939 resultados para ethylene cracking
Resumo:
There is much talk of =the crisis‘ in higher education, often expressed in fatalistic narratives about the (im)possibility of critical resistance or alternatives to the deepening domination of neoliberal rationality and capitalist power throughout social life. But how precisely are we to make sense of this situation? In what ways is it experienced? And what knowledges and practices may help us to respond? These questions form the basis for a series of explorations of the history and character of this crisis, the particular historical conjuncture that we occupy today, and the different types of theoretical analysis and political response it seems to be engendering. Our talk will explore the tensions between readings of the situation as a paralyzing experience of domination, loss and impossibility, on the one hand, and radical transformation and the opening of future possibilities, on the other. We will finally consider what implications new forms of political theory being created in the new student movements have for reconceptualising praxis in higher education today, and perhaps for a wider imagination of post-capitalist politics.
Resumo:
The main aim of this work was two fold, firstly to investigate the effect of a highly reactive comonomer, divinylbenzene (DVB), on the extent of melt grafting of glycidyl methacrylate (GMA) on ethylene-propylene rubber (EPR) using 2,5-dimethyl-2,5-bis-(tert-butyl peroxy) hexane (Trigon ox 101, Tl 01) as a free radical initiator, and to compare the results with a conventional grafting of the same monomer on EPR. To achieve this, the effect of processing conditions and chemical composition including the concentration of peroxide, GMA and DVB on the extent of grafting was investigated. The presence of the comonomer (DVB) in the grafting process resulted in a significant increase in the extent of the grafting using only a small concentration of peroxide. It was also found that the extent of grafting increased drastically with increasing the DVB concentration. Interestingly, in the comonomer system, the extent of the undesired side reaction, normally the homopolymerisation of GMA (polyGMA) was shown to have reduced tremendously and in most cases the level of polyGMA was immeasurable in the samples. Compared to a conventional EPR-g-GMACONV (in the absence of a comonomer), the presence of the comonomer DVB in the grafting system was shown to result in more branching and crosslinking (shown from an increase in melt flow index (MFI) and torque values) and this was paralleled by an increase in DVB concentration. In contrast, the extent of grafting in conventional system increased with increasing the peroxide concentration but the level of grafting was much lower than in the case of DVB. Homopolymerisation of GMA and excessive crosslinking of EPR became dominant at high peroxide concentration and this. reflects that the side reactions were favorable in the conventional grafting system. The second aim was to examine the effect of the in-situ functionalised EPR when used as a compatibiliser for binary blends. It was found that blending PET with functionalised EPR (ƒ-EPR) gave a significant improvement in terms of blend morphology as well as mechanical properties. The results showed clearly that, blending PET with ƒ-EPRDVB (prepared with DVB) was much more effective compared to the corresponding PET/ƒ-EPRCONV (without DVB) blends in which ƒ-EPRDVB having optimum grafting level of 2.1 wt% gave the most pronounced effect on the morphology and mechanical properties. On the other hand, blends of PET/ƒ-EPRDVB containing high GMA/DVB ratio was found to be unfavorable hence exhibited lower tensile properties and showed unfavorable morphology. The presence of high polyGMA concentration in ƒ-EPRCONV was found to create damaging effect on its morphology, hence resulting in reduced tensile properties (e.g. low elongation at break). However, the use of commercial terpolymers based on ethylene-methacrylate-glycidyl methacrylate (EM-GMA)or a copolymer of ethylene-glycidyl methacrylate (E-GMA) containing various GMA levels as compatibilisers in PET/EPR blends was found to be more efficient compared to PET/EPR/ƒ-EPR blends with the former blends showing finer morphology and high elongation at break. The high efficiency of the terpolymers or copolymers in compatibilising the PET/EPR blends is suggested to be partly, higher GMA content compared to the amount in ƒ-EPR and due to its low viscosity.
Resumo:
The melt stabilising efficiency of antioxidants with different structures based on hindered phenols, phosphite esters, phosphonite and a lactone was examined during multi-pass extrusions at 265 °C in three metallocene ethylene-1-octene copolymers (m-LLDPE) having different extent of short chain branching (SCB) and one Zeigler copolymer (z-LLDPE) containing the same level of SCB corresponding to one of the m-LLDPE polymers. The effect of the different antioxidants, when used separately and in combination, was investigated by characterising the changes in the polymer's rheological behaviour, colour formation and structural changes based on unsaturated groups and carbonyl content during five multi-pass extrusions. The results showed that all stabilisation systems examined offered higher efficiency in the metallocene polymers compared to the Zeigler. The effect of the extent of SCB in the metallocene polymers on the stabilising efficacy of the antioxidant systems was also examined, and it was shown that it had a significant effect, with both single and combinations of antioxidants giving higher efficiency in the m-LLDPE polymer containing higher extent of SCB. The presence of the lactone HP136 in mixtures containing hindered phenol–phosphite antioxidant systems gave a higher melt stabilisation efficiency than in its absence and this has been attributed to a co-operative antioxidant reaction steps that take place between the antioxidants resulting in the possible regeneration of the lactone antioxidant through a redox reaction. In all the metallocene PE polymers examined, the biologically hindered phenol, Irganox E, was shown to be more effective than the conventionally hindered phenol Irganox 1076, when examined alone or in combination with phosphite esters.
Resumo:
We have studied the kinetics of the phase-separation process of mixtures of colloid and protein in solutions by real-time UV-vis spectroscopy. Complementary small-angle X-ray scattering (SAXS) was employed to determine the structures involved. The colloids used are gold nanoparticles functionalized with protein resistant oligo(ethylene glycol) (OEG) thiol, HS(CH(2))(11)(OCH(2)CH(2))(6)OMe (EG6OMe). After mixing with protein solution above a critical concentration, c*, SAXS measurements show that a scattering maximum appears after a short induction time at q = 0.0322 angstrom(-1) stop, which increases its intensity with time but the peak position does not change with time, protein concentration and salt addition. The peak corresponds to the distance of the nearest neighbor in the aggregates. The upturn of scattering intensities in the low q-range developed with time indicating the formation of aggregates. No Bragg peaks corresponding to the formation of colloidal crystallites could be observed before the clusters dropped out from the solution. The growth kinetics of aggregates is followed in detail by real-time UV-vis spectroscopy, using the flocculation parameter defined as the integral of the absorption in the range of 600-800 nm wavelengths. At low salt addition (<0.5 M), a kinetic crossover from reaction-limited cluster aggregation (RLCA) to diffusion-limited cluster aggregation (DLCA) growth model is observed, and interpreted as being due to the effective repulsive interaction barrier between colloids within the depletion potential. Above 0.5 M NaCl, the surface charge of proteins is screened significantly, and the repulsive potential barrier disappeared, thus the growth kinetics can be described by a DLCA model only.
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We demonstrate that a controllable cracking can be realized in Si with a buried strain layer when hydrogen is introduced using traditional H-ion implantation techniques. However, H stimulated cracking is dependent on H projected ranges; cracking occurs along a Si0.8Ge0.2 strain layer only if the H projected range is shallower than the depth of the strained layer. The absence of cracking for H ranges deeper than the strain layer is attributed to ion-irradiation induced strain relaxation, which is confirmed by Rutherford-backscattering-spectrometry channeling angular scans. The study reveals the importance of strain in initializing continuous cracking with extremely low H concentrations.
Resumo:
The main aim of this work was to investigate the effect of a highly reactive comonomer, divinylbenzene (DVB), on the extent of melt grafting of glycidyl methacrylate (GMA) on ethylene-propylene rubber (EPR) using 2,5-dimethyl-2,5-bis-(tert-butyl peroxy) hexane (Trigonox 101, T101) as a free radical initiator, and to compare the results with a conventional grafting of the same monomer on EPR. To achieve this, the effect of processing conditions and chemical composition including the concentration of peroxide, GMA and DVB on the extent of grafting was investigated. The presence of the comonomer (DVB) in the grafting process resulted in a significant increase in the extent of the grafting using only a small concentration of peroxide. It was also found that the extent of grafting increased drastically with the increasing DVB concentration. Interestingly, in the comonomer system, the extent of the undesired side reaction, normally the homopolymerisation of GMA (polyGMA) was shown to have reduced tremendously and in most cases the level of polyGMA was immeasurable in the samples. In contrast, the extent of grafting in conventional system increased with increasing the peroxide concentration but the level of grafting was much lower than in the case of DVB. Homopolymerisation of GMA and excessive crosslinking of EPR became dominant at high peroxide concentration and this reflects that the side reactions were favourable in the conventional grafting system.
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The effect of organically modified clay on the morphology, rheology and mechanical properties of high-density polyethylene (HDPE) and polyamide 6 (PA6) blends (HDPE/PA6 = 75/25 parts) is studied. Virgin and filled blends were prepared by melt compounding the constituents using a twin-screw extruder. The influence of the organoclay on the morphology of the hybrid was deeply investigated by means of wide-angle X-ray diffractometry, transmission and scanning electron microscopies and quantitative extraction experiments. It has been found that the organoclay exclusively places inside the more hydrophilic polyamide phase during the melt compounding. The extrusion process promotes the formation of highly elongated and separated organoclay-rich PA6 domains. Despite its low volume fraction, the filled minor phase eventually merges once the extruded pellets are melted again, giving rise to a co-continuous microstructure. Remarkably, such a morphology persists for long time in the melt state. A possible compatibilizing action related to the organoclay has been investigated by comparing the morphology of the hybrid blend with that of a blend compatibilized using an ethylene–acrylic acid (EAA) copolymer as a compatibilizer precursor. The former remains phase separated, indicating that the filler does not promote the enhancement of the interfacial adhesion. The macroscopic properties of the hybrid blend were interpreted in the light of its morphology. The melt state dynamics of the materials were probed by means of linear viscoelastic measurements. Many peculiar rheological features of polymer-layered silicate nanocomposites based on single polymer matrix were detected for the hybrid blend. The results have been interpreted proposing the existence of two distinct populations of dynamical species: HDPE not interacting with the filler, and a slower species, constituted by the organoclay-rich polyamide phase, which slackened dynamics stabilize the morphology in the melt state. In the solid state, both the reinforcement effect of the filler and the co-continuous microstructure promote the enhancement of the tensile modulus. Our results demonstrate that adding nanoparticles to polymer blends allows tailoring the final properties of the hybrid, potentially leading to high-performance materials which combine the advantages of polymer blends and the merits of polymer nanocomposites.
Resumo:
Polymer scaffolds play an important role in tissue engineering applications. Poly(ethylene glycol) based hydrogels have received a lot of attention in this field because of their high biocompatibility and ease of processing. However, in many cases they do not exhibit proper tissue invasion and nutrient transport because of their dense structure. In the present work, several approaches were developed and compared to each other to produce interconnected macroporous poly(ethylene glycol) hydrogels by including different types of porogens in the photocrosslinking reaction. The swelling capacity of the resulting hydrogels was analyzed and compared to non-porous hydrogel samples. Moreover, the obtained materials were characterized by means of mechanical properties and porosity using rheometry, scanning electron microscopy, and mercury intrusion porosimetry. Results showed that interconnected and uniform pores were obtained when a porogen template was used during hydrogel fabrication by photocrosslinking. On the other side, when the porogen particles were dispersed into the macromer solution before matrix photocrosslinking the interconnexion was negligible. The templates must be dissolved before the hydrogel's cell-seeding in vitro, while the dispersed porogen can be used in situ in the in vitro seeding tests. Copyright © 2013 Taylor & Francis Group, LLC.
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Hydrogels containing carbon nanotubes (CNTs) are expected to be promising conjugates because they might show a synergic combination of properties from both materials. Most of the hybrid materials containing CNTs only entrap them physically, and the covalent attachment has not been properly addressed yet. In this study, single-walled carbon nanotubes (SWNTs) were successfully incorporated into a poly(ethylene glycol) (PEG) hydrogel by covalent bonds to form a hybrid material. For this purpose, SWNTs were functionalized with poly(ethylene glycol) methacrylate (PEGMA) to obtain water-soluble pegylated SWNTs (SWNT–PEGMA). These functionalized SWNTs were covalently bonded through their PEG moieties to a PEG hydrogel. The hybrid network was obtained from the crosslinking reaction of poly(ethylene glycol) diacrylate prepolymer and the SWNT–PEGMA by dual photo-UV and thermal initiations. The mechanical and swelling properties of the new hybrid material were studied. In addition, the material and lixiviates were analyzed to elucidate any kind of SWNT release and to evaluate a possible in vitro cytotoxic effect. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.
Resumo:
Poly(ethylene oxide) has been coupled to poly(3-hexylthiophene) using esterification to produce pure diblock copolymers, highly relevant for use in organic electronic devices. The new synthetic route described herein uses a metal-free coupling step, for the first time, to afford well-defined polymers in high yields following facile purification.
Resumo:
Synthetic hydrogel polymers were prepared by free radical photopolymerization in aqueous solution of the sodium salt of 2-acrylamido-2-methylpropane sulfonic acid (Na-AMPS). Poly(ethylene glycol) diacrylate (PEGDA) and 4,4'-azo-bis(4-cyanopentanoic acid) were used as the crosslinker and UV-photoinitiator, respectively. The effects of varying the Na-AMPS monomer concentration within the range of 30-50% w/v and the crosslinker concentration within the range of 0.1-1.0% mol (relative to monomer) were studied in terms of their influence on water absorption properties. The hydrogel sheets exhibited extremely high swelling capacities in aqueous media which were dependent on monomer concentration, crosslink density, and the ionic strength and composition of the immersion medium. The effects of varying the number-average molecular weight of the PEGDA crosslinker from = 250 to 700 were also investigated. Interestingly, it was found that increasing the molecular weight and therefore the crosslink length at constant crosslink density decreased both the rate of water absorption and the equilibrium water content. Cytotoxicity testing by the direct contact method with mouse fibroblast L929 cells indicated that the synthesized hydrogels were nontoxic. On the basis of these results, it is considered that photopolymerized Na-AMPS hydrogels crosslinked with PEGDA show considerable potential for biomedical use as dressings for partial thickness burns. This paper describes some structural effects which are relevant to their design as biomaterials for this particular application. © 2013 Copyright Taylor and Francis Group, LLC.
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Pulsating; tension fatigue tests have been carried out on edge notched specimens of a mild steel. An electrical potential drop technique was used to determine the number of cycles taken to initiate cracks and the rate at which the cracks grew across the specimen. The results could be described by the range of stress intensity factor, which for crack initiation was modified to take account of the notch root radius. Analysis of elastic stress distributions at cracks and notches and models of plasticity at crack tips are used to discuss the results. Limited evidence in the literature indicates that the fracture mechanics approach may provide a general description of crack initiation and growth in notched specimens, and a simple graphical method of calculating fatigue lives is described. The results are used to illustrate the effects of specimen size and geometry on the fatigue life of notched specimens. The relevance of the work to the assessment of the significance of defects in welds is discussed.
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The interactions between proteins and gold colloids functionalized with protein-resistant oligo(ethylene glycol) (OEG) thiol, HS(CH(2))(11) (OCH(2)CH(2))(6)OMe (EG(6)OMe), in aqueous solution have been studied by small-angle X-ray scattering (SAXS) and UV-vis spectroscopy. The mean size, 2R, and the size distribution of the decorated gold colloids have been characterized by SAXS. The monolayer-protected gold colloids have no correlations due to the low volume fraction in solution and are stable in a wide range of temperatures (5-70 degrees C, pH (1.3-12.4), and ionic strength (0-1.0 M). In contrast, protein (bovine serum albumin) solutions with concentrations in the range of 60-200 mg/mL (4.6-14.5 vol show a pronounced correlation peak in SAXS, which results from the repulsive electrostatic interaction between charged proteins. These protein interactions show significant dependence on ionic strength, as would be expected for an electrostatic interaction (Zhang et al. J. Phys. Chem. B 2007, 111, 251). For a mixture of proteins and gold colloids, the protein-protein interaction changes little upon mixing with OEG-decorated gold colloids. In contrast, the colloid-colloid interaction is found to be strongly dependent on the protein concentration and the size of the colloid itself. Adding protein to a colloidal solution results in an attractive depletion interaction between functionalized gold colloids, and above a critical protein concentration, c*, the colloids form aggregates and flocculate. Adding salt to such mixtures enhances the depletion effect and decreases the critical protein concentration. The aggregation is a reversible process (i.e., diluting the solution leads to dissolution of aggregates). The results also indicate that the charge of the OEG self-assembled monolayer at a curved interface has a rather limited effect on the colloidal stabilization and the repulsive interaction with proteins.
Resumo:
Metallocene ethylene-1-octene copolymers having different densities and comonomer content ranging from 11 to 36 wt% (m-LLDPE), and a Ziegler copolymer (z-LLDPE) containing the same level of short-chain branching (SCB) corresponding to one of the m-LLDPE polymers, were subjected to extrusion. The effects of temperature (210-285 °C) and multi-pass extrusions (up to five passes) on the rheological and structural characteristics of these polymers were investigated using melt index and capillary rheometry, along with spectroscopic characterisation of the evolution of various products by FTIR, C-NMR and colour measurements. The aim is to develop a better understanding of the effects of processing variables on the structure and thermal degradation of these polymers. Results from rheology show that both extrusion temperature and the amount of comonomer have a significant influence on the polymer melt thermo-oxidative behaviour. At low to intermediate processing temperatures, all m-LLDPE polymers exhibited similar behaviour with crosslinking reactions dominating their thermal oxidation. By contrast, at higher processing temperatures, the behaviour of the metallocene polymers changed depending on the level of comonomer content: higher SCB gave rise to predominantly chain scission reactions whereas polymers with lower level of SCB continued to be dominated by crosslinking. This temperature dependence was attributed to changes in the different evolution of carbonyl and unsaturated compounds including vinyl, vinylidene and trans-vinylene. © 2007 Elsevier Ltd. All rights reserved.
Resumo:
The influence of the comonomer content in a series of metallocene-based ethylene-1-octene copolymers (m-LLDPE) on thermo-mechanical, rheological, and thermo-oxidative behaviours during melt processing were examined using a range of characterisation techniques. The amount of branching was calculated from 13C NMR and studies using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were employed to determine the effect of short chain branching (SCB, comonomer content) on thermal and mechanical characteristics of the polymer. The effect of melt processing at different temperatures on the thermo-oxidative behaviour of the polymers was investigated by examining the changes in rheological properties, using both melt flow and capillary rheometry, and the evolution of oxidation products during processing using infrared spectroscopy. The results show that the comonomer content and catalyst type greatly affect thermal, mechanical and oxidative behaviour of the polymers. For the metallocene polymer series, it was shown from both DSC and DMA that (i) crystallinity and melting temperatures decreased linearly with comonomer content, (ii) the intensity of the ß-transition increased, and (iii) the position of the tan δmax peak corresponding to the a-transition shifted to lower temperatures, with higher comonomer content. In contrast, a corresponding Ziegler polymer containing the same level of SCB as in one of the m-LLDPE polymers, showed different characteristics due to its more heterogeneous nature: higher elongational viscosity, and a double melting peak with broader intensity that occurred at higher temperature (from DSC endotherm) indicating a much broader short chain branch distribution. The thermo-oxidative behaviour of the polymers after melt processing was similarly influenced by the comonomer content. Rheological characteristics and changes in concentrations of carbonyl and the different unsaturated groups, particularly vinyl, vinylidene and trans-vinylene, during processing of m-LLDPE polymers, showed that polymers with lower levels of SCB gave rise to predominantly crosslinking reactions at all processing temperatures. By contrast, chain scission reactions at higher processing temperatures became more favoured in the higher comonomer-containing polymers. Compared to its metallocene analogue, the Ziegler polymer showed a much higher degree of crosslinking at all temperatures because of the high levels of vinyl unsaturation initially present.