Luminescent copolymers for applications in multicolor‐light‐emitting devices

Light‐emitting diodes based on organic materials [organic light‐emitting diodes (OLEDs)] have attracted much interest over the past decade. Several different attempts have been made to realize multicolor OLEDs. This article describes a new approach based on energy transfer in a donor/acceptor system. A copolymer containing both donor and acceptor compounds as comonomer units is prepared. The polymer consists of a derivative of a luminescent dye [4‐dicyanmethylene‐2‐methyl‐6‐4H‐pyran (DCM); acceptor compound], which is copolymerized with fluorene (donor compound) to combine the properties of an electroactive polymer with a highly luminescent dye. Photochemical processing is achieved by UV irradiation of this copolymer in the presence of gaseous trialkylsilanes. This reagent selectively saturates the C?C bonds in the DCM comonomer units while leaving the fluorene units essentially unaffected. As a result of the photochemical process, the red electroluminescence of the acceptor compound vanishes, and the blue‐green electroluminescence from the polyfluorene units is recovered. Compared with previous approaches based on polymer blends, this copolymer approach avoids problems associated with phase‐separation phenomena in the active layer of OLEDs. © 2006Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4317–4327, 2006     

Evaluation of piezoelectric PVDF polymers for use in space environments. III. Comparison of the effects of vacuum UV and gamma radiation

Films of piezoelectric PVDF and P(VDF‐TrFE) were exposed to vacuum UV (115–300 nm VUV) and γ‐radiation to investigate how these two forms of radiation affect the chemical, morphological, and piezoelectric properties of the polymers. The extent of crosslinking was almost identical in both polymers after γ‐irradiation, but surprisingly, was significantly higher for the TrFE copolymer after VUV‐irradiation. Changes in the melting behavior were also more significant in the TrFE copolymer after VUV‐irradiation due to both surface and bulk crosslinking, compared with only surface crosslinking for the PVDF films. The piezoelectric properties (measured using d₃₃ piezoelectric coefficients and D‐E hysteresis loops) were unchanged in the PVDF homopolymer, while the TrFE copolymer exhibited more narrow D‐E loops after exposure to either γ‐ or VUV‐radiation. The more severe damage to the TrFE copolymer in comparison with the PVDF homopolymer after VUV‐irradiation is explained by different energy deposition characteristics. The short wavelength, highly energetic photons are undoubtedly absorbed in the surface layers of both polymers, and we propose that while the longer wavelength components of the VUV‐radiation are absorbed by the bulk of the TrFE copolymer causing crosslinking, they are transmitted harmlessly in the PVDF homopolymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3253–3264, 2006     

Methods in carbon K-edge NEXAFS: Experiment and analysis

Near-edge X-ray absorption spectroscopy (NEXAFS) is widely used to probe the chemistry and structure of surface layers. Moreover, using ultra-high brilliance polarised synchrotron light sources, it is possible to determine the molecular alignment of ultra-thin surface films. However, the quantitative analysis of NEXAFS data is complicated by many experimental factors and, historically, the essential methods of calibration, normalisation and artefact removal are presented in the literature in a somewhat fragmented manner, thus hindering their integrated implementation as well as their further development. This paper outlines a unified, systematic approach to the collection and quantitative analysis of NEXAFS data with a particular focus upon carbon K-edge spectra. As a consequence, we show that current methods neglect several important aspects of the data analysis process, which we address with a combination of novel and adapted techniques. We discuss multiple approaches in solving the issues commonly encountered in the analysis of NEXAFS data, revealing the inherent assumptions of each approach and providing guidelines for assessing their appropriateness in a broad range of experimental situations.     

Quantitative determination of UV filters in sunscreen lotions using microemulsion electrokinetic chromatography

Microemulsion electrokinetic chromatography (MEEKC) has been applied to the separation of some UV filters (Eusolex 4360, Eusolex 6300, Eusolex OCR, Eusolex 2292, Eusolex 6007, Eusolex 9020, Eusolex HMS, Eusolex OS, and Eusolex 232) commonly used in sunscreen lotions. Use of a MEEKC buffer with a mixed surfactant system to stabilize the oil droplets and an organic modifier in the aqueous phase allowed separation of most of the selected analytes in a single run in a system fitted with a diode array detector recording three wavelengths (240 nm, 300 nm, and 380 nm) simultaneously. The microemulsion employed consisted of 2.25 g of SDS, 0.75 g of Brij 35, 6.6 g 1‐butanol, 0.8 g n‐octane, 17.5 g 2‐propanol, and 72.1 g of 10 mM borate buffer (pH 9.2). Detection limits from 0.65 to 6.0 μg/mL were obtained and the calibration plots were linear over at least one order of magnitude for all analytes. The developed method could be applied to the determination of UV filters in several sun protection products including lotions, milks, and oils. Comparison of the obtained data with those from an HPLC method described in the literature showed acceptable agreement.     

Bestimmung von Melment in Zementmischungen durch UV-Spektralphotometrie

Ohne Zusammenfassung

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Determination of melment in cement mixtures by UV-spectrophotometry

     

High-Resolution,Higher-Order UV/VIS Derivative Spectrophotometry

Derivative spectrophotometry has gained increasing importance in the past two years and is currently experiencing vigorous development. Following and introduction the present article provides a review of this extremely effective method. In particular, the advantages of higher-order derivative spectrophotometry (HODS method, n > 2) are discussed on the basis of practical examples from a wide range of analytical fields. The results are achieved with the aid of a newly developed analog computer unit, whereby for the first time readily reproducible, low-noise, on-line spectra can be obtained up to the 7th order and even, in favorable cases, up to the 9th order. In practice it has proved valuable to work with spectra of the 3rd to 5th order; but even higher derivations could be profitable for the separation of strongly superposed signals or for “fingerprinting”.     

Stabilisation of ultra-high molecular weight polyethylene with Vitamin E

Ultra-high molecular weight polyethylene (UHMWPE) has been the material of choice for load-bearing articular components used in total joint arthroplasty in the past 30 years. However, the durability of the whole implant has often been compromised by oxidation of UHMWPE components. Since the use of a suitable, biocompatible stabilizer would minimize this inconvenience, the possibility of adding synthetic Vitamin E to medical grade UHMWPE is currently under investigation.In the present work, medical grade UHMWPE was blended with 0.05, 0.1 or 0.5 w/w% of α-tocopherol and consolidated by compression moulding. Small blocks of reference UHMWPE and of each blend were then gamma irradiated to 30 or 100 kGy. FTIR spectroscopy was used to monitor changes in both the polymer and the additive. Thin sections of virgin and α-tocopherol doped UHMWPE irradiated and unirradiated were aged in a ventilated oven at 90 °C and the kinetic of oxidation was followed by FTIR. In addition, CL-imaging curves were recorded at 180 °C on both irradiated and unirradiated samples.Phenol loss is observed in all the α-tocopherol doped samples upon irradiation. Hypotheses on the rearrangements of the additive structure include the formation of quinonoid products. Nevertheless, all the additive-containing samples exhibit better oxidation resistance compared to the virgin material, indicating stabilizing activity of the α-tocopherol derivatives.     

Synthesis of metal/polymer nanocomposite by UV-radiation curing

Nanocomposite polymers containing bismuth nanoparticles (2 wt%) have been obtained by photopolymerization of acrylic resins. The bismuth nanoparticles have been synthesized by reduction of BiCl₃ with t-BuONa activated sodium hydride. In situ t-BuONa stabilization protects the metallic particles against aggregation. Transmission electron microscopy (TEM) analysis has shown that the bismuth nanoparticles are well dispersed in the acrylic resin. The curing process was followed quantitatively by infrared spectroscopy through the decrease upon UV exposure of the IR bands characteristic of the functional groups. The bismuth nanoparticles were found to have no detrimental effect on the photopolymerization kinetics. Dynamic mechanical analysis (DMA) has shown that the viscoelastic properties of the nanocomposite photopolymer are significantly modified in comparison with corresponding UV-cured polymer. The addition of metal nanoparticles was found to greatly reduce the gloss of UV-cured coatings.     

Sequential injection analysis for benzophenone-4 and phenylbenzimidazole sulphonic acid in sunscreen sprays by solid-phase extraction coupled with ultraviolet spectrometry

A sequential injection UV method was developed to determine benzophenone-4 (BZ4) and phenylbenzimidazole sulphonic acid (PBS) simultaneously, these being the most commonly used UV-filters in aqueous formulations used as sunscreen sprays. The selective elution of both was performed by on-line solid-phase extraction, by retention on a SAX microcolumn and separation by varying the pH of elution. The sensitivity obtained was 0.042±0.001 ml μg⁻¹ for PBS and 0.0159±0.0003 ml μg⁻¹ for BZ4. The limit of detection was 1.6 μg ml⁻¹ for PBS and 0.6 μg ml⁻¹ for BZ4. The R.S.D. of the results was 1-6% for PBS and 1-12% for BZ4. The method was validated using commercial sunscreen formulations with concentrations determined by a liquid chromatographic procedure. The two procedures gave comparable results. Automation of the method means the amount of reagents used and residues generated are decreased. The system allows the required analysis sequence to be programmed using suitable software.     

Thermal degradation behavior of radiation synthesized polydiallyldimethylammonium chloride

Thermogravimetric analysis (TGA) and differential scanning calorimetric (DSC) studies were carried out on gamma radiation synthesized polydiallyldimethylammonium chloride (PDADMAC). The polymer was found to undergo thermal degradation in two stages. The first stage showed a weight loss of 33% and the second stage showed a weight loss of 67%. The DSC thermogram shows two endothermic peaks corresponding to the two stages in the TG thermogram and the experimental enthalpy change associated with the first and second stages were 650 J g⁻¹ and 129.5 J g⁻¹, respectively. The nth-order kinetic parameters (order of the reaction, activation energy and the pre-exponential factor) were determined from a single dynamic DSC or thermogravimetric (TG) thermogram by the method of least square. Theoretical TG/differential thermogravimetric (DTG) and DSC thermograms derived from the calculated kinetic parameters were in good agreement with the experimental ones at the heating rate employed. However, the kinetic parameters determined using TG and DSC were different. This leads to the conclusion that the degradation mechanism could be complicated and may consists of a number of parallel or consecutive reactions. The glass transition temperature (T_g) of the polymer was found to be around 150 °C depending on the test method employed.