889 resultados para Twin coronet porphyrins


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A committee of the Mars Exploration Program Analysis Group (MEPAG) has reviewed and updated the description of Special Regions on Mars as places where terrestrial organisms might replicate (per the COSPAR Planetary Protection Policy). This review and update was conducted by an international team (SR-SAG2) drawn from both the biological science and Mars exploration communities, focused on understanding when and where Special Regions could occur. The study applied recently available data about martian environments and about terrestrial organisms, building on a previous analysis of Mars Special Regions (2006) undertaken by a similar team. Since then, a new body of highly relevant information has been generated from the Mars Reconnaissance Orbiter (launched in 2005) and Phoenix (2007) and data from Mars Express and the twin Mars Exploration Rovers (all 2003). Results have also been gleaned from the Mars Science Laboratory (launched in 2011). In addition to Mars data, there is a considerable body of new data regarding the known environmental limits to life on Earth—including the potential for terrestrial microbial life to survive and replicate under martian environmental conditions. The SR-SAG2 analysis has included an examination of new Mars models relevant to natural environmental variation in water activity and temperature; a review and reconsideration of the current parameters used to define Special Regions; and updated maps and descriptions of the martian environments recommended for treatment as “Uncertain” or “Special” as natural features or those potentially formed by the influence of future landed spacecraft. Significant changes in our knowledge of the capabilities of terrestrial organisms and the existence of possibly habitable martian environments have led to a new appreciation of where Mars Special Regions may be identified and protected. The SR-SAG also considered the impact of Special Regions on potential future human missions to Mars, both as locations of potential resources and as places that should not be inadvertently contaminated by human activity. Key Words: Martian environments—Mars astrobiology—Extreme environment microbiology—Planetary protection—Exploration resources. Astrobiology 14, 887–968.

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Grinding solid reagents under solvent-free or low-solvent conditions (mechanochemistry) is emerging as a general synthetic technique which is an alternative to conventional solvent-intensive methods. However, it is essential to find ways to scale-up this type of synthesis if its promise of cleaner manufacturing is to be realised. Here, we demonstrate the use of twin screw and single screw extruders for the continuous synthesis of various metal complexes, including Ni(salen), Ni(NCS)(2)(PPh3)(2) as well as the commercially important metal organic frameworks (MOFs) Cu-3(BTC)(2) (HKUST-1), Zn(2-methylimidazolate)(2) (ZIF-8, MAF-4) and Al(fumarate)(OH). Notably, Al(fumarate)(OH) has not previously been synthesised mechanochemically. Quantitative conversions occur to give products at kg h(-1) rates which, after activation, exhibit surface areas and pore volumes equivalent to those of materials produced by conventional solvent-based methods. Some reactions can be performed either under completely solvent-free conditions whereas others require the addition of small amounts of solvent (typically 3-4 mol equivalents). Continuous neat melt phase synthesis is also successfully demonstrated by both twin screw and single screw extrusion for ZIF-8. The latter technique provided ZIF-8 at 4 kg h(-1). The space time yields (STYs) for these methods of up to 144 x 10(3) kg per m(3) per day are orders of magnitude greater than STYs for other methods of making MOFs. Extrusion methods clearly enable scaling of mechanochemical and melt phase synthesis under solvent-free or low-solvent conditions, and may also be applied in synthesis more generally.

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While investigating the destruction of the cyanobacterial hepatotoxin microcystin-LR in the presence of phycocyanin pigment via semiconductor photocatalysis, it became apparent that the pigment was catalysing the toxin decomposition. The mechanism of this process in terms of phycocyanin acting as a photo-oxygenation sensitizer via singlet oxygen and superoxide attack is explored. The absorption and fluorescence spectra of phycocyanin have been obtained and data on the properties of the excited state calculated. The established photo-oxygenation sensitizer rose bengal was also used as a catalyst for the photolytic decomposition of microcystin-LR to help elucidate the decomposition mechanism. 

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Graphene, due to its outstanding properties, has become the topic of much research activity in recent years. Much of that work has been on a laboratory scale however, if we are to introduce graphene into real product applications it is necessary to examine how the material behaves under industrial processing conditions. In this paper the melt processing of polyamide 6/graphene nanoplatelet composites via twin screw extrusion is investigated and structure–property relationships are examined for mechanical and electrical properties. Graphene nanoplatelets (GNPs) with two aspect ratios (700 and 1000) were used in order to examine the influence of particle dimensions on composite properties. It was found that the introduction of GNPs had a nucleating effect on polyamide 6 (PA6) crystallization and substantially increased crystallinity by up to 120% for a 20% loading in PA6. A small increase in crystallinity was observed when extruder screw speed increased from 50 rpm to 200 rpm which could be attributed to better dispersion and more nucleation sites for crystallization. A maximum enhancement of 412% in Young's modulus was achieved at 20 wt% loading of GNPs. This is the highest reported enhancement in modulus achieved to date for a melt mixed thermoplastic/GNPs composite. A further result of importance here is that the modulus continued to increase as the loading of GNPs increased even at 20 wt% loading and results are in excellent agreement with theoretical predictions for modulus enhancement. Electrical percolation was achieved between 10–15 wt% loading for both aspect ratios of GNPs with an increase in conductivity of approximately 6 orders of magnitude compared to the unfilled PA6.

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In this paper, the processing and characterization of Polyamide 6 (PA6) / graphite nanoplatelets
(GNPs) composites is reported. PA6/GNPs composites were prepared by melt-mixing using an
industrial, co-rotating, intermeshing, twin-screw extruder. A bespoke screw configuration was used
that was designed in-house to enhance nanoparticle dispersion into a polymer matrix. The effects of
GNPs type (xGnP® M-5 and xGnP® C-500), GNPs content, and extruder screw speed on the bulk
properties of the PA6/GNPs nanocomposites were investigated. Results show a considerable
improvement in the thermal and mechanical properties of PA6/GNPs composites, as compared with
the unfilled PA6 polymer. An increase in crystallinity (%Xc) with increasing GNPs content, and a
change in shape of the crystallization exotherms (broadening) and melting endotherms, both suggest a
change in the crystal type and perfection. An increase in tensile modulus of as much as 376% and
412% was observed for PA6/M-5 xGnP® and PA6/C-500 xGnP® composites, respectively, at filler
contents of 20wt%. The enhancement of Young’s modulus and yield stress can be attributed to the
reinforcing effect of GNPs and their uniform dispersion in the PA6 matrix. The rheological response
of the composite resembles that of a ‘pseudo-solid’, rather than a molten liquid, and analysis of the
rheological data indicates that a percolation threshold was reached at GNPs contents of between 10–
15wt%. The electrical conductivity of the composite also increased with increasing GNPs content,
with an addition of 15wt% GNPs resulting in a 6 order-of-magnitude increase in conductivity. The
electrical percolation thresholds of all composites were between 10–15wt%.

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In this paper, the processing and characterization of Polyamide 6 (PA6) nanocomposites containing graphite nanoplatelets (GNPs) is reported. PA6 nanocomposites were prepared by melt-mixing using an industrial, co-rotating, intermeshing, twin-screw extruder. A bespoke screw configuration was used that was designed in-house to enhance nanoparticle dispersion into a polymer matrix. The effects of nano-filler type (xGnPTM M-5 and xGnPTM C-500), nano-filler content, and extruder screw speed on the bulk properties of the PA6 nanocomposites were investigated. The crystalline structures of PA6 nanocomposites are related to thermal treatment, stress history and the presence of moisture and nanofillers. DSC, Raman and XRD studies show an increase in crystallinity with increasing GNP content and a phase transformation between α-form to γ-form crystals as a result of the heterophase nucleation effect. The effect of uniaxial stretching on PA6 nanocomposites was investigated by drawing specimens heated at temperatures below the melting temperature. DSC and Raman studies on the drawn samples show an increase in yield stress as the GNP content increases due to the strain induced crystallization and γ—β transition during stretching. The rheological response of the nanocomposites resemble that of a ‘pseudo-solid’, rather than a molten liquid, and analysis of the rheological data indicates that a percolation threshold was reached at GNP contents of between 10–15wt%. An increase in tensile modulus of as much as 412% was observed for PA6/C-500 xGnPTM composites, at a filler content of 20wt%. The enhancement of Young’s modulus and yield stress can be attributed to the reinforcing effect of GNPs and their uniform dispersion in the PA6 matrix. The electrical conductivity of the composite also increased with increasing GNP content, with an addition of 15wt% GNP resulting in a 6 order-of-magnitude increase in conductivity. The effects of uniaxial-drawing and the inclusion of multiple nano-filler varieties on the electrical and mechanical properties are currently under investigation.

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National park models have evolved in tandem with the emergence of a multifunctional countryside. Sustainable development has been added to the traditional twin aims of conservation and recreation. This is typified by recent national park designations, such as the Cairngorms National Park in Scotland. A proposed Mournes national park in Northern Ireland has evolved a stage further with a model of national park to deliver national economic goals envisaged by government. This seeks to commodify the natural landscape. This paper compares Cairngorm and Mourne stakeholders’ views on the principal features of both models: park aims, management structures and planning functions. While Cairngorm stakeholders were largely positive from the outset, the model of national park introduced is not without criticism. Conversely, Mourne stakeholders have adopted an anti-national park stance. Nevertheless, the model of national park proposed possessing a strong economic imperative, an absence of the Sandford Principle as a means to manage likely conflicts, and lacking any planning powers in its own right, may still be insufficient to bring about widespread support for a Mourne national park. Such a model is also likely to accelerate the degradation of the Mourne landscape. Competing national identities (British and Irish) provide an additional dimension to the national park debate in Northern Ireland. Deep ideological cleavages are capable of derailing the introduction of a national park irrespective of the model proposed. In Northern Ireland the national park debate is not only about reconciling environmental and economic interests but also political and ethno-national differences.

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Melt-mixed high density polyethylene (HDPE)/multi-walled carbon nanotube (MWCNT) nanocomposites with 1–10 wt% MWCNTs were prepared by twin screw extrusion and compression moulded into sheet form. The compression moulded nanocomposites exhibit a 112% increase in modulus at a MWCNT loading of 4 wt%, and a low electrical percolation threshold of 1.9 wt%. Subsequently, uniaxial, sequential (seq-) biaxial and simultaneous (sim-) biaxial stretching of the virgin HDPE and nanocomposite sheets was conducted at different strain rates and stretching temperatures to investigate the processability of HDPE with the addition of nanotubes and the influence of deformation on the structure and final properties of nanocomposites. The results show that the processability of HDPE is improved under all the uniaxial and biaxial deformation conditions due to a strengthened strain hardening behaviour with the addition of MWCNTs. Extensional deformation is observed to disentangle nanotube agglomerates and the disentanglement degree is shown to depend on the stretching mode, strain rate and stretching temperatures applied. The disentanglement effectiveness is: uniaxial stretching < sim-biaxial stretching < seq-biaxial stretching, under the same deformation parameters. In sim-biaxial stretching, reducing the strain rate and stretching temperature can lead to more nanotube agglomerate breakup. Enhanced nanotube agglomerate disentanglement exhibits a positive effect on the mechanical properties and a negative effect on the electrical properties of the deformed nanocomposites. The ultimate stress of the composite containing 4 wt% MWCNTs increased by ∼492% after seq-biaxial stretching, while the resistivity increased by ∼1012 Ω cm.

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High density polyethylene (HDPE)/multi-walled carbon nanotube (MWCNT) nanocomposites were prepared by melt mixing using twin-screw extrusion. The extruded pellets were compression moulded at 200°C for 5min followed by cooling at different cooling rates (20°C/min and 300°C/min respectively) to produce sheets for characterization. Scanning electron microscopy (SEM) shows that the MWCNTs are uniformly dispersed in the HDPE. At 4 wt% addition of MWCNTs composite modulus increased by over 110% compared with the unfilled HDPE (regardless of the cooling rate). The yield strength of both unfilled and filled HDPE decreased after rapid cooling by about 10% due to a lower crystallinity and imperfect crystallites. The electrical percolation threshold of composites, irrespective of the cooling rate, is between a MWCNT concentration of 1∼2 wt%. Interestingly, the electrical resistivity of the rapidly cooled composite with 2 wt% MWCNTs is lower than that of the slowly cooled composites with the same MWCNT loading. This may be due to the lower crystallinity and smaller crystallites facilitating the formation of conductive pathways. This result may have significant implications for both process control and the tailoring of electrical conductivity in the manufacture of conductive HDPE/MWCNT nanocomposites.

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The garment we now recognise as the Aran jumper emerged as an international symbol of Ireland from the twin twentieth century transatlantic flows of migration and tourism. Its power as a heritage object derives from: 1) the myth commonly associated with the object, in which the corpse of a drowned fisherman is identified and claimed by his family due to the stitch patterns of his jumper (Pádraig Ó Síochain 1962; Annette Lynch and Mitchell Strauss 2014); 2) the meanings attached to those stitch patterns, which have been read, for example, as genealogical records, representations of the natural landscape and references to Christian and pre-Christian ‘Celtic’ religion (Heinz Kiewe 1967; Catherine Nash 1996); and 3) booming popular interest in textile heritage on both sides of the Atlantic, fed by the reframing of domestic crafts such as knitting as privileged leisure pursuits (Rachel Maines 2009; Jo Turney 2009). The myth of the drowned fisherman plays into transatlantic migration narratives of loss and reclamation, promising a shared heritage that needs only to be decoded. The idea of the garment’s surface acting as text (or map) situates it within a preliterate idyll of romantic primitivism, while obscuring the circumstances of its manufacture. The contemporary resurgence in home textile production as recreation, mediated through transnational online networks, creates new markets for heritage textile products while attracting critical attention to the processes through which such objects, and mythologies, are produced. The Aran jumper’s associations with kinship, domesticity and national character make it a powerful tool in the promotion of ancestral (or genealogical) tourism, through marketing efforts such as The Gathering 2013. Nash’s (2010; 2014) work demonstrates the potential for such touristic encounters to disrupt and enrich public conceptions of heritage, belonging and relatedness. While the Aran jumper has been used to commodify a simplistic sense of mutuality between Ireland and north America, it carries complex transatlantic messages in both directions.

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Among various technologies to tackle the twin challenges of sustainable energy supply and climate change, energy saving through advanced control plays a crucial role in decarbonizing the whole energy system. Modern control technologies, such as optimal control and model predictive control do provide a framework to simultaneously regulate the system performance and limit control energy. However, few have been done so far to exploit the full potential of controller design in reducing the energy consumption while maintaining desirable system performance. This paper investigates the correlations between control energy consumption and system performance using two popular control approaches widely used in the industry, namely the PI control and subspace model predictive control. Our investigation shows that the controller design is a delicate synthesis procedure in achieving better trade-o between system performance and energy saving, and proper choice of values for the control parameters may potentially save a significant amount of energy

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Shape stabilised phase change materials (SSPCMs) based on a high density poly(ethylene)(hv-HDPE) with high (H-PW, Tm = 56–58 °C) and low (L-PW, Tm = 18–23 °C) melting point paraffin waxes were readily prepared using twin-screw extrusion. The thermo-physical properties of these materials were assessed using a combination of techniques and their suitability for latent heat thermal energy storage (LHTES) assessed. The melt processing temperature (160 °C) of the HDPE used was well below the onset of thermal decomposition of H-PW (220 °C), but above that for L-PW (130 °C), although the decomposition process extended over a range of 120 °C and the residence time of L-PW in the extruder was <30 s. The SSPCMs prepared had latent heats up to 89 J/g and the enthalpy values for H-PW in the respective blends decreased with increasing H-PW loading, as a consequence of co-crystallisation of H-PW and hv-HDPE. Static and dynamic mechanical analysis confirmed both waxes have a plasticisation effect on this HDPE. Irrespective of the mode of deformation (tension, flexural, compression) modulus and stress decreased with increased wax loading in the blend, but the H-PW blends were mechanically superior to those with L-PW.

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PTF11iqb was initially classified as a TypeIIn event caught very early after explosion. It showed narrow Wolf-Rayet (WR) spectral features on day 2, but the narrow emission weakened quickly and the spectrum morphed to resemble those of Types II-L and II-P. At late times, Halpha emission exhibited a complex, multipeaked profile reminiscent of SN1998S. In terms of spectroscopic evolution, we find that PTF11iqb was a near twin of SN~1998S, although with weaker interaction with circumstellar material (CSM) at early times, and stronger CSM interaction at late times. We interpret the spectral changes as caused by early interaction with asymmetric CSM that is quickly (by day 20) enveloped by the expanding SN ejecta photosphere, but then revealed again after the end of the plateau when the photosphere recedes. The light curve can be matched with a simple model for weak CSM interaction added to the light curve of a normal SN~II-P. This plateau requires that the progenitor had an extended H envelope like a red supergiant, consistent with the slow progenitor wind speed indicated by narrow emission. The cool supergiant progenitor is significant because PTF11iqb showed WR features in its early spectrum --- meaning that the presence of such WR features in an early SN spectrum does not necessarily indicate a WR-like progenitor. [abridged] Overall, PTF11iqb bridges SNe~IIn with weaker pre-SN mass loss seen in SNe II-L and II-P, implying a continuum between these types.

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Composites of Linear Low Density Polyethylene (LLDPE) and Graphene Nanoplatelets (GNPs) were processed using a twin screw extruder under different extrusion conditions. The effects of screw speed, feeder speed and GNP content on the electrical, thermal and mechanical properties of composites were investigated. The inclusion of GNPs in the matrix improved the thermal stability and conductivity by 2.7% and 43%, respectively. The electrical conductivity improved from 10−11 to 10−5 S/m at 150 rpm due to the high thermal stability of the GNPs and the formation of phonon and charge carrier networks in the polymer matrix. Higher extruder speeds result in a better distribution of the GNPs in the matrix and a significant increase in thermal stability and thermal conductivity. However, this effect is not significant for the electrical conductivity and tensile strength. The addition of GNPs increased the viscosity of the polymer, which will lead to higher processing power requirements. Increasing the extruder speed led to a reduction in viscosity, which is due to thermal degradation and/or chain scission. Thus, while high speeds result in better dispersions, the speed needs to be optimized to prevent detrimental impacts on the properties.