Influence of argon plasma on the deposition of Al2O3 film onto the PET surfaces by atomic layer deposition

In this paper, polyethyleneterephthalate (PET) films with and without plasma pretreatment were modified by atomic layer deposition (ALD) and plasma-assisted atomic layer deposition (PA-ALD). It demonstrates that the Al₂O₃ films are successfully deposited onto the surface of PET films. The cracks formed on the deposited Al₂O₃ films in the ALD, plasma pretreated ALD, and PA-ALD were attributed to the energetic ion bombardment in plasmas. The surface wettability in terms of water contact angle shows that the deposited Al₂O₃ layer can enhance the wetting property of modified PET surface. Further characterizations of the Al₂O₃ films suggest that the elevated density of hydroxyl -OH group improve the initial growth of ALD deposition. Chemical composition of the Al₂O₃-coated PET film was characterized by X-ray photoelectron spectroscopy, which shows that the content of C 1s reduces with the growing of O 1s in the Al₂O₃-coated PET films, and the introduction of plasma in the ALD process helps the normal growth of Al₂O₃ on PET in PA-ALD.     

Hydrophilic CaCO3 nanoparticles designed for poly (ethylene terephthalate)

In this work, a new kind of the hydrophilic CaCO₃ nanoparticles modified by polyethylene glycol phosphate (PGP) was designed for the in-situ preparation of poly (ethylene terephthalate) (PET). It was confirmed that PGP induced the growth of calcite and coated the surface of calcite by the covalent bond. PGP not only adjusts the morphology and the size of CaCO₃ nanoparticles, but also solve the main problems in the in-situ preparation of CaCO₃/PET: (a) the reaction of CaCO₃ with TPA; (b) the agglomeration of CaCO₃ nanoparticles. Compared to the nanocomposite filled with the pure CaCO₃, the resulting nanocomposite filled with the modified CaCO₃ exhibits a better dispersion of the nanoparticles, a higher polymerization degree and a better thermal stability. The results related to the covalent bond formed by PGP on the surface of CaCO₃ and PET during the polymerization of the nanocomposite.     

Study and optimization of a flexible electrochromic device based on polyaniline

The synthesis of polyaniline (PANI) thin films was made onto commercially available  cm polyethylene terephthalate (PET)/indium tin oxide (ITO) substrates. By depositing a gold frame previously to the electrochemical PANI synthesis, homogeneous electrochromic PANI layers were obtained. Complete flexible cells could then be built by using a transparent gel electrolyte and a simple PET/ITO counter-electrode. Branched poly(ethyleneimine) (BPEI)-H₃PO₄ and polymethylemethacrylate (PMMA)-PC-LiClO₄ were both tested as electrolytes, but only the latter led to a non-degrading system when the device undergoes several switching potential steps. This flexible, middle-scale and inexpensive device enabled to get a 18% transmission contrast at 780 nm within 3 min.     

Solubility of CO2 in solid-state PET measured by pressure-decay method

The solubility of CO₂ in solid-state PET was measured using a pressure-decay method. In order to calculate the solubility of CO₂ in the amorphous region of PET, the crystallinity of solid state PET dissolved in CO₂ at different pressures and temperatures was measured by differential scanning calorimetry (DSC). The solubility increases with increasing pressure and it follows a linear relationship and obeys Henry’s law when the pressure is below 8 MPa. The effect of temperature on solubility is weak and the solubilities at different temperatures are almost the same under low pressures. At higher pressure, the solubility decreases with an increase in temperature. The solubility of CO₂ in the amorphous region of PET at 373.15 K, 398.15 K and 423.15 K was correlated with the Sanchez-Lacombe equation of state with a maximal correlation error of 6.69%. __________ Translated from Journal of East China University of Technology (Natural Science Edition), 2007, 33(4): 445–449 [译自: 华东理工大学学报(自然科学版)]     

Effects of CO2 treatments on the dual glassy relaxations and dual melting peaks in poly(ethylene terephthalate)

In this study, poly(ethylene terephthalate) (PET), an important packaging material for carbonated beverages, was investigated on its glassy relaxations and melt crystallizations in CO₂ in a high-pressure differential scanning calorimeter (PDSC) and a high-pressure thermostat chamber as a function of CO₂ pressure, time, CO₂ depressurization rate, and PET crystallinity. DSC measurements found a low glass transition temperature (T_gL) at near 50 °C in the wholly amorphous PET and a high glass transition temperature (T_gH) at near 70 °C in the PET sample with a fairly high crystallinity (X_c 50%). Both T_gL and T_gH decreased with increasing time in CO₂, attributed to plasticization by CO₂. PET sample with a moderate crystallinity (X_c 42%), however, exhibited both T_gL and T_gH corresponding to the relaxations of the dual amorphous phases as confirmed by dynamic mechanical analysis, with the T_gL assigned to the free amorphous phase and the T_gH to the constrained amorphous phase. The T_gL is much farther apart from T_gH than those obtained in N₂. The T_gL and T_gH in PET with a moderate crystallinity unexpectedly appeared to be insignificantly varied with time in CO₂; however, the magnitude of the T_gL signal increased but the T_gH signal decreased with increasing time in CO₂, attributed to disentanglement of polymer chains by CO₂. Dual melting peaks in PET were found after nonisothermal crystallization from the melt in CO₂. Temperature-modulated DSC (TMDSC) analysis indicated that melting-recrystallization model and double lamellar thickness model were both responsible for the appearance of the dual melting peaks.     

Investigation of the miscibility of polycarbonate–poly(ethyleneterephthalate) blends: Solid-state 1H-NMR T1 relaxation time measurements,transmission electron microscopy,and structure–properties relationship

Solid-State ¹H-NMR measurements of T₁ relaxation times performed on polycarbonate-poly(ethyleneterephthalate) (PC–PET) blends point out the presence of two separate domains with apparent dimensions of about 80 nm. The variation of PET domain relaxation time with the increase of PC content is explained in terms of an interface in which parts of the PC molecules are finely dispersed into the PET matrix. Relaxation parameters and compositions match very well an equation that quantitatively describes a three-phase model formed by two domains separated by an interface of mixed components. Micrographs obtained by transmission electron microscopy (TEM) clearly reveal the presence of two separate domains with a phase inversion at 40/60 wt% composition. PET domains, although larger than expected from NMR analysis, are characterized by a dispersion of small PC particles that are considered responsible for the observed diffusion of magnetization from PET to PC domains. The partial miscibility seems to be physical in nature rather than due to transesterification processes between the components, as stem from ¹H-NMR spectra in solution of PET and PC–PET blends. T₁ relaxation times measured in the same way on totally immiscible PC–PA-6 blends, support, by contrast, the NMR interpretation of PC–PET results. The mechanical properties of PC–PET blends exhibit ductile behavior throughout the entire range of composition. This indicates that PC and PET are mechanically compatible. This is also in agreement with the isothermal crystallization data for PET at various compositions of PC–PET. These results are in agreement with the existence of a partial miscibility between PET and PC. © 1994 John Wiley & Sons, Inc.     

Nonisothermal crystallization of poly(ethylene terephthalate) and its blends in the injection-molding process

We investigated the nonisothermal crystallization during the cooling process of injection molding of poly(ethylene terephthalate) (PET), PET/talc, and PET/Surlyn blends. We applied the isothermal crystallization parameters obtained by the Hoffman–Lauritzen theory to the kinetics of nonisothermal crystallization and then calculated the relative crystallinity χ/χ_c as a function of the mold temperature. χ/χ_c were nicely interpreted by calculation without effect of the pressure history on crystallization in PET and PET/talc (1 wt %) blends. In contrast, in the PET/Surlyn (3 wt %) blend, crystallization occurred at a lower mold temperature than predicted by our calculation. The transmission electron micrograph near the surface of the injection-molded PET/Surlyn blend showed deformation and stretching of dispersed Surlyn particles, suggesting that orientation of the PET matrix proceeds with the flow in processing. The orientation of the PET matrix resulted in acceleration of the crystallization in the injection molding. © 1995 John Wiley & Sons, Inc.     

Poly(ethylene terephthalate) nanofibers prepared by CO2 laser supersonic drawing

Poly(ethylene terephthalate) (PET) nanofibers were prepared by irradiating a PET fiber with radiation from a carbon dioxide (CO₂) laser while drawing it at supersonic velocities. A supersonic jet was generated by blowing air into a vacuum chamber through the fiber injection orifice. The flow velocity from the orifice was estimated by computer simulation; the fastest flow velocity was calculated to be 401 m s⁻¹ at a chamber pressure of 6 kPa. A nanofiber obtained using a laser power of 8 W and a chamber pressure of 6 kPa had an average diameter of 193 nm and a draw ratio of about 900,000. This technique is a novel method for producing nanofibers.     

Structure development and isothermal crystallization behaviour of compatibilized PET/expandable fluorine mica hybrid nanocomposite

Summary The compatibilized PET/expandable fluorine mica (ME) hybrid nanocomposite (CN) prepared by in situ polymerization technique showed a partially exfoliated structure of ME in PET matrix by XRD analysis, owing to its broad crystalline peak accompanied by an increase of d-spacing as compared to PET/ME uncompatibilized composite (UC). The analysis by TEM revealed a better dispersion of ME in PET for CN as compared to aggregates of ME in case of UC. Further, the isothermal crystallization behaviour studied using DSC for the same at different crystallization temperature (T _c,) revealed a significant decrease of crystallization half time and remarkable increase of crystallization rates (almost 2 times than pure PET) for CN in contrast to UC. The Avrami exponent n lowered to 2.3 for CN as compared to 3.1-3.4 for pure PET at various T _c. The activation energy (E _a) determined from Arrhenius equation reduced dramatically for CN. These various observations could be explained based on the nucleation efficiency by ME accompanied by different crystallization/growth process occurring in case of hybrid nanocomposite.     

Oxygen solubility and specific volume of rigid amorphous fraction in semicrystalline poly(ethylene terephthalate)

The existence of rigid amorphous fraction (RAF) in semicrystalline poly(ethylene terephthalate) (PET) is associated with the lamellar stack crystalline morphology of this polymer, the regions where several crystalline lamellas are separated by very thin (20-40 Å) amorphous layers. In contrast, regular or mobile amorphous fraction is associated with much thicker interstack regions. The oxygen transport properties of PET isothermally crystallized from the melt (melt-crystallization) or quenched to the glassy state and then isothermally crystallized by heating above T_g (cold-crystallization) were examined at 25 °C. Explanation of unexpectedly high solubility of crystalline PET was attributed to the formation of RAF, which in comparison with mobile amorphous phase is constrained and vitrifies at much higher than T_g temperature thus developing an additional excess-hole free volume upon cooling. Measurements of crystallinity and jump in the heat capacity at T_g were used to determine the amount of mobile and rigid amorphous fractions. Overall oxygen solubility was associated with the solubility of mobile and rigid amorphous fractions. The oxygen solubility of the RAF was determined and related to the specific volume of this fraction. The specific volume of the RAF showed a direct correlation with the crystallization temperature. It was shown that upon crystallization from either melt or glassy state, the constrained between crystalline lamellas PET chains consisting of the RAF, vitrify at the crystallization temperature and resemble the glassy behavior despite high temperature. When cooled to room temperature, the RAF preserves a memory about the melt state of polymer, which is uniquely defined by the crystallization temperature.     

Development of 18F-Labeled Radiotracers for PET Imaging of the Adenosine A2A Receptor: Synthesis,Radiolabeling and Preliminary Biological Evaluation

The adenosine A_2A receptor (A_2AR) represents a potential therapeutic target for neurodegenerative diseases. Aiming at the development of a positron emission tomography (PET) radiotracer to monitor changes of receptor density and/or occupancy during the A_2AR-tailored therapy, we designed a library of fluorinated analogs based on a recently published lead compound (PPY). Among those, the highly affine 4-fluorobenzyl derivate (PPY1; K_i(hA_2AR) = 5.3 nM) and the 2-fluorobenzyl derivate (PPY2; K_i(hA_2AR) = 2.1 nM) were chosen for ¹⁸F-labeling via an alcohol-enhanced copper-mediated procedure starting from the corresponding boronic acid pinacol ester precursors. Investigations of the metabolic stability of [¹⁸F]PPY1 and [18F]PPY2 in CD-1 mice by radio-HPLC analysis revealed parent fractions of more than 76% of total activity in the brain. Specific binding of [¹⁸F]PPY2 on mice brain slices was demonstrated by in vitro autoradiography. In vivo PET/magnetic resonance imaging (MRI) studies in CD-1 mice revealed a reasonable high initial brain uptake for both radiotracers, followed by a fast clearance.     

Thermal,mechanical, and barrier properties of polyethylene terephthalate‐platelet nanocomposites prepared by in situ polymerization

This study used in situ polymerization to prepare polyethylene terephthalate (PET) nanocomposites incorporating Ethoquad‐modified montmorillonite (eMMT), unmodified hectorite (HCT), or phenyl hectorite (phHCT) particles to study the impact of platelet surface chemistry and loading on thermal, mechanical, and gas barrier properties. eMMT platelets reduced the PET crystallization rate without altering the ultimate degree of crystallinity. In contrast, HCT and phHCT platelets accelerated the polymer's crystallization rate and increased its crystallinity. DMA results for thermally‐quenched samples showed that as T increased past glass transition temperature (T_g), HCT and phHCT nanocomposites (and control PET) manifested precipitous drops in G′ followed by increasing G′ due to cold crystallization; in contrast, eMMT nanocomposites had much higher G′ values around T_g. This provides direct evidence of eMMT reinforcement in thermally‐quenched eMMT nanocomposites. These results suggest that eMMT has a strong, favorable interaction with PET, possibly through Ethoquad‐PET entanglement. HCT and phHCT have a fundamentally different interaction with PET that increases crystallization rate and T_g by 11 to 17°C. Water barrier improvement in eMMT nanocomposites agrees with previously published oxygen barrier results and can be rationalized in terms of a tortuous path gas barrier model. POLYM. ENG. SCI., 52:1888–1902, 2012. © 2012 Society of Plastics Engineers     

Drawing in high pressure CO2—a new route to high performance fibers in memory of late Roger Porter

In this paper, we introduce a new draw technique for polymer orientation and apply it to different polymer fibers: poly(ethylene terephthalate) or PET, nylon 6,6, and ultra‐high molecular polyethylene (UHMWPE). In this technique, a polymer is drawn uniaxially in supercritical CO₂ using a custom high‐pressure apparatus. This technique can be used in replacement of a traditional drawing process or as a post‐treatment process. With PET, the technique is not effective at temperatures at or below 130°. In contrast, the process is highly effective for nylon 6,6 where CO₂ drawn fibers show significantly higher crystallinity and orientation along with improved mechanical properties. While the fibers are plasticized, the drawability of the fibers is only slightly dependent on temperature. High pressure CO₂ drawing of ultrahigh molecular weight polyethylene (UHMWPE) fibers is equally effective. Commercial high performance fibers can be drawn up to a ratio of 1.9 in asecond stage, resulting in large increases in tensile modulus and small improvements in tensile strength.     

Non-Invasive Assessment of Locally Overexpressed Human Adenosine 2A Receptors in the Heart of Transgenic Mice

A_2A adenosine receptors (A_2A-AR) have a cardio-protective function upon ischemia and reperfusion, but on the other hand, their stimulation could lead to arrhythmias. Our aim was to investigate the potential use of the PET radiotracer [¹⁸F]FLUDA to non-invasively determine the A_2A-AR availability for diagnosis of the A_2AR status. Therefore, we compared mice with cardiomyocyte-specific overexpression of the human A_2A-AR (A_2A-AR TG) with the respective wild type (WT). We determined: (1) the functional impact of the selective A_2AR ligand FLUDA on the contractile function of atrial mouse samples, (2) the binding parameters (B_{max and} K_D) of [¹⁸F]FLUDA on mouse and human atrial tissue samples by autoradiographic studies, and (3) investigated the in vivo uptake of the radiotracer by dynamic PET imaging in A_2A-AR TG and WT. After A_2A-AR stimulation by the A_2A-AR agonist CGS 21680 in isolated atrial preparations, antagonistic effects of FLUDA were found in A_2A-AR-TG animals but not in WT. Radiolabelled [¹⁸F]FLUDA exhibited a K_D of 5.9 ± 1.6 nM and a B_max of 455 ± 78 fmol/mg protein in cardiac samples of A_2A-AR TG, whereas in WT, as well as in human atrial preparations, only low specific binding was found. Dynamic PET studies revealed a significantly higher initial uptake of [¹⁸F]FLUDA into the myocardium of A_2A-AR TG compared to WT. The hA_2A-AR-specific binding of [¹⁸F]FLUDA in vivo was verified by pre-administration of the highly affine A_2AAR-specific antagonist istradefylline. Conclusion: [¹⁸F]FLUDA is a promising PET probe for the non-invasive assessment of the A_2A-AR as a marker for pathologies linked to an increased A_2A-AR density in the heart, as shown in patients with heart failure.     

Morphology–property relationships in ABS/PET blends. I. Compositional effects

Novel blends of PET and ABS were prepared by extrusion and injection molding. DSC and DMTA studies show that PET and ABS are immiscible and that the blends consist of four phases: SAN, grafted polybutadiene, amorphous PET, and minor amounts of crystalline PET. The morphology was investigated by transmission electron microscopy on OsO₄-stained and unstained sections and by scanning electron microscopy of alkali- and solvent-etched surfaces. These techniques reveal that the two major domains, SAN and amorphous PET, interpenetrate and are cocontinuous over the compositional range of 30–70 wt % PET. The yield stress and flexural modulus increase in an almost linear fashion as the weight fraction of PET in the blend is increased. In contrast, the notched Izod impact energy passes through a maximum and the Dart impact energy shows a step transition at 50 wt % PET. SEM studies of the Izod fracture surfaces exhibit considerable plastic deformation in both domains when the specimens are tough, indicating that both phases participate in the toughening process. © 1996 John Wiley & Sons, Inc.     

Oil–Water Separation Using Superhydrophobic PET Membranes Fabricated Via Simple Dip‐Coating Of PDMS–SiO2 Nanoparticles

The surfaces of commercially available polyester (PET) and polypropylene (PP) are superhydrophobically modified via the deposition of polydimethylsiloxane (PDMS)‐coated SiO₂ nanoparticles (P‐SiO₂) and PDMS binder. The adhesion of P‐SiO₂ is stronger on PET than on PP due to a stronger chemical interaction between PET and PDMS, which is attributed to the higher surface energy of PET than PP. The waterproof ability and oil separation rate of the P‐SiO₂‐coated PET (dip‐PET) membranes are studied as a function of membrane thickness, and the influence of oil viscosity on the oil separation efficiency is investigated. Optimal membrane thickness should be selected in a given environment for the facile oil–water separation and the dip‐PET membrane is chemically stable and can be used repetitively for oil–water separation. Finally, an automated prototype instrument is introduced for the dip‐coating process. It is suggested that our dip‐PET is a promising solution for oil–water separation in real‐world oil‐spill applications.     

Poly(ethylene terephthalate) (PET) degradation during the Zn catalysed transesterification with dibutyl maleate functionalized polyolefins

The chemical reactions occurring during the melt blending between a dibutyl maleate functionalized polyolefin (POF) and poly(ethylene terephthalate) (PET) in the presence of Zn(OOCCH₃)₂·2H₂O were studied as a function of blending conditions, such as the preliminary drying of PET, the presence of a nitrogen flow during blending and the time of blending. The selective extraction of POF/PET 30/70 by weight blends to remove unreacted PET and the determination of its molecular weight by viscosimetric measurements allowed to evaluate both the grafting points' number and the molecular weight of PET. In this way the impact of degradation of PET onto its grafting by transesterification onto POF was investigated. The examined blending conditions were shown to affect both PET degradation and POF-PET copolymer formation. In order to correlate data about macromolecular and morphological structure with the final properties of the blends, differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and tensile tests were also carried out.     

Combined effect of isophthalic acid and polyethylene glycol in polyethylene terephthalate polymer on thermal,mechanical, and gas transport properties

The objective of this article is to study the combined effect of isophthalic acid (IPA) and polyethylene glycol (PEG‐400) in PET polymer and film on thermal, mechanical, and gas transport properties. The purpose of developing this material is to reduce the melting point, improve mechanical, thermal, and gas barrier properties. The chosen raw materials, namely, IPA and PEG for copolyester synthesis will replace partially the acid and diol monomers of PET. The molar concentration of comonomers (IPA and PEG‐400) were varied from 2 to 50% and the result shows that the gas barrier properties (namely O₂, CO₂, N₂, and water vapor transmission rate), mechanical, and thermal properties were lesser than that of PET polymer. On improving the crystallinity of PET‐isophthalate‐PEG (PET‐IP) copolymer, barrier properties are improved than that of PET polymer. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Calendar of events

The growth of Cu and Al films thermally evaporated onto polyethylene (PE) and polyethyleneterephthalate (PET) surfaces is followed in situ by XPS (X-ray Photoelectron Spectroscopy) and XAES (X-ray Auger Electron Spectroscopy) from the early submonolayer stages up to the completion of a metallic film. PE and PET surfaces were metallized first without any preliminary treatment. A second series of metallization experiments were run on the polymer surfaces but pretreated by a remote O₂ microwave plasma (2.45 GHz). These metal films have also been investigated by AFM (Atomic Force Microscopy) in air. Both metals are shown not to undergo chemical interaction with low surface energy polyolefin such as PE. While an abrupt interface is seen with A1, a diffusion of Cu into the bulk of the polymer is demonstrated. Large size clusters are evidenced by AFM in the initial steps of deposition. Cu and A1 are both shown to react with PET, but not in the same way. In the case of A1, the chemical interaction across the metal/polymer interface proceeds through an electron transfer from the metal toward the ester group O=C-O. With Cu, the chemical interaction is not so clearly evidenced and the Cu is found to diffuse into the PET. Oxygenated functionalities grafted by O₂ plasma on PE and PET are C-O, C=O, O-C-O, O-C=O, and O₂C=O. The roughness of the PE and PET surfaces is observed by AFM to increase with the plasma treatment. A metal-CO type complex is clearly observed with Al/treated PE and Cu/treated PET. No chemical interaction was observed at the Cu/treated PE interface.     

Photocatalytic decomposition of gaseous HCHO over a titanium dioxide film formed on a hydrophobic PET sheet

BACKGROUND: The authors (Chem Eng J 148, 234 (2009)) previously demonstrated the excellent performance of a photocatalytic reactor with a parallel array of nine light sources. To enhance the possibility of practical application of this reactor, the present work explores the use of a PET (polyethylene terephthalate) sheet as a new cheap material to support TiO₂, as an alternative to glass tubes. A method of coating the hydrophobic PET sheet with a TiO₂ film using an aqueous coating solution is investigated and the performance of the TiO₂‐PET sheet prepared evaluated. RESULTS: The affinity of the coating solution for the PET sheet is greatly enhanced by addition of 0.01% (w/w) nonionic surfactant (polyoxyethylene lauryl ether). A relatively uniform thin TiO₂ film is formed on the entire surface of the PET sheet by applying the coating solution to the PET sheet and drying it at 100 °C. Decomposition experiments of gaseous HCHO indicate that the photocatalytic activity, although initially low, is increased with repeated use. This is because surfactant molecules added interfere initially with the decomposition of HCHO. After their decomposition, the TiO₂–PET sheet decomposes HCHO at almost the same rate as does the TiO₂–glass tube. CONCLUSION: The photocatalytic reactor with a parallel array of nine light sources can utilize a PET sheet as TiO₂ support with a reduction in material cost. Copyright © 2011 Society of Chemical Industry