Spherulites Formed Under Compressed CO2

Melt crystallization of PEO-b-PCL thin films was conducted under compressed CO₂ and the morphology of the spherulites obtained at various pressures was investigated by polarizing optical microscopy (POM) and atomic force microscopy (AFM). At 3 MPa CO₂ classical ring-banded spherulites with periodical twisting lamellae formed. However, in the spherulites with concentric ring-banded structures formed at 5 MPa CO₂, the rings were formed due to periodical variations in thickness along the radial direction.     

Rheology Behavior of Hydrophobically Modified Poly(acrylic acid) with Twin-Tailed Pendant in Water—Ethylene Glycol Mixture

A hydrophobically modified poly(acrylic acid) (HMPA) with twin-tailed hydrophobic pendant side groups was prepared by precipitation polymerization. The rheology behavior of HMPA was examined in mixtures of water and ethylene glycol (EG) of different proportions. It was shown that the solvent had a direct impact on both the steady and dynamic rheology behaviors of the HMPA solutions. The change of hydrophobic interactions in the EG-rich mixtures may be attributed to the observed decrease in polymer coil dimension together with a lower tendency of the hydrophobes to form junctions. As the temperature decreased, the viscosities and numbers of active junctions of HMPA in water–EG mixtures increased.     

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.     

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.