Infrared spectroscopic investigation of the effects of titania photocatalyst on the degradation of linear low density polyethylene film for commercial applications

There is a need in industry for a commodity polyethylene film with controllable degradation properties that will degrade in an environmentally neutral way, for applications such as shopping bags and packaging film. Additives such as starch have been shown to accelerate the degradation of plastic films, however control of degradation is required so that the film will retain its mechanical properties during storage and use, and then degrade when no longer required. By the addition of a photocatalyst it is hoped that polymer film will breakdown with exposure to sunlight. Furthermore, it is desired that the polymer film will degrade in the dark, after a short initial exposure to sunlight. Research has been undertaken into the photo- and thermo-oxidative degradation processes of 25 ìm thick LLDPE (linear low density polyethylene) film containing titania from different manufacturers. Films were aged in a suntest or in an oven at 50 °C, and the oxidation product formation was followed using IR spectroscopy. Degussa P25, Kronos 1002, and various organic-modified and doped titanias of the types Satchleben Hombitan and Hunstsman Tioxide incorporated into LLDPE films were assessed for photoactivity. Degussa P25 was found to be the most photoactive with UVA and UVC exposure. Surface modification of titania was found to reduce photoactivity. Crystal phase is thought to be among the most important factors when assessing the photoactivity of titania as a photocatalyst for degradation. Pre-irradiation with UVA or UVC for 24 hours of the film containing 3% Degussa P25 titania prior to aging in an oven resulted in embrittlement in ca. 200 days. The multivariate data analysis technique PCA (principal component analysis) was used as an exploratory tool to investigate the IR spectral data. Oxidation products formed in similar relative concentrations across all samples, confirming that titania was catalysing the oxidation of the LLDPE film without changing the oxidation pathway. PCA was also employed to compare rates of degradation in different films. PCA enabled the discovery of water vapour trapped inside cavities formed by oxidation by titania particles. Imaging ATR/FTIR spectroscopy with high lateral resolution was used in a novel experiment to examine the heterogeneous nature of oxidation of a model polymer compound caused by the presence of titania particles. A model polymer containing Degussa P25 titania was solvent cast onto the internal reflection element of the imaging ATR/FTIR and the oxidation under UVC was examined over time. Sensitisation of 5 ìm domains by titania resulted in areas of relatively high oxidation product concentration. The suitability of transmission IR with a synchrotron light source to the study of polymer film oxidation was assessed as the Australian Synchrotron in Melbourne, Australia. Challenges such as interference fringes and poor signal-to-noise ratio need to be addressed before this can become a routine technique.

The concentric all-polyethylene Exeter acetabular component in primary total hip replacement

We report the long term outcome of the flangeless, cemented all polyethylene Exeter cup at a mean of 14.6 years (range 10-17) after operation. Of the 263 hips in 243 patients, 122 hips are still in situ, 112 patients (119 hips) have died, eighteen hips were revised, and three patients (four hips) had moved abroad and were lost to follow-up (1.5%). Radiographs demonstrated two sockets had migrated and six more had radiolucent lines in all three zones. The Kaplan Meier survivorship at 15 years with endpoint revision for all causes is 89.9% (95% CI 84.6 to 95.2%) and for aseptic cup loosening or lysis 91.7% (CI 86.6 to 96.8%). In 210 hips with a diagnosis of primary osteoarthritis survivorship for all causes is 93.2% (95% CI 88.1 to 98.3%), and for aseptic cup loosening 95.0% (CI 90.3 to 99.7%). The cemented all polyethylene Exeter cup has an excellent long-term survivorship.

meso-Porphyrinylphosphine Oxides: Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric [10,20-Diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph2] and Polymeric Self-Coordinated ([10,20-Diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph2])

A series of porphyrins substituted in one or two meso-positions by diphenylphosphine oxide groups has been prepared by the palladium catalysed reaction of diphenylphosphine or its oxide with the corresponding bromoporphyrins. Compounds {MDPP-[P(O)Ph2]n} (M = H2, Ni, Zn; H2DPP = 5,15-diphenylporphyrin; n = 1, 2) were isolated in yields of 60-95%. The reaction is believed to proceed via the conventional oxidative addition, phosphination and reductive elimination steps, as the stoichiometric reaction of η1-palladio(II) porphyrin [PdBr(H2DPP)(dppe)] (H2DPP = 5,15-diphenylporphyrin; dppe = 1,2-bis(diphenylphosphino)ethane) with diphenylphosphine oxide also results in the desired mono-porphyrinylphosphine oxide [H2DPP-P(O)Ph2]. Attempts to isolate the tertiary phosphines failed due to their extreme air-sensitivity. Variable temperature 1H NMR studies of [H2DPP-P(O)Ph2] revealed an intrinsic lack of symmetry, while fluorescence spectroscopy showed that the phosphine oxide group does not behave as a "heavy atom" quencher. The electron withdrawing effect of the phosphine oxide group was confirmed by voltammetry. The ligands were characterised by multinuclear NMR and UV-visible spectroscopy as well as mass spectrometry. Single crystal X-ray crystallography showed that the bis(phosphine oxide) nickel(II) complex {[NiDPP-[P(O)Ph2]2} is monomeric in the solid state, with a ruffled porphyrin core and the two P=O fragments on the same side of the average plane of the molecule. On the other hand, the corresponding zinc(II) complex formed infinite chains through coordination of one Ph2PO substituent to the neighbouring zinc porphyrin through an almost linear P=O---Zn unit, leaving the other Ph2PO group facing into a parallel channel filled with disordered water molecules. These new phosphine oxides are attractive ligands for supramolecular porphyrin chemistry.

Nanostructured metal oxides as adsorbents and photocatalysts

This research underlines the extensive application of nanostructured metal oxides in environmental systems such as hazardous waste remediation and water purification. This study tries to forge a new understanding of the complexity of adsorption and photocatalysis in the process of water treatment. Sodium niobate doped with a different amount of tantalum, was prepared via a hydrothermal reaction and was observed to be able to adsorb highly hazardous bivalent radioactive isotopes such as Sr2+ and Ra2+ions. This study facilitates the preparation of Nb-based adsorbents for efficiently removing toxic radioactive ions from contaminated water and also identifies the importance of understanding the influence of heterovalent substitution in microporous frameworks. Clay adsorbents were prepared via a two-step method to remove anionic and non-ionic herbicides from water. Firstly, layered beidellite clay was treated with acid in a hydrothermal process; secondly, common silane coupling agents, 3-chloro-propyl trimethoxysilane or triethoxy silane, were grafted onto the acid treated samples to prepare the adsorption materials. In order to isolate the effect of the clay surface, we compared the adsorption property of clay adsorbents with ƒ×-Al2O3 nanofibres grafted with the same functional groups. Thin alumina (£^-Al2O3) nanofibres were modified by the grafting of two organosilane agents 3-chloropropyltriethoxysilane and octyl triethoxysilane onto the surface, for the adsorptive removal of alachlor and imazaquin herbicides from water. The formation of organic groups during the functionalisation process established super hydrophobic sites along the surfaces and those non-polar regions of the surfaces were able to make close contact with the organic pollutants. A new structure of anatase crystals linked to clay fragments was synthesised by the reaction of TiOSO4 with laponite clay for the degradation of pesticides. Based on the Ti/clay ratio, these new catalysts showed a high degradation rate when compared with P25. Moreover, immobilized TiO2 on laponite clay fragments could be readily separated out from a slurry system after the photocatalytic reaction. Using a series of partial phase transition methods, an effective catalyst with fibril morphology was prepared for the degradation of different types of phenols and trace amount of herbicides from water. Both H-titanate and TiO2-(B) fibres coated with anatase nanocrystal were studied. When compared with a laponite clay photocatalyst, it was found that anatase dotted TiO2-(B) fibres prepared by a 45 h hydrothermal treatment followed by calcination were not only superior in performance in photocatalysis but could also be readily separated from a slurry system after photocatalytic reactions. This study has laid the foundation for the development of the ability to fabricate highly efficient nanostructured solids for the removal of radioactive ions and organic pollutants from contaminated water. These results now seem set to contribute to the development of advanced water purification devices in the future. These modified nanostructured materials with unusual properties have broadened their application range beyond their traditional use as adsorbents, to also encompass the storage of nuclear waste after concentrating from contaminated water.

Nanowires of metal oxides for gas sensing applications

Nanowires of different metal oxides (SnO2, ZnO) have been grown by evaporation-condensation process. Their chemical composition has been investigated by using XPS. The standard XPS quantification through main photoelectron peaks, modified Auger parameter and valence band spectra were examined for the accurate determination of oxidation state of metals in the nanowires. Morphological investigation has been conducted by acquiring and analyzing the SEM images. For the simulation of working conditions of sensor, the samples were annealed in ultra high vacuum (UHV) up to 500°C and XPS analysis repeated after this treatment. Finally, the nanowires of SnO 2 have were used to produce a novel gas sensor based on Pt/oxide/SiC structure and operating as Schottky diode. Copyright © 2008 John Wiley & Sons, Ltd.

Reduction of functionalized graphite oxides by trioctylphosphine in non-polar organic solvents

Graphene, functionalized with oleylamine (OA) and soluble in non-polar organic solvents, was produced on a large scale with a high yield by combining the Hummers process for graphite oxidation, an amine-coupling process to make OA-functionalized graphite oxide (OA-GO), and a novel reduction process using trioctylphosphine (TOP). TOP acts as both a reducing agent and an aggregation-prevention surfactant in the reduction of OA-GO in 1,2-dichlorobenzene (DCB). The reduction of OA-GO is confirmed by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and Raman spectroscopy. The exfoliation of GO, OA GO, and OA-functionalized graphene (OA-G) is verified by atomic force microscopy. The conductivity of TOP-reduced OA G, which is deduced from the current–voltage characteristics of a vacuum-filtered thin film, shows that the reduction of functionalized GO by TOP is as effective as the reduction of GO by hydrazine.

Molecular dynamics studies of the effects of branching characteristics on the crystalline structure of polyethylene

Molecular dynamics simulations were carried out on single chain models of linear low-density polyethylene in vacuum to study the effects of branch length, branch content, and branch distribution on the polymer’s crystalline structure at 300 K. The trans/gauche (t/g) ratios of the backbones of the modeled molecules were calculated and utilized to characterize their degree of crystallinity. The results show that the t/g ratio decreases with increasing branch content regardless of branch length and branch distribution, indicating that branch content is the key molecular parameter that controls the degree of crystallinity. Although t/g ratios of the models with the same branch content vary, they are of secondary importance. However, our data suggests that branch distribution (regular or random) has a significant effect on the degree of crystallinity for models containing 10 hexyl branches/1,000 backbone carbons. The fractions of branches that resided in the equilibrium crystalline structures of the models were also calculated. On average, 9.8% and 2.5% of the branches were found in the crystallites of the molecules with ethyl and hexyl branches while C13 NMR experiments showed that the respective probabilities of branch inclusion for ethyl and hexyl branches are 10% and 6% [Hosoda et al., Polymer 1990, 31, 1999–2005]. However, the degree of branch inclusion seems to be insensitive to the branch content and branch distribution.

Interstellar titanium-oxides in interplanetary dust

Interstellar gas abundances (Clayton et al., 1986) suggest that titanium may be bound up in dust and indeed, excess titanium in carbonaceous chondrites is attributed to mixing of interstellar and Solar System materials (Morton, 1974). Fine-grained chondritic interplanetary dust particles (lOPs) of cometary origin are relatively pristine early Solar System materials (Mackinnon and Rietmeijer, 1987; Rietmeijer, 1987) and show chemical and mineralogical signatures related to a pre-solar or nebular origin. For example, large OtH ratios suggest a presolar or interstellar dust component in some chondritic lOPs(Mackinnon and Rietmeijer, 1987). Ti/Si ratios (normalized to bulk CI) in lOPs and carbonaceous chondrite matrices exceed solar abundances but are similar to dust from comet Halley (Jessberger et al., 1987). The Ti-distribution in chondritic lOPs shows major, small-scale « 0.1 urn) variations (Flynn et al., 1978) consistent with heterogeneously distributed Ti-bearingphases. Analytical electron microscope (AEM) studies, in fact, have identified platey grains of Ti-metal, Ti407 and Ti s09 in two different lOPs (Mackinnon and Rietmeijer, 1987). The occurrence of Ti407 was related in situ low-temperature aqueous alteration and therefore implied the presence of BaTi03 (Rietmeijer and Mackinnon, 1984). Yet, the presence ofTis09 in an lOp which shows no evidence of aqueous alteration (Rietmeijer.and McKay, 1986) requires a different interpretation. The distribution of Ti-oxides in chondritic lOPs were investigated with ultra-microtomed thin sections of fluffy chondri tic lOP U2011*B (lSC allocation U2011C2) using a lEOL 2000FX AEM operating at an accelerating voltage of 200kV and with an attached Tracor Northern TN5500 energy dispersive spectrometer.

Synthesis of discrete allyl-functional polyethylene glycol for efficient hydrophilization of dihydr (polydimethylsiloxane)

Amphiphilic poly(ethylene glycol)-block-pol (dimethylsiloxane)-block-poly(ethylene glycol)(PEG-block-PDMS block-PEG) triblock copolymers have been successfully prepared via hydrosilylation using discrete and polydisperse PEG of various chain lengths. Facile synthesis of discrete PEG (dPEG) is achieved via systematic tosylation and etherification of lower glycols. Amphiphilicity of the dPEG block-PDMS-block-dPEG triblock copolymer is illustrated by dynamic light scattering (DLS) and measurement of the critical micelle concentration (CMC).

The effect of polystyrene sodium sulfonate grafting on polyethylene terephthalate artificial ligaments on in vitro mineralisation and in vivo bone tissue integration

This study investigates the impact of polystyrene sodium sulfonate (PolyNaSS) grafting onto the osseo-integration of a polyethylene terephthalate artificial ligament (Ligament Advanced Reinforcement System, LARS™) used for Anterior Cruciate Ligament (ACL). The performance of grafted and non-grafted ligaments was assessed in vitro by culturing human osteoblasts under osteogenic induction and this demonstrated that the surface modification was capable of up-regulating the secretion of ALP and induced higher level of mineralisation as measured 6 weeks post-seeding by Micro-Computed Tomography. Grafted and non-grafted LARS™ were subsequently implanted in an ovine model for ACL reconstruction and the ligament-to-bone interface was evaluated by histology and biomechanical testings 3 and 12 months post-implantation. The grafted ligaments exhibited more frequent direct ligament-to-bone contact and bone formation in the core of the ligament at the later time point than the non-grafted specimens, the grafting also significantly reduced the fibrous encapsulation of the ligament 12 months post-implantation. However, this improved osseo-integration was not translated into a significant increase in the biomechanical pull-out loads. These results provide evidences that PolyNaSS grafting improved the osseo-integration of the artificial ligament within the bone tunnels. This might positively influence the outcome of the surgical reconstructions, as higher ligament stability is believed to limit micro-movement and therefore permits earlier and enhanced healing.

Process and catalysts for the methanation of oxides of carbon

The present invention is directed to catalysts for the conversion of oxides of carbon to methane and/or other hydrocarbons and to precursors of such catalysts. The catalyst precursors include one or more refractory oxides selected from the group consisting of rare earth oxides and rare earth contg. perovskites, the precursor including nickel or nickel cations sufficient for a catalyst obtainable by reducing the precursor to be capable of at least partially reducing an oxide of carbon to a hydrocarbon product. Processes for the prepn. of such catalysts and catalyst precursors are also disclosed, as are processes for the conversion of oxides of carbon to methane and/or other hydrocarbons. [on SciFinder(R)]

Method of making metal oxides

A method for producing particles having at least regions of at least one metal oxide having nano-sized grains comprises providing particles of material having an initial, non-equiaxed particle shape, making a mixture of the particles of material and one or more precursors of the metal oxide, and treating the mixture such that the one or more precursors of the metal oxide react with the particles of material to thereby form at least regions of metal oxide on or within the particles, wherein atoms from the particles of material form part of a matrix of the at least one metal oxide and the at least one metal oxide has nano-sized grains and wherein at least some of the regions of metal oxide on or within the particles have a non-equiaxed grain shape.