Rheological evaluation of the influence of polymer concentration and molar mass distribution on the formation and performance of asymmetric gas separation membranes prepared by dry phase inversion

Asymmetric gas separation membranes were prepared by the dry-casting technique from PEEKWC, a modified amorphous glassy poly(ether ether ketone). The phase inversion process and membrane performance were correlated to the properties of the polymer and the casting solution (molar mass, polymer concentration, solution rheology and thermodynamics). It was found that a broad molar mass distribution of the polymer in the casting solution is most favourable for the formation of a highly selective membrane with a dense skin and a porous sub-layer. Thus, membranes with an effective skin thickness of less than 1 μm were obtained, exhibiting a maximum O₂/N₂ selectivity of 7.2 and a CO₂/CH₄ selectivity of 39, both significantly higher than in a corresponding thick dense PEEKWC membrane and also comparable to or higher than that of the most commonly used polymers for gas separation membranes. The CO₂ and O₂ permeance were up to 9.5×10⁻³ and 1.8×10⁻³ m³/(m² h bar) (3.5 and 0.67 GPU), respectively.     

Crystallization of amorphous indium zinc oxide thin films produced by radio-frequency magnetron sputtering

In this work we studied indium zinc oxide (IZO) thin films deposited by r.f. magnetron sputtering at room temperature. The films were annealed at high temperature (1100 K) in vacuum, and the oxygen exodiffusion was monitored in-situ. The results showed three main peaks, one at approximately 600 K, other at approximately 850 K and the last one at 940 K, which are probably from oxygen bonded in the film surface and in the bulk, respectively. The initial amorphous structure becomes microcrystalline, according to the X-ray diffraction. The electrical conductivity of the films decreases (about 3 orders of magnitude), after the annealing treatment.This behavior could be explained by the crystallization of the structure, which affects the transport mechanism. Apart from the changes in the material structure, a small variation was observed on the absorption coefficient.     

Influence of the layer thickness and hydrogen dilution on electrical properties of large area amorphous silicon p–i–n solar cell

The aim of this work is to present data concerning the optimization of performances of a large area amorphous silicon p–i–n solar cell (30×40 cm²) deposited by plasma enhanced chemical vapour deposition (PECVD) at 27.12 MHz. In this work the solar cell was split into small areas of 0.126 cm², aiming to study the device performance uniformity, where emphasis was put on the role of the n-layer thickness. The solar cells were studied through the spectral response behaviour in the 400–750 nm range as well as by the behaviour of the AC impedance. Solar cells with fill factor of 0.58, open circuit voltage of 0.83 V, short circuit current density of 17.14 mA/cm² and an efficiency of 8% were obtained at growth rates higher than 0.3 nm/s.     

Silicon thin films prepared in the transition region and their use in solar cells

Diphasic silicon films (nc-Si/a-Si:H) have been prepared by a new regime of plasma enhanced chemical vapour deposition in the region adjacent of phase transition from amorphous to microcrystalline state. Comparing to the conventional amorphous silicon (a-Si:H), the nc-Si/a-Si:H has higher photoconductivity (σ_ph), better stability, and a broader light spectral response range in the longer wavelength range. It can be found from Raman spectra that there is a notable improvement in the medium range order. The blue shift for the stretching mode and red shift for the wagging mode in the IR spectra also show the variation of the microstructure. By using this kind of film as intrinsic layer, a p–i–n junction solar cell was prepared with the initial efficiency of 8.51% and a stabilized efficiency of 8.01% (AM1.5, 100 mw/cm²) at room temperature.     

Evaluation of a single-capillary viscometer detector on line to a SEC system used with a new pulse-free pump

A single-capillary viscometer (SCV) used as an on-line viscosity-sensitive detector for size exclusion chromatography (SEC) presents considerable interest. Unfortunately, the commercially available version, which uses a traditional HPLC pump and a pulse dampener, presents serious problems and can give poor performance. Flow rate fluctuations are the main problems in the use of the on-line SCV detector. The pulse dampener resolves the flow fluctuations problems that are intrinsic to a reciprocating pump. Unfortunately, the pulse dampener introduces secondary, yet variable, flow fluctuations that make the SCV unreliable. In the past, several solutions to the problem have been described. Our proposal is to use the SCV on-line detector with a new commercial pulse-free pump without a pulse dampener. A detailed evaluation of this new SEC–SCV system has been performed using various polymers. Molar mass distribution, intrinsic viscosity distribution, and constants of the Mark–Houwink–Sakurada relationship have been determined. The used polymers were soluble both in organic solvent (PS, PMMA, PVAc, PVC, polyalkylthiofene) and in aqueous solvent (PEO, PEG, pullulan, and hyaluronan). The results obtained are encouraging. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1651–1659, 1998     

Films made from polyethylene‐co‐acrylic acid and soluble biopolymers sourced from agricultural and municipal biowaste

Blends were obtained from polyethylene‐co‐acrylic acid (PEAA) with 248 kDa molecular weight and two water soluble biopolymers isolated from the hydrolysate of postharvest tomato plant and urban biowaste compost. The two hydrolysates were constituted respectively from a polysaccharide (SP) with 27 kDa molecular weight and a lignin‐like polymer (LP) with 75 kDa molecular weight containing aliphatic and aromatic C moieties substituted by carboxyl, hydroxyl, and amino groups. Evidence was obtained for reactions occurring between the biopolymers and the synthetic polymer leading to new polymers with 151 to 1243 kDa molecular weights. The thermal and mechanical properties of the blends were studied. Compared with neat PEAA, the PEAA‐LP blends containing 5 to 10% LP exhibited 2 to 5× higher molecular weights, 10 to 50% lower crystallinity, 2 to 6× higher Young's modulus, over 3× higher stress at yield point and somewhat lower strain at break (55–280% vs. over 300%). On the contrary the PEAA‐SP blends exhibited 6 to 13% lower crystallinity and the same mechanical properties as neat PEAA. The results offer scope for investigating biopolymers sourced from other biowastes to understand more the reasons of the observed effects and exploit their full potential to modify or to replace synthetic polymers. Perspectives of economic and environmental benefits are discussed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41909.     

Highly stable transparent and conducting gallium-doped zinc oxide thin films for photovoltaic applications

Transparent and highly conducting gallium zinc oxide (GZO) films were successfully deposited by RF sputtering at room temperature. A lowest resistivity of ∼2.8×10⁻⁴ Ω cm was achieved for a film thickness of 1100 nm (sheet resistance ∼2.5 Ω/□), with a Hall mobility of 18 cm²/V s and a carrier concentration of 1.3×10²¹ cm⁻³. The films are polycrystalline with a hexagonal structure having a strong crystallographic c-axis orientation. A linear dependence between the mobility and the crystallite size was obtained. The films are highly transparent (between 80% and 90% including the glass substrate) in the visible spectra with a refractive index of about 2, very similar to the value reported for the bulk material. These films were applied to single glass/TCO/pin hydrogenated amorphous silicon solar cells as front layer contact, leading to solar cells with efficiencies of about 9.52%. With the optimized deposition conditions, GZO films were also deposited on polymer (PEN) substrates and the obtained results are discussed.     

Application of liquid chromatography-direct-electron ionization-MS in an in vitro dermal absorption study: quantitative determination of trans-cinnamaldehyde

We propose a new analytical approach, based on liquid chromatography (LC) coupled to electron ionization mass spectrometry (EI-MS), using a Direct-EI interface, for dermal absorption evaluation studies. Penetration through the skin of a given compound is evaluated by means of in vitro assays using diffusion cells. Currently, the most popular approach for the analysis of skin and fluid samples is LC coupled to electrospray ionization tandem mass spectrometry (ESI-MS/MS). However, this technique is largely affected by sample matrix interferences that heavily affect quantitative evaluation. LC-Direct-EI-MS is not affected by matrix interference and produces accurate quantitative data in a wide range of concentrations. Trans-cinnamaldehyde was chosen as test substance and applied in a suitable dosing vehicle on dermatomed human skin sections. This compound was then quantified in aliquots of receptor solution, skin extract, cell wash, skin wash, carbon filter extract, cotton swab extract, and tape strip digest. On column limits of detection (LOD) and limits of quantitation (LOQ) of 0.1 and 0.5 ng/μL, respectively, were achieved. Calibration showed satisfactory linearity and precision for the concentration range of interest. Matrix effects (ME) were evaluated for all sample types, demonstrating the absence of both signal enhancement and signal suppression. The Direct-EI absorption profile was compared with that obtained with liquid scintillation counting (LSC), a recognized ME free approach. A good correlation was found with all samples and for the overall recovery of the dosed substance.     

Extruded versus solvent cast blends of poly(vinyl alcohol‐co‐ethylene) and biopolymers isolated from municipal biowaste

Water‐soluble biopolymers (SBO) were isolated from the alkaline hydrolysate of two materials sampled from an urban waste treatment plant; that is, an anaerobic fermentation digestate and a compost. The digestate biopolymers contained more lipophilic and aliphatic C, and less acidic functional groups than the compost biopolymers. The SBO were blended with poly (vinyl alcohol‐co‐ethylene), hereinafter EVOH. The blends were extruded and characterized by FTIR spectroscopy, size exclusion chromatography (SEC)– multi angle static light scattering (MALS) analysis, and for their thermal, rheological, and mechanical properties. The blends behavior depended on the type of SBO and its relative content. Evidence was obtained for a condensation reaction occurring between the EVOH and SBO. The best results were obtained with the blends containing up to 10% SBO isolated from the biowaste anaerobic digestate. Compared with the neat EVOH, these blends exhibited lower melt viscosity and no significant or great difference in mechanical properties. The results on the extrudates, compared with those previously obtained on the same blends obtained by solvent casting, indicate that the blends properties depend strongly also on the processing technology. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43009.     

PPO–PC block‐copolymers used as compatibilizers in PS/PC blends

Block‐copolymers containing poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) and polycarbonate of bisphenol A (PC) segments were employed as compatibilizers in polystyrene (PS)/PC blends. Block‐copolymers were prepared starting from oligomeric diols‐terminated PPO and PC. The poly(phenylene ethers) was obtained by oxidative coupling of 2,6‐dimethyl‐phenol in presence of tetramethyl bisphenol A. The copolymers were obtained with a chain extension reaction between the starting oligomers using bischloroformate of bisphenol A or phosgene as coupling agent. PS/PC blends, cast from chloroform solutions or mixed by melt, were studied by differential scanning calorimeter (DSC), dynamic‐mechanical thermal analysis (DMTA), and optical microscopy (OP). The thermal and morphological analyses showed a clear compatibilization effect between PS and PC, if PPO–PC copolymer is added when blending is performed in the melt; in addition, also mechanical properties are increased when compared with blends without PPO–PC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4654–4660, 2006