Angle dependent laser nanopatterning of poly(ethylene terephthalate) surfaces

Interference effects can lead to the formation of ripple structures at laser-irradiated poly(ethylene terephthalate) surfaces. Poly(ethylene terephthalate) surface was irradiated with linearly polarized light of a pulsed 157 nm laser. In a certain range of irradiation parameters, the irradiation resulted in the formation of coherent ripples patterns. The dimension of the pattern depends on the angle of the laser beam incidence. The surface morphology of the nano-patterned poly(ethylene terephthalate) was analyzed by atomic force microscopy and focused ion beam-scanning electron microscopy. Oxygen concentration in the modified polymer surface was studied by angular resolved X-ray induced photo-electron spectroscopy. Gold nano-layers were consecutively sputtered onto the laser irradiated poly(ethylene terephthalate) surfaces. The morphology of the sputtered gold nano-layers was investigated with atomic force microscopy too. We found that the morphology of the gold nano-layers changes and depends on the surface pattern of the laser irradiated poly(ethylene terephthalate). Formation of gold “nano-hills” is observed at the ridges of the ripple structures. The amount of oxygen together with the morphology of prepared polymer pattern may be the dominant factors controlling the gold layer growth. The present results are compared with those obtained earlier on PET irradiated with krypton fluoride laser.     

Electron beam induced modification of poly(ethylene terephthalate) films

Electron beam processing of poly(ethylene terephthalate) (PET) films is found to promote significant changes in the melting heat, intrinsic viscosity and polymer film-liquid (water, isooctane and toluene) boundary surface tension. These properties are featured with several maximums depending on the absorbed dose and correlating with the modification of PET surface functionality. Studies using adsorption of acid-base indicators and IR-spectroscopy revealed that the increase of PET surface hydrophilicity is determined by the oxidation of methylene and methyne groups. Electron beam treatment of PET films on the surface of N-vinylpyrrolidone aqueous solution provided graft copolymerization with this comonomer at optimum process parameters (energy 700 keV, current 1 mA, absorbed dose 50 kGy).     

Grafting onto poly(ethylene terephthalate) driven by 172 nm UV light

The reactivity of the surface of poly(ethylene terephthalate) (PET) film under 172 nm UV irradiation (xenon excimer lamp) towards nitrogen-borne 1-octene, n-nonane and heptafluorodecene vapor was investigated. Materials receiving from 0 to 24 J/cm² of UV were examined by X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectroscopy (ToF/SIMS), water and mineral oil contact angle measurement and atomic force microscopy (AFM). A uniform nanoscale layer developed on PET surface attributed to the grafting reaction between photolytically-produced polymer radicals and vapor phase molecules.     

Crystallization Behavior of Modified Polyester with Varied Macromolecular Architecture

Several modified polyesters with varied macromolecular architecture, such as branched poly(ethylene terephthalate) (PET) based on glycerol (GL) from 0.004 to 0.05 mol ratio as a branching agent, blocked and branched poly(butylene terephthalate)‐polyether containing poly(tetramethylene oxide) (PTMO) as soft segment and GL as a branching unit, as well as segmented poly(ethylene terephthalate)‐polyether,were prepared. Their crystallization behavior was studied by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), and polarized optical microscopy (POM). It was found that a small extent of branching may enhance the crystallization of poly(ethylene terephthalate), while high degrees of branching (0.035–0.05) could block the development of crystallization. On the other hand, for even a small extent of incorporation of GL in the more flexible poly(butylene terephthalate)‐polyether chains, no enhanced crystallization was observed; blocking of crystallization from a branching defect may play the main role. The introduction of PTMO in poly(ethylene terephthalate) chains to a small degree facilitated the nucleation and speeded crystallization, but decreased the melting points of the polymers. A small number of nuclei and the greater induction time were found for branched PETs. The spherulities developed in branched PETs were larger and more perfect than those in PET due to less truncation of spherulites resulting from fewer nuclei, whereas the size of spherulities in poly(ethylene terephthalate)‐polyether became smaller with the increase of PTMO.     

Diffraction filters based on polyimide and poly(ethylene naphthalate) track membranes

The problem of optical filters for soft x rays and extreme ultraviolet that provide a high degree of blocking ultraviolet and visible background radiations is considered. The subject of discussion is the filter based on a track membrane, a polymer film with micrometer and submicrometer pores, rather than the standard thin-film system. It is proposed that the membranes be made of poly(ethylene naphthalate) or polyimide, the UV absorption edge of which lies near the boundary of the visible range. The properties of poly(ethylene naphthalate) and polyimide membranes are contrasted with those of conventional porous poly(ethylene terephthalate) films, which are obtained by ion track etching. The spectral characteristics of poly(ethylene naphthalate) and polyimide films, as well as the formation of “track” pores when the specimens are successively treated by fast ions and chemicals, are studied. The basic parameters of the resulting porous structures are examined, and treatment conditions under which desired optical properties of the membranes are achieved are found. Filters based on poly(ethylene naphthalate) and polyimide track membranes may be applied in x-ray astronomy as constituents of detectors incorporated into solar telescopes and in experiments with the laboratory plasma.     

Immobilization of poly(?-caprolactone)-poly(ethylene oxide)-poly(?-caprolactone) triblock copolymer on poly(lactide-co-glycolide) surface and dual biofunctional effects

Poly(?-caprolactone)-poly(ethylene oxide)-poly(?-caprolactone) (PCL-PEG-PCL) triblock copolymer was covalently immobilized onto poly(lactide-co-glycolide) (PLGA) surface with the precursor of photopolymerizable and biodegradable PCL-PEG-PCL diacrylates. Argon plasma technique was exploited to obtain hydrophilic PLGA surface (HPLGA). The surface properties were characterized by Water contact angle and X-ray photoelectron spectroscopy (XPS) techniques. PCL-PEG-PCL surface modified hydrophobic PLGA and hydrophilic PLGA results in different surface physicochemical properties. PCL-PEG-PCL modified hydrophobic PLGA surface (PLGA-PCL-PEG-PCL) demonstrates excellent inhibition of platelet adhesion and activation; while PCL-PEG-PCL modified hydrophilic PLGA surface (HPLGA-PCL-PEG-PCL) results in good cytocompatibility. The possible mechanism was discussed and the driven force was ascribed to the different assembly behavior of PCL-PEG-PCL on PLGA surface dependant on the hydrophilic/hydrophobic property of PLGA. This simple and effective surface engineering method is also suitable for the other biomaterials such as polyurethane (PU), silicon rubber and poly(ethylene terephthalate) (PET) to obtain the enhanced biocompatibility.     

Persistent internal polarizations in poly(ethylene terephthalate) films. III. Cold crystallization

A polarization process, which may be induced in commercial poly(ethylene terephthalate) films by annealing, has been found to exhibit a current peak under zero bias near 120[ddot]C. This process is identified as the “cold crystallization” phenomenon, and involves the simultaneous gauche-to-trans isomerization and paracrystalline ordering of the glycol linkages.     

Investigation of structural relaxation and surface modification of ultrathin films of poly(ethylene terephthalate)

We studied dynamic properties of ultrathin films of poly(ethylene terephthalate) spincoated on different substrates, by means of dielectric spectroscopy and surface patterning experiments. We did not observe any variations of structural dielectric relaxation dynamics for films spincoated on aluminium substrate having thicknesses down to 40 nm. On the same substrate, 13 nm thick films are instead characterized by a reduction of the chains mobility. Surprisingly the chains dynamics as probed by a surface nanopatterning experiment evidenced a strong dependence on the substrate interaction even for 50 nm thick films, where dielectric relaxation dynamics is unaffected. It can be deduced that different length scales characterise dielectric relaxation dynamics and the processes related to the surface patterning, even if both are related to the chain mobility. Further experiments are wished to better understand this intriguing scenario.     

A PMMA optical diffuser fabricated using an electrospray method

To coat microsized poly(methyl methacrylate) (PMMA) particles of uniform size and density on poly(ethylene terephthalate) (PET) films, we introduce an electrospraying technique that uses a target electrode applied with an ac electric field. Using the apparatus and various material properties, we could achieve good collection and a uniform size distribution of hemispherical droplets on the PET film. The optical properties, transmittance, and light diffusivity of the films electrosprayed with the PMMA were characterized and the sprayed particles appear to act as a good optical diffuser, like microlenses. PACS 47.65.-d; 42.70.Jk; 81.15.-z     

Surface properties of UV-irradiated poly(vinyl alcohol) films containing small amount of collagen

The surface properties of poly(vinyl alcohol) (PVA) films in the presence of 1%, 3% and 5% of collagen before and after UV-irradiation have been studied by atomic force microscopy (AFM) and by contact angle measurements. PVA films have been obtained by solvent evaporation from water solution of PVA and PVA containing small amount of collagen. After drying, the samples were irradiated with UV light wavelength λ = 254 nm in air. Surface properties before and after UV-irradiation were observed using AFM. Contact angles of two liquids: diiodomethane (D) and glycerol (G) on polymeric films were measured at constant temperature using goniometer.The results have shown that the contact angle and the surface free energy for PVA films were altered by UV-irradiation. These alterations indicate photooxidation and an increase of polarity of the surface. The comparison of surface properties of PVA films and PVA containing collagen points out that collagen is more sensitive to photooxidation than PVA and PVA/collagen blends. PVA films containing collagen easier undergo photooxidation process with formation of new polar groups than pure PVA films.     

Glass transition of poly(ethylene terephthalate)

It has been found that commercial poly(ethylene terephthalate) film exhibits current glow curves which have maxima at 73.5 ± 3.4°C and at 105.3 ± 3.4°C. These current glow curves were obtained by measuring the current flowing under zero bias as the temperature was raised 1°C/min. A typical curve, for untreated 1-mil du Pont Mylar A, is seen in Fig. 1. Although a paper on this study will shortly be submitted for publication, some conclusions of that paper may be stated here.     

Probing mechanical properties of thin film and ceramic materials in micro- and nano-scale using indentation techniques

In this study, we report on the mechanical properties, failure and fracture modes in two cases of engineering materials; that is transparent silicon oxide thin films onto poly(ethylene terephthalate) (PET) membranes and glass-ceramic materials. The first system was studied by the quazi-static indentation technique at the nano-scale and the second by the static indentation technique at the micro-scale. Nanocomposite laminates of silicon oxide thin films onto PET were found to sustain higher scratch induced stresses and were effective as protective coating material for PET membranes. Glass-ceramic materials with separated crystallites of different morphologies sustained a mixed crack propagation pattern in brittle fracture mode.     

伽马射线辐射原位强化增韧含三羟甲基丙烷三丙烯酸酯的PET/弹性体合金

在少量的交联剂三羟甲基丙烷三丙烯酸酯存在下,研究了高能伽马射线辐射对PET/弹性体（ST2000）合金的原位强化增韧效应.在PET合金熔融共混的高温下,TMPTA可与PET和ST2000的分子链发生反应,使PET和ST2000发生分子内和分子间的交联,增强界面相互作用,使得PET合金的冲击性能提高,但拉伸强度有所下降.PET合金经过高吸收剂量的伽马射线辐照后,可以原位增加体系内部弹性相和界面相的化学交联程度,进一步提升PET合金的综合力学性能.当吸收剂量为100 kGy时,样条在冲击测试条件下未发生断裂,同时拉伸强度几乎保持不变.     

Electroless plating of nickel–phosphorous on surface-modified poly(ethylene terephthalate) films

Chemical surface preparation for Ni–P electroless metallization of poly(ethylene terephthalate) (PET) films without using Chromium-based chemicals, was studied. The applicability of this method was verified by a subsequent metallization process. Thermal analysis was conducted to observe the main thermal transitions and stability of the polymer and metallized films. Contact angle analysis was performed to assess the surface hydrophilicity so as to optimize the substrate preparation process. X-ray diffraction, EDAX and SEM analysis were used to understand the composition and morphology of the polymeric substrate and Ni–P coat growing process. Adherence strength, contact sheet resistivity and optical diffuse reflection were measured on the metallized films. The time of chemical etching affects the polymer surface hydrophilicity, polymer/metal adherence strength, surface resistance and optical diffuse reflection, while Ni coating morphology is controlled by the pH of the electroless bath. High wettability of the polymer surface, adherence strength of 800 N cm⁻², high optical diffuse reflection and low surface resistivity of the Ni coating, were found for films etched for 60 min. Metallizations performed at pH 7.5 produce Ni–P coatings with 12.0 wt.% phosphorous content, which were amorphous and flexible. The contact sheet resistivity of the plated films is sensitive to roughness variations of the substrate. The method proposed in this work allows the production of metallized films appropriate for the fabrication of flexible circuits.     

Hydrophobic Modification of Poly(Ethylene Terephthalate) with Epoxy-Modified Polysiloxane by Reactive Extrusion

Hydrophobic poly(ethylene terephthalate) (PET) was prepared by reactive blending of PET with double epoxy groups modified polysiloxane (diepsi) or multiepoxy groups modified polysiloxane (multiepsi). The structure of the modified PET was characterized by ¹H NMR and intrinsic viscosity. The grafted ratio of diepsi and multiepsi was 1.3 and 0.03 wt%, respectively. With the introduction of diepsi and multiepsi to PET, the water contact angle of modified PET increased from 73° to a maximum of 106°, showing the good hydrophobicity of the modified PET. The samples of modified PET were washed with different solvents and their water contact angles did not significantly decrease, indicating good durability of the hydrophobicity. Moreover, the films of modified PET prepared by solution casting (phenol and 1, 1, 2, 2-tetrachloroethane mixed solution) showed excellent hydrophobicity with the contact angle 151°. Scanning electron microscopy images showed the surface of the modified PET films to be rougher than those of unmodified PET because the introduction of polysiloxane to PET resulted in phase separation during the solvent evaporation process.     

An electrosprayed coating process for fabricating hemispherical PMMA droplets for an optical diffuser

A modified electrospraying process is proposed for fabricating uniform microsized poly(methyl methacrylate) (PMMA) hemispherical droplets on poly(ethylene terephthalate) films for use as optical diffusers. In this process, an electrode controlled by an electric field is attached to a rotating collector, and various electric field conditions are applied to the droplets ejected from a positively charged nozzle. The distribution of small hemispherical droplets and the surface roughness resulting from this modified electrospraying process are more uniform than those achieved in the normal electrospraying process. The frequency of the field applied to the electrode is not critical to the production of stable PMMA droplets. The optical diffusivity of the PMMA film fabricated using this process is greater than that of normally fabricated film, demonstrating the feasibility of using this process to create newly designed optical diffusers.     

Highly flexible,transparent, conductive and antibacterial films made of spin-coated silver nanowires and a protective ZnO layer

We prepared highly flexible, transparent, conductive and antibacterial film by spin coating a silver nanowire suspension on a poly (ethylene terephthalate) (PET) substrate. The ZnO layer covered the conductive silver nanowire (AgNW) network to protect the metal nanowires from oxidization and enhance both wire-to-wire adhesion and wire-to-substrate adhesion. It is found that the number of AgNW coatings correlates with both the sheet resistance (R_s) and the transmittance of the AgNW/ZnO composite films. An excellent 92% optical transmittance in the visible range and a surface sheet resistance of only 9 Ω sq⁻¹ has been achieved, respectively. Even after bending 1000 times (5 mm bending radius), we found no significant change in the sheet resistance or optical transmittance. The real-time sheet resistance measured as a function of bending radius also remains stable even at the smallest measured bending radius (1 mm). The AgNW/ZnO composite films also show antibacterial effects which could be useful for the fabrication of wearable electronic devices.     

The preparation of clay nanosheets-poly(ethylene terephthalate) hybrid materials

The preparation of hybrid materials of poly(ethylene terephthalate) (PET) with montmorillonite (Mont) clay was investigated using anchor monomers, i.e. hydroxyethyl isonicotinamide (HENA) or hydroxypentyltrimethylammonium iodide (HPTA), which both have cationic substituents to adsorb onto clay surfaces and a hydroxyethyl moiety (–CH₂CH₂OH) to react with the polymer chain terminal of PET. The condensation of the mixtures of the intercalation compounds, bis (2-hydroxyethyl) terephthalate (BHET) and HENA/Mont or HPTA/Mont, led to a homogenous and transparent PET hybrid in which the Mont clay particles were scattered homogenously. The HPTA/Mont hybrid films copolymerized with BHET exhibited a dramatic improvement in such characteristics as tensile strength and optical transparency.     

A new approach to the immobilisation of poly(ethylene oxide) for the reduction of non-specific protein adsorption on conductive substrates

Biomedical and biotechnological devices often require surface modifications to improve their performance. In most cases, uniform coatings are desired which provide a specific property or lead to a specific biological response. In the present work, we have generated pinhole-free coatings providing amine functional groups achieved by electropolymerisation of tyramine on highly doped silicon substrates. Furthermore, amine groups were used for the subsequent grafting of poly(ethylene oxide) aldehyde via reductive amination. All surface modification steps were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The results indicate that the stability and the density of amine functional groups introduced at the surface via electropolymerisation compare favourably with alternative coatings frequently used in biomedical and biotechnological devices such as plasma polymer films. Furthermore, protein adsorption on amine and poly(ethylene oxide) coatings was studied by XPS and a colorimetric assay to test enzymatic activity. The grafting of poly(ethylene oxide) under cloud point conditions on electropolymerised tyramine layers resulted in surfaces with extremely low protein fouling character.     

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.