Water diffusion in polyethylene modified by ion irradiation

Water diffusion in polyethylene (PE) modified by irradiation with 40keV Ar⁺ ions to fluences of 1 × l0¹² to 1 × l0¹⁵cm⁻² was studied. The diffusion experiments were performed in a temperature interval from 25 to 100 °C and for diffusion times of up to 3 h. The water incorporated was detected by infra-red spectroscopy, microgravimetry and by measuring contact angles. Maximum water uptake observed for the ion fluence of 1 × 10¹³cm⁻² may be connected with an increase in free volume fraction and oxidative processes in the PE surface layer modified by ion irradiation. For higher ion fluences, the available free volume is reduced owing to carbonization and crosslinking of the polymer and, accordingly, the water content decreases. The water incorporated in PE is mostly in the form of isolated molecules. At elevated temperature rediffusion of water is observed.     

Dichroic polyethylene terephthalate films based upon compounds containing dyestuffs

An experimental study of the dichroism of uniaxial and biaxial orientation of polyethylene terephthalate films containing dichroic dyestuffs is described. It is found that hydrophobic dyestuffs orient more and cause greater dichroism than do hydrophilic dyes. Dyestuffs which can induce dichroism in cellulosic films are not effective with PET films. The more anisotropic the hydrophobic dyestuff molecule, the more effective it is in inducing dichroism. At low stretch ratios, the dichroism (D ₁₂–1)/(D ₁₂+2) (whereD ₁₂ isA ₁/A₂) increases linearly with birefringence, but at higher stretch ratios the rate of increase is slower. This may be attributed to crystallization and reduced orientations in the amorphous regions. Biaxial stretching generally lowersD ₁₂.     

Adsorption of anionic surfactant on porous and non-porous polyethylene terephthalate films

We study the adsorption of anionic surfactant, sodium dodecyl diphenyloxide disulfonate (SDDD) on three types of polyethylene terephthalate substrates from aqueous solutions of SDDD of different concentrations. Neutral electrolyte (KCl) was added to the solutions to vary the ionic strength. The three types of substrates were: (1) original polymer film, (2) etched non-porous film, which was obtained from pristine film by chemical etching and bears negative charge on the surface, (3) etched porous membranes, which were fabricated from pristine film by ion irradiation and subsequent chemical etching. The membranes have negative charge on the flat surface and on the inner pore walls. The comparison of original and etched nonporous films shows that the negative charge on the flat surface has weak effect on adsorption of the anionic surfactant. The comparison of etched non-porous and porous films shows that the SDDD adsorption on the inner walls of pores is much weaker than on flat surface—even in case the pore radius is significantly larger than the Debye length. This “exclusion” effect strongly depends on ionic strength of solution. For the porous films, the effect of the pore size and shape on the anionic surfactant adsorption is presented and discussed.     

Structure of ultrathin polyethylene layers in multilayer films

The crystalline structures of “microlayer” and “nanolayer” polyethylene have been examined in coextruded films comprised of alternating layers of high-density polyethylene and polystyrene. Transmission electron microscopy (TEM), small-angle x-ray scattering (SAXS), and wide-angle x-ray scattering (WAXS) reveal that microlayer polyethylene, where the layer thickness is on the order of several microns, crystallizes with the normal unoriented lamellar morphology. In nanolayer films, where the film thickness of tens of nanometers is on the size scale of molecular dimensions, lamellae are oriented with the long axes perpendicular to the extrusion direction in a row-nucleated morphology similar to structures described in the literature. The lamellae are partially twisted about the long axes. The preferred twist angles of ±40° orient the lamellar surfaces normal to the layer surface. The row-nucleated morphology imparts highly anisotropic mechanical properties to the nanolayer polyethylene.     

Surface grafting of polyethylene by mutual irradiation in methyl acrylate vapor. II. High-energy electrons irradiation

Vapor-phase mutual grafting of methyl acrylate (MA) onto polyethylene (PE) at high dose rates from an electron accelerator yields the same surface graft structure as does the grafting at low dose rates from ⁶⁰Co sources; i.e., a homopolymer layer (consisting of only MA component) is easily formed on the inner graft copolymer layer (consisting of both MA and PE components) as a result of the continuously increasing surface graft composition. To produce the surface layer, 4-MeV electron irradiation with a linear electron accelerator requires only less than 3 min of irradiation time at dose rates of more than 2 Mrad/min, whereas γ irradiation with a ⁶⁰Co source requires at least 1 hr at dose rates of less than 2 × 10³ rad/min. The rate of monomer consumption (or polymerization) in the surface homopolymer layer shows no dependence of irradiation time and a positive dependence of dose rate. It has been suggested that this kinetic feature at the high dose rates shows some contribution of vapor-phase homopolymerization and subsequent deposition (onto the grafting surface) followed by recombination with the grafted side chain radicals, although secondary graft copolymerization from the grafted chain radicals is still the principal process for the growth of the surface homopolymer layer.     

Strain softening of rolled polyethylene terephthalate films under transverse tension

The plastic flow of glassy polyethylene terephthalate films under tension perpendicular to the preliminary rolling axis was studied. An unexpectedly strong strain softening was detected, which consisted in a decrease in the yield stress under transverse tension. The upper yield point at a degree of rolling of Λ = 1.7 was lower by a factor of 1.8 than that of the unrolled material. Recovery of the polymer under room conditions led to a gradual restoration of the properties of the unrolled polymer.     

Electrically conducting plastic films from polyethylene terephthalate for optoelectronic applications

Iodine doping of polyethylene terephthalate (PET) has been made to develop intrinsically conducting plastic films. The doped material is investigated in terms of structure and morphology, electrical and optical characteristics. Considerable decrease in the value of the degree of crystallinity is observed on doping the samples. Further there are discernible shifts found in the energy gap and band edge towards lower energies on doping with iodine. The refractive index of the complex films is also found to increase.     

Engineering of superhydrophobic silica microparticles and thin coatings on polymeric films by ultrasound irradiation

Superhydrophobic coatings are one of the recent hot topics in industrial applications as well as academic studies. The mimicking lotus leaves' superhydrophobic properties have been successfully transferred to real-life applications. However, the current preparation methods used to obtain superhydrophobic coatings are still complex, commonly are not transparent and/or not durable.In the present study, a new relatively simple way to prepare superhydrophobic coatings on polymeric films is described. First, superhydrophobic silica microparticles (MPs) were synthesized by fluorination of SiO₂ MPs produced by a modified Stöber method. Briefly, tetraethyl orthosilicate was polymerized in an ethanol/water continuous phase under basic conditions, and the resultant SiO₂ MPs were dispersed in heptane as a continuous phase and reacted with 1H,1H,2H,2H-perfluorododecyltrichlorosilane (FTS) to yield FTS-SiO₂ MPs, which were dried and dispersed in decane. Superhydrophobic thin coatings were then produced by a ‘throwing stones’ sonication technique and deposited onto polycarbonate, polypropylene, polyethylene, and polyurethane films. The coatings are durable, may be transparent, and exhibit self-cleaning properties for the specific practical applications. The MPs and coated polymeric films were characterized by dynamic light scattering, high-resolution scanning electron microscopy, water contact and sliding angle measurements, and infrared and x-ray photoelectron spectroscopy. This ultrasound-assisted coating process may be upscaled and applied to many polymeric films, for instance polymethyl methacrylate, polystyrene, and polyvinyl chloride. Various applications are envisaged, including but not limited to self-cleaning windows, anti-sticking of snow to antennas and windows, solar panels, roof tiles, agricultural applications, corrosion resistance, and anti-biofouling.     

Surface characteristics of low-density polyethylene films modified by oxyfluorination-assisted graft polymerization

In this study, a unique two-step process, i.e., an oxyfluorination-assisted graft polymerization (OAGP), was used to modify the surface properties of low-density polyethylene (LDPE) films. Based on the results of the 1,1-diphenyl-2-picrylhydrazyl (DPPH) method, which was performed to estimate the amount of hydroperoxides generated by oxyfluorination, oxyfluorination conditions that maximize the amount of hydroperoxide groups were selected. Hydroperoxides were generated by oxyfluorination to provide active sites for the OAGP of the different monomers. Depending on the type of monomers used, two different graft polymerization behaviors were observed. Hydrophilic methacrylic acid (MA) monomers were graft polymerized onto the oxyfluorinated LDPE (OFPE) surface in a perpendicular direction, forming a spike-shaped morphology. On the other hand, hydrophobic styrene (ST) monomers were graft polymerized parallel to the OFPE surface, forming a valley-shaped morphology. By changing the type of vinyl monomers, two different surfaces could be prepared using the hydroperoxides generated by oxyfluorination. After OAGP with MA monomers, a hydrophilic surface following the Wenzel model was obtained, whereas after OAGP with ST monomers, a hydrophobic surface following the Cassie–Baxter model was obtained. Therefore, the OAGP process may be an efficient method for preparing two different surfaces by changing the monomer used.     

Excitation and emission spectra of polyethylene terephthalate and polyethylene 2,6‐naphthalate films

With excitation by the light of the wavelengths longer than 320 nm, fluorescence spectra of polyethylene terephthalate (PET) films had somewhat different shapes from those excited below 300 nm through the intrinsic absorption of PET molecules. Also, in the measurements taken with a polarizer in front of the receiving monochoromator but none before the sample, the intensity ratio of parallel (to the draw axis of the film) and perpendicular components of the emission spectra was different if excited above 320 nm or below 300 nm. Discussion was made about the first step of pumping photon energy at the wavelengths above 320 nm. Fluorescence spectra of polyethylene 2,6‐naphthalate films showed a mirror image of their absorption spectra, consisting of one broad band having the same polarization as their absorption spectra. Their fluorescence occurred from the lowest excited level, conforming to the Kasha law. Copyright © 1999 John Wiley & Sons, Ltd.     

Fabrication and characterization of orientation in skew stretched polyethylene terephthalate films

Skew stretched films were prepared by first unaxial stretching and subsequently skew stretching at 30 and 60 angles to various stretch ratios. The films were characterized by refractive index (birefringence), infrared absorption (dichroism) and wide-angle x-ray diffraction measurements. The data are represented in terms of ellipsoids and symmetry axes were determined. The results from the different methods are compared. Biaxial orientation factors are computed based on the experimentally determined axes.     

Effect of tensile speed on mechanical characteristics of preliminary rolled polyethylene terephthalate films

The effect of tensile speed on the mechanical properties of amorphous polyethylene terephthalate films is studied. The films are oriented by rolling on laboratory rollers at room temperature. In the samples with the rolling degree of two, the subsequent tension with the velocity of 5 mm/min does not afford a neck. As the tensile speed increases to 500 mm/min, a neck results from instability of the deformation process, which is caused by the polymer heating. Upon high-speed tension, the temperature of the rolled samples exceeds the glass-transition point of polyethylene terephthalate. Despite the polymer heating, the rolling completely suppresses the formation of pores. The rolling leads to the delocalization of flow over the region of polymer transfer to the neck. While in the nonrolled films the flow occurs in the zone with the length on the order of the film thickness, after the rolling, the size of the flow zone increases, and the region with the length on the order of the film width is deformed.     

Removal of anionic dyes with glycidyl methacrylate-grafted polyethylene terephthalate (PET) fibers modified with ethylenediamine

Research on Chemical Intermediates - In this work, the epoxy groups of poly (ethylene terephthalate) PET copolymers grafted with glycidyl methacrylate (GMA) were modified with ethylenediamine (EDA)...     

Polyphosphazene microspheres modified with transition metal hydroxystannate for enhancing the flame retardancy of polyethylene terephthalate

A novel PZS@CS hybrid structure was synthesized for enhancing the flame retardancy of polyethylene terephthalate (PET). The PZS@CS hybrids showed significant flame retardance. For example, the incorporation of 6 wt% PZS@CS obviously brought about an 8.8% increase of limiting oxygen index value (29.3%) and passed the vertical burning test UL‐94 V‐0 level, accompanied with the sharp reduction of heat and smoke release. The flame retardant mechanism of PZS@CS hybrids was fully studied by the Thermogravimetric Analysis (TGA), pyrolysis‐gas chromatography‐mass spectrometry, and Raman methods, and the results showed that the improvement of flame retardancy was mainly ascribed to the synergistic effect of PZS and CS phases in both the condensed and the gas phase. Rheological results showed that PZS@CS hybrids improved the melt complex viscosity of PET composites and the well compatibility of PET matrix and PZS@CS hybrids was also proved by the improvement of mechanical properties.     

Preparation of conductive,flexible and transparent films by in situ deposition of polypyrrole nanoparticles on polyethylene terephthalate

In this study polypyrrole (PPy) nanoparticles were deposited as a thin film on the modified surface of polyethyleneterephthalate (PET) by in situ chemical polymerization in the presence of sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (DBSNa) and mixture of them as the surfactant. The surface of PET was modified by KOH before deposition and was investigated for conductivity and adhesion of PPy nanoparticles to PET. Resulting conductive flexible films were characterized by UV–Vis spectroscopy, fieldemission scanning electron microscopy, contact angle measurements and four-point-probe technique for conductivity. Direct morphological observation (FESEM) and electrical measurements indicated that the morphology, conductivity and the nature of deposited PPy films depend on surfactant, surface modification of PET and monomer concentration. In optimized process condition, uniform conductive films of PPy were obtained with good adhesion to PET.     

Potentiostatic formation of semipenetrable polymeric acrylamideformaldehyde films and the electrochemical behavior of electrodes modified by such films

The potentiostatic formation of an acrylamideformaldehyde copolymer film on a platinum cathode is studied by the voltammetry and impedance methods. As the process is nonstationary in time, the film has a complex nonuniform structure, and the film’s density depends on potential and electrolysis duration. The electrochemical behavior of the electrode-polymeric film composition is examined. The polymer is electrochemically stable at 0.5 to -0.7 V (Ag/AgCl) and contains no electron-exchange or ion-exchange functional groups that could undergo redox conversions in this potential range. The synthesized film is semipenetrable and has ultrafiltration characteristics. The diffusion mobility of depolarizers in the film is lower than that in solution and is determined by the nature and properties of species moving in the electrical field and by the ratio between sizes of depolarizer ions and pores of the film.     

Oxygen‐barrier properties of polyethylene terephthalate modified with a small amount of aromatic comonomer

The oxygen‐barrier properties of amorphous copolyesters based on ethylene terephthalate with 10%, or less, of an acid comonomer were examined. Comonomer units were isophthalate, phthalate, 1,5‐naphthalate, 1,8‐naphthalate, 2,6‐naphthalate, 1,8‐anthracenate, 2,6‐anthracenate, and 2,7‐pyrenate. Even 2.5 mol % comonomer significantly affected the permeability. Linear comonomers decreased the permeability. In contrast, small amounts of a kinked comonomer increased the permeability. However, increasing the amount of kinked comonomer further (gradually) decreased permeability P below that of polyethylene terephthalate. Generally, comonomer affected solubility S less than diffusivity D; therefore, changes in P reflected primarily changes in D. The solubility and diffusivity depended on copolymer composition in accordance with static and dynamic free‐volume concepts of gas permeability in glassy polymers. The solubility correlated with the amount of free volume, as determined by the glass‐transition temperature. This study also explored the relationship of dynamic free volume, which determines D, to thermally accessible segmental motions of the polymer chain. The effect of comonomer on D correlated with the intensity of the gauche component of the subambient γ relaxation. Changes in the fraction of gauche‐glycol conformations resulting from copolymerization were confirmed by Fourier transform infrared spectroscopy. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1900–1910, 2001     

Interaction forces in thin liquid films stabilized by hydrophobically modified inulin polymeric surfactant. 2. Emulsion films

The interaction forces in emulsion films stabilized using hydrophobically modified inulin (INUTEC SP1) were investigated by measuring the disjoining pressure of a microscopic horizontal film between two macroscopic emulsion drops of isoparaffinic oil (Isopar M). A special measuring cell was used for this purpose whereby the disjoining pressure Pi was measured as a function of the equivalent film thickness hw. The latter was determined using an interferometric method. In this way Pi-hw curves were established at a constant INUTEC SP1 concentration of 2x10(-5) mol.dm-3 and at various NaCl concentrations. At a constant disjoining pressure of 36 Pa, a constant temperature of 22 degrees C, and a film radius of 100 microm, hw decreased with an increase in the NaCl concentration, Cel, and reached a constant value of 11 nm at Cel=5x10(-2) mol.dm-3. This reduction in film thickness is due to the compression of the electrical double layer, and at the above critical NaCl concentration any electrostatic repulsion is removed and only steric interaction remains. This critical electrolyte concentration represents the transition from electrostatic to steric interaction. At a NaCl concentration of 2x10(-4) mol.dm-3 the Pi-hw isotherms showed a gradual decrease in hw with an increase in capillary pressure, after which there was a jump in hw from approximately 30 to approximately 7.2 nm when Pi reached a high value of 2-5.5 kPa. This jump is due to the formation of a Newton black film (NBF), giving a layer thickness of the polyfructose loops of approximately 3.6 nm. The film thickness did not change further when the pressure reached 45 kPa, indicating the high stability of the film. Pi-hw isotherms were obtained at various NaCl concentrations, namely, 5x10(-2), 5x10(-1), 1.0, and 2.0 mol.dm-3. The initial thicknesses are within the range 9-11 nm, after which a transition zone starts, corresponding to a pressure of about 0.5 kPa. In this zone all films transform to an NBF with a jump, after which the thickness remains constant with a further increase in the disjoining pressure up to 45 kPa, with no film rupture. This indicates the very high stability of the NBF in the presence of high electrolyte concentrations. The high emulsion film stability (due to strong steric repulsions between the strongly hydrated loops of polyfructose) is correlated with the bulk emulsion stability.     

Interaction forces in thin liquid films stabilized by hydrophobically modified inulin polymeric surfactant. 1. Foam films

Using the interferometric method of Scheludko-Exerowa for investigation of foam films, we have obtained results using a hydrophobically modified inulin polymeric surfactant (INUTEC SP1). Measurements were carried out at constant INUTEC SP1 concentration of 2 x 10(-)(5) mol.dm(-)(3) and at various NaCl concentrations (in the range 1 x 10(-)(4) to 2 mol.dm(-)(3)). At constant capillary pressure of 50 Pa, the film thickness decreased gradually with an increase in NaCl concentration up to 10(-)(2) mol.dm(-)(3) NaCl above which the film thickness remains virtually constant at about 16 nm. This reduction in film thickness with an increase in NaCl concentration is due to the compression of the double layer and at the critical electrolyte concentration (C(el,cr) = 10(-)(2) mol.dm(-)(3)) the electrostatic component of the disjoining pressure is completely screened and the remaining pressure is due to the steric interaction between the adsorbed polymer layers. Disjoining pressure-thickness (Pi-h) isotherms were obtained at C(el) < C(el,cr) (10(-)(4) - 10(-)(3) mol.dm(-)(3)) and C(el) > C(el,cr) (0.5, 1, and 2 mol.dm(-)(3)). In the first case, the disjoining pressure isotherms could be fitted using the classical DLVO theory, Pi = Pi(el) + Pi(vw), and using the constant charge model. At C(el) > C(el,cr), the main repulsion is due to the steric interaction between the polyfructose loops that exist at the air-water interface, i.e., Pi = Pi(st) + Pi(vw). Under these conditions, there is a sharp transition from DLVO to non-DLVO forces. In the latter case, the interaction could be described using the de Gennes' scaling theory. This gave an adsorbed layer thickness of 6.5 nm which is in reasonable agreement with the values obtained at the solid-solution interface. The Pi-h isotherms showed that these foam films are not very stable and they tend to collapse above a critical capillary pressure (of about 1 x 10(3) Pa), and these results could be used to predict the foam stability.