Charging of Polycarbonate Films in a Direct-Current Discharge

The effect of treatment of Diflon, Makrolon^®, and Lexan^® polycarbonate films in the cathode fall of a dc discharge was studied. Plasma treatment was shown to result in the hydrophilization of the film surface. The dependence of the contact angle on the discharge current and treatment time was examined. It was found that the discharge induced a negative charge on the polycarbonate surface. The surface-charge density was correlated with the contact angle for various treatment conditions. Space charging processes in glow discharge-treated films were investigated using the thermally stimulated relaxation and depolarization techniques. The role of produced charged entities in an increase in the surface energy of modified polycarbonate films was revealed.     

Attenuated total reflectance-fourier transform infrared microspectroscopy of copper(II) complexes with reduced dextran derivatives

Dextran is a water-soluble, extracellular neutral polysaccharide with a linear flexible chain of α-(1 → 6)-linked α-D-glucopyranose units, in a single compounds. In alkali solutions Cu(II) ion forms complexes with reduced low-molar dextran (RLMD). The metal content and the solution composition depended on pH. The complexing process begins in weak alkali solution (pH > 7), and involves OH groups in C2 and C3 dextran monomer units. Synthesized copper(II) complexes with RLMD, of average molar mass M _w = 5000 g/mol were investigated by attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and FTIR imaging microscopy. ATR-FTIR microspectroscopic data of synthesized complexes are rare in literature. The changes in intensity and width of the IR bands in region 1500-1000 cm⁻¹ were related to changes in conformation and short-range interactions of the ligand dextran. FTIR microscopy images shows more and less ordered structures of the Cu(II)-RLMD complexes. ATR-FTIR microspectroscopic data shows homogeneity of the Cu(II)-RLMD samples and green color of the samples confirm existence of Cu(II) ions. The article is published in the original.     

The Pharmaceutical Use of Captisol®: Some Surprising Observations

The purpose of this paper is to share some recent observations on the pharmaceuticaluses and properties of Captisol^® or SBE_7M--CD in controlled porosity osmotic pump tablets (CP-OPT) and the underlying mechanism/sthat lead to apparent zero-order drug release pattern. It would have been simple toattribute the apparent zero-order release mechanism/s of poorly water-soluble drugsfrom CP-OPTs and pellets utilizing Captisol^®as both a solubilizing andosmotic agent, to purely osmotic and diffusional components. However, the mechanismmay be more related to a counterbalancing of physical properties as the concentration of Captisol^®changes within the matrix. Specifically, the initial concentration of Captisol^®within a core is 0.3–0.4M. When this drops to lower values an osmotic pressure drop occurs across the membrane. Therefore, drug release should not follow apparent zero-order kinetics if all the drug is solubilized. However, as the viscosity within the tablet also drops, the apparent diffusion coefficient of both Captisol^® and drug increases. Therefore, it appears that there is an initial resistance (hydraulic pressure) to fluid flow from the tablet through the rate-limiting microporous membrane. This resistance decreases so that even as osmotic pressure and concentration differences drop with time, counterbalancing faster release occurs. Osmotic driving force appears to be the most important initial driving force but a diffusional component becomes more significant with time.     

Perfluoroelastomer and fluoroelastomer seals for semiconductor wafer processing equipment

Parts made from fluorinated elastomers, e.g., Kalrez^® perfluoroelastomer parts, parts made from Viton^® fluoroelastomer, are widely used as seals on semiconductor wafer processing equipment. Many of these seals are required to function in harsh chemical environments and at process temperatures ranging from 25 to 300 °C. Fluoroelastomers, including those of the perfluoroelastomer type, have extraordinary resistance to chemicals and heat, enabling them to withstand virtually any process media, including reactive plasmas, at temperatures as high as 316 °C.This paper is a review of perfluoroelastomers and fluoroelastomers used in semiconductor wafer processing. These seals offer cleanliness and lack of contamination while maintaining sealing functionality in aggressive media. Applications requiring resistance to both “wet” and “dry” process chemistry include etching, ashing, stripping, copper plating and chemical vapor deposition. Applications requiring thermal resistance include LPCVD, diffusion furnace and rapid thermal processing (RTP). A relative comparison of the various types of perfluoroelastomers used as well as a comparison to other elastomeric materials will also be discussed.     

Effect of carbon molecular sieve sizing with poly(vinyl pyrrolidone) K-15 on carbon molecular sieve–polysulfone mixed matrix membrane

Mixed matrix membranes (MMMs) comprising polysulfone (PSF) Udel^® P-1700 and 30 wt% carbon molecular sieve (CMS) particles (<25 μm) have been fabricated and characterized. CMS particles were treated in poly(vinyl pyrrolidone) kollidone 15 (PVP K-15) sizing bath solution (1–10 wt% in isopropanol) prior to embedment into the matrix solution to improve matrix–sieve interfacial adhesion. This study investigated the effects of CMS sizing with PVP K-15 on the morphology and the gas separation performance of PSF–CMS MMMs. The fabricated MMMs were characterized using TGA, DSC, FESEM, ATR-FTIR and single gas permeation test using high purity O₂ and N₂. A dramatic improvement in CMS–PSF adhesion was observed using FESEM micrographs upon incorporation of PVP K-15-sized CMS particles. ATR-FTIR results suggest the occurrence of intermolecular interaction between PVP K-15 sizing layer on the outer surface of CMS particles and PSF matrix. A substantial recovery of separation performance was achieved whereby the PSF–PVP-sized CMS MMM exhibited 1.7 times higher O₂/N₂ selectivity compared to that of unmodified MMM.     

Green Synthesis of UV-Reactive Polycarbonates from Levoglucosenone and 5-Hydroxymethyl Furfural

This study focuses on the synthesis of fully renewable polycarbonates (PCs) starting from cellulose-based platform molecules levoglucosenone (LGO) and 2,5-bis(hydroxymethyl)furan (BHMF). These unique bio-based PCs are obtained through the reaction of a citronellol-containing triol (Triol-citro) derived from LGO, with a dimethyl carbonate derivative of BHMF (BHMF-DC). Solvent-free polymerizations are targeted to minimize waste generation and promote an eco-friendly approach with a favorable environmental factor (E-factor). The choice of metal catalyst during polymerization significantly influences the polymer properties, resulting in high molecular weight (up to 755 kDa) when Na₂CO₃ is employed as an inexpensive catalyst. Characterization using nuclear magnetic resonance confirms the successful incorporation of the furan ring and the retention of the terminal double bond of the citronellol pendant chain. Furthermore, under UV irradiation, the presence of both citronellol and furanic moieties induces singular structural changes, triggering the formation of three distinct structures within the polymer network, a phenomenon herein occurs for the first time in this type of polymer. These findings pave the way to new functional materials prepared from renewable monomers with tunable properties.     

Biomass‐derived furanic polycarbonates: Mild synthesis and control of the glass transition temperature

Bis(hydroxymethyl)furan (BHMF) is a promising biomass‐derived polymer platform, but it is incompatible with traditional methods used for synthesizing polycarbonates (PCs) owing to its thermal instability. In this study, BHMF‐based furanic (FR) PCs were prepared successfully at a relatively low temperature through the mediation of carbonyldiimidazole. The low T_g of aliphatic FR‐PCs was controlled elaborately, exploiting the reactivity of furan in the Diels–Alder reactions and the molecular rigidity of the resulting oxabicycles. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1796–1800     

Biosynthesis of Cd-bound phytochelatins by <Emphasis Type="Italic">Phaeodactylum tricornutum</Emphasis> and their speciation by size-exclusion chromatography and ion-pair chromatography coupled to ICP–MS

Cd-bound phytochelatins (Cd–PCs) have been synthesised by incubation of Phaeodactylum tricornutum cell cultures with Cd and purified by size-exclusion chromatography–UV–Vis. These complexes, which were identified in previous work, have now been used as model substances to develop and optimise ion-pair chromatography (IPC) coupled to inductively coupled plasma–mass spectrometry (ICP–MS) for analysis of Cd–PCs. Subsequent analysis of samples taken from Silene vulgaris plants cultivated under heavy metal stress conditions revealed Cd signals but no Cd–PC signals. By use of isotopically enriched ¹¹⁶Cd–PCs the sample preparation steps were verified to determine the stability of the analytes. We observed species transformation between Cd–PCs and other unidentified Cd complexes. Consequently, the kinetic and thermodynamic lability of Cd–PCs are decisive factors in their detection.     

Novel perfluoropolyethers containing 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxole blocks: synthesis and characterization

Peroxidic perfluoropolyethers (PFPEs) are industrial intermediates used by Solvay Solexis for the preparation of different classes of (per)fluoropolyethers (Fomblin^®, Galden^®, Solvera^®, Fluorolink^®). The chemistry of these peroxidic compounds has been recently exploited for the synthesis of novel PFPE block copolymers. In the present work we report the synthesis, the structural and physical-chemical characterization of block copolymers obtained by the reaction of peroxidic PFPEs with 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxole, a cyclic homopolymerizable perfluoroolefin. These block copolymers combine the most attractive properties of the PFPEs, like the excellent lubrication, the high thermal stability and the optical transparency, with new specific properties which are related to the perfluorodioxolenic blocks.     

Study of Structural Surface Modified Tin Oxide Membrane Prepared by Sol-Gel Route Sintered at 400°C

This work describes the chemical modification by Tiron® molecules of the surface of SnO₂ nanoparticles used to prepare nanoporous membranes. Samples prepared with Tiron® content between 1 and 20 wt% and fired at 400°C were characterised by X-Ray Powder Diffraction (XRPD), Extended X-ray Absorption Fine Structure (EXAFS), N₂ adsorption isotherms analysis and permeation experiments. XRPD and EXAFS results show a continuous reduction of crystallite size by increasing the Tiron® contents until 7.5 wt%. The control exercised by Tiron® modifying agent in crystallite growth allows the fine tuning of the average pore size that can be screened from 0.4 to 4 nm as the amount of grafted molecules decreases from 10 to 0 wt%. In consequence, the membrane cut-off can be screened from 1500 to 3500 g · mol^–1.     

Melt-processable poly(tetrafluoroethylene)—compounding, fillers and dyes

Recently, a window of molar mass has been identified where poly(tetrafluoroethylene) (PTFE) homopolymer can be processed from the melt, but at the same time has good mechanical properties in the solid state, so called HD-PTFE^®. This research evaluates the use of conventional melt-compounding with a co-rotating twin-screw to introduce a variety of fillers in this material. It was found that melt-compounding is indeed an efficient way to achieve a filler distribution of excellent homogeneity in HD-PTFE^®.     

Synthesis and thermochemistry of phenylmaleimide- and phenylnadimide-terminated bisphenol A polycarbonates

Phenylmaleimide (PMI)- and phenylnadimide (PNI)-terminated bisphenol A polycarbonates (PCs) were prepared by solution or interfacial phosgenation processes, and their thermal crosslinking, both with and without a free radical initiator, and the thermal stability of the resultant network polymers were investigated. m-PMI PCs were prepared by interfacial phosgenation of bisphenol A and m-hydroxyphenylmaleimide, but p-hydroxyphenylmaleimide caused rapid phosgene hydrolysis under interfacial conditions and PCs from it could only be made by solution phosgenation. The degree of crosslinking of PMI PCs, as measured by their gel fraction, heated in the absence of a free radical initiator was generally higher at 250°C than at 300°C and increased with the concentration of PMI end groups. m- and p-PMI PCs form thermosets having nearly complete gel fractions by radical initiated curing at 150–200°C. The gel fraction of these thermosets decreases with exposure to higher temperatures (300°C). This behavior is attributed to BA PC chain degradation induced by nitrogen-containing maleimide reaction products. p-PNI PC was prepared by solution phosgenation and the thermal reaction of it in the presence of the initiator produced only a small increase in molecular weight. © 1997 John Wiley & Sons, Inc.     

Isolation of Pu-isotopes from environmental samples using ion chromatography for accelerator mass spectrometry and alpha spectrometry

A radiochemical method for the isolation of plutonium-isotopes from environmental samples, based on the use of specific extraction chromatography resins for actinides (TEVA^®, Eichrom Industries, Inc.), has been set up in our laboratory and optimised for their posterior determination by alpha spectrometry (AS) or accelerator mass spectrometry (AMS). The proposed radiochemical method has replaced in our lab a well-established one based on the use of a relatively un-specific anion-exchange resin (AG^® 1X8, Bio-rad Laboratories, Inc.), because it is clearly less time consuming, reduces the amounts and molarities of acid wastes produced, and reproducibly gives high radiochemical yields.In order to check the reliability of the proposed radiochemical method for the determination of plutonium-isotopes in different environmental matrixes, twin aliquots of a set of samples were prepared with TEVA^® and with AG^® 1X8 resins and measured by AS. Some samples prepared with TEVA^® resins were measured as well by AMS. As it is shown in the text, there is a comfortable agreement between AS and AMS, which adequately validates the method.     

Studies of environmental stress-crack propagation in low-density polyethylene

Correlations of the stress-intensity factor K with crack speed a have been obtained for environmental stress cracking (ESC) of a series of low-density polyethylenes in detergent. In the majority of the materials, the crack speed increases initially with increasing K, then becomes constant, and finally starts decreasing. The ESC resistance increases with increasing molecular weight and, in general, the quenched materials show greater ESC resistance than slowly cooled ones. The crack propagation results agree well with the ESC model of Williams. Attempts have also been made to understand the micromechanics of ESC failure from a combined approach of K, the crack tip characteristics, and the fracture surface appearance. The roughness of the fracture surface increases with increasing K.     

The effect of spatial confinement of Nafion in porous membranes on macroscopic properties of the membrane

Polyelectrolytes were incorporated into porous reinforcing materials to study the properties of ionomers in confined spaces and to determine the effect of the porous material on the behaviour of the membranes. Nafion^® was imbibed into porous polypropylene (Celgard^®), ultra-high-molecular weight polyethylene (Daramic^®), and polytetrafluoroethylene (PTFE) films. Through the use of reinforcing materials, it is possible to prepare membranes that are thinner, but stronger than pure ionomer membranes. Thin reinforced membranes have advantages such as lower areal resistance (as low as 0.14 Ω cm² for 57 μm CG3501 + Nafion^® compared to 0.34 Ω cm² for 89 μm cast Nafion^®) and lower dimensional changes due to swelling (as low as a 4% change in length and width for WDM + Nafion^® compared to 13% for cast Nafion^®). Using reinforcing materials results in a reduction in important membrane properties compared to bulk Nafion^®, such as proton conductivity (as low as 0.016 S cm⁻¹ for CG3401 + Nafion^® compared to 0.076 S cm⁻¹ for cast Nafion^®), effective proton mobility (as low as 3.2 × 10⁻⁴ cm² V⁻¹ s⁻¹ CG3401 + Nafion^® compared to 7.6 × 10⁻⁴ cm² V⁻¹ s⁻¹ for cast Nafion^®), and water vapour permeance (as low as 0.036 g h⁻¹ Pa⁻¹ m⁻² for WDM + Nafion^® compared to 0.056 g h⁻¹ Pa⁻¹ m⁻² for cast Nafion^®). By normalizing the membrane properties with respect to ionomer content, it was possible to examine the properties of the Nafion^® inside the pores of the membranes. The proton conductivity (as low as 0.032 S cm⁻¹ for CG3401 + Nafion^®), effective proton mobility (as low as 3.6 × 10⁻⁴ cm² V⁻¹ s⁻¹ for CG3401 + Nafion^®), and water vapour permeability (as low as 2.7 × 10⁻⁶ g h⁻¹ Pa⁻¹ m⁻¹ for PTFE MP 0.1 + Nafion^®) of the ionomer in the membrane are also diminished compared to bulk Nafion^® due to decreased connectivity of the ionomer and a restriction in macromolecular motions caused by the pore walls. A series of porous materials with increasing pore were also examined. As the pore size of the PTFE MP materials increased from 0.1 μm to 10 μm, the proton conductivity (0.022 S cm⁻¹ to 0.041 S cm⁻¹), effective proton mobility ((4.1 to 5.6) × 10⁻⁴ cm² V⁻¹ s⁻¹), and water vapour permeability ((2.4 to 4.3) × 10⁻⁶ g h⁻¹ Pa⁻¹ m⁻¹) of the reinforced membranes improved with increasing pore size and the properties of the ionomer inside the membranes approached the value of bulk Nafion^®.     

Spectroscopic,thermal, and mechanical characterization of the polymeric fabrics used in extreme low-temperature protective garments

This paper presents the study of the chemical and physico-mechanical properties of the natural and synthetic fabrics used in extreme low-temperature (?20 °C) gloves. The essential properties, such as the weight of the gloves, cold insulation, and surface water repellency, were studied. In-depth analysis by ¹³C solid-state nuclear magnetic resonance spectroscopy (¹³C SSNMR), attenuated total reflectance fourier transform infrared spectroscopy (ATR-FTIR), and differential scanning calorimetry (DSC) techniques were undertaken to understand the chemical and thermal characteristics of the fabrics. The physico-mechanical properties, such as thickness, weight, softness, tear strength, abrasion resistance, blade cut resistance, and puncture resistance, of each fabric used in the gloves, were also studied. Finally, the physico-mechanical properties were correlated with the chemical nature of the fabrics and the garment's performance properties.The present study will guide in the selection of materials for designing low-temperature protective garments. The in-depth analysis presented in this work will also help the researchers in the chemical identification of natural and synthetic polymeric fabrics using solid-state NMR, ATR-FTIR, and DSC techniques.     

Synthesis and polymerisation of α,ω-bis(3-pyrrolyl)alkanes

The synthesis, characterisation and polymerisation studies of a homologous series of α,ω-bis(pyrrolyl)alkanes are described. These α,ω-bis(pyrrolyl)alkanes were produced using Friedel-Crafts acylation followed by reduction of the carbonyl group using Red-Al^®. Chemical polymerisation of the resultant dimers using FeCl₃ produced poly(α,ω-bis(pyrrolyl)alkane) films, which were characterised by SEM, FTIR and tested for conductivity.     

Comparison of three different enrichment strategies for serum low molecular weight protein identification using shotgun proteomics approach

Serum low-molecular weight (LMW) proteins potentially contain useful biological information and their identification can be used to discover novel potential biomarkers. Given the high complexity of serum samples, in the last years several different prefractionation and enrichment strategies have been developed. In this study three different methods, i.e. hydrogel nanoparticles, Proteominer^® peptide ligand affinity beads and Sartorius Vivaspin^® centrifugal ultrafiltration device, were compared and evaluated in order to select the best strategy for the enrichment and prefractionation of LMW proteins. A shotgun proteomics approach was adopted, with in-solution proteolytic digestion of the whole protein mixture and determination of the resulting peptides by nanoHPLC coupled with a high-resolution Orbitrap LTQ-XL mass spectrometer. Data analysis, focusing on the LMW proteome (MW ≤ 40 kDa), has shown that the hydrogel nanoparticles performed better in enriching the LMW protein profiles, with 115 proteins identified against 93 and 95 for Proteominer^® beads and Sartorius Vivaspin^® device, respectively.     

Improvement of environmental stress cracking resistance of polycarbonate by silicone coating

To explore the possibility of using surface coating to reduce environmental stress cracking (ESC) of transparent polycarbonate (PC) parts, silicone coated and SiO₂ coated PC were tested in a self-made three-point bending apparatus in the presence of ethanol. The variation of stress with time was recorded, and the surface cracking was observed to evaluate the ESC resistance of samples. Slower stress relaxation rates and fewer surface cracks indicated that silicone coating improved the ESC resistance of PC, but SiO₂ coated PC was found to be no better than that of uncoated PC. Silicone coating reduced the absorption of ethanol in PC, weakening the surface plasticization, thus hindering the formation and development of cracks in PC. Nanoindentation test results showed that the mechanical properties such as hardness and elastic modulus of silicone coating are a better match for PC than SiO₂ coating. This allows the silicone coating to have a favorable effect in providing continuous protection for PC under the combined action of ethanol and stress.     

The influence of sub-Tg annealing on environmental stress cracking resistance of polycarbonate

To explore the effect of physical aging on environmental stress cracking (ESC) behavior of polycarbonate (PC), sub-T_g annealing was utilized as a method for accelerated aging. Injection molded samples were annealed at 130 °C for different time varying up to 96 h. A three point bending apparatus was used to evaluate critical stress for crazing and to record the variation of stress with immersion time at constant strain. The ESC results indicated that the critical stress for crazing initiation of PC in ethanol is increased by sub-T_g annealing. However, the resistance of annealed PC to ESC with immersion time during the stress relaxation test depends on the level of initial stress. When a relatively low initial stress was used, a short time (24 h) of sub-T_g annealing reduced the stress relaxation rate and decreased the number of cracks on the surface of PC. However, under higher initial stress, the stress relaxation rate of PC had a slight change only when the annealing time was prolonged about threefold (72 h). This can be explained by the formation of cohesional entanglement sites during the sub-T_g annealing process, which was demonstrated by the thermal and dynamic mechanical tests.