The role of organoclay in promoting co-continuous morphology in high-density poly(ethylene)/poly(amide) 6 blends

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.

A low mortality, high morbidity Reduced Intensity Status Epilepticus (RISE) model of epilepsy and epileptogenesis in the rat

Animal models of acquired epilepsies aim to provide researchers with tools for use in understanding the processes underlying the acquisition, development and establishment of the disorder. Typically, following a systemic or local insult, vulnerable brain regions undergo a process leading to the development, over time, of spontaneous recurrent seizures. Many such models make use of a period of intense seizure activity or status epilepticus, and this may be associated with high mortality and/or global damage to large areas of the brain. These undesirable elements have driven improvements in the design of chronic epilepsy models, for example the lithium-pilocarpine epileptogenesis model. Here, we present an optimised model of chronic epilepsy that reduces mortality to 1% whilst retaining features of high epileptogenicity and development of spontaneous seizures. Using local field potential recordings from hippocampus in vitro as a probe, we show that the model does not result in significant loss of neuronal network function in area CA3 and, instead, subtle alterations in network dynamics appear during a process of epileptogenesis, which eventually leads to a chronic seizure state. The model’s features of very low mortality and high morbidity in the absence of global neuronal damage offer the chance to explore the processes underlying epileptogenesis in detail, in a population of animals not defined by their resistance to seizures, whilst acknowledging and being driven by the 3Rs (Replacement, Refinement and Reduction of animal use in scientific procedures) principles.

Investigation of the effects of low energy high dose ion bombardment in metals and compound semiconductors

The effect of low energy nitrogen molecular ion beam bombardment on metals and compound semiconductors has been studied, with the aim to investigate at the effects of ion and target properties. For this purpose, nitrogen ion implantation in aluminium, iron, copper, gold, GaAs and AIGaAs is studied using XPS and Angle Resolve XPS. A series of experimental studies on N+2 bombardment induced compositional changes, especially the amount of nitrogen retained in the target, were accomplished. Both monoenergetic implantation and non-monoenergetic ion implantation were investigated, using the VG Scientific ESCALAB 200D system and a d. c. plasma cell, respectively. When the samples, with the exception of gold, are exposed to air, native oxide layers are formed on the surfaces. In the case of monoenergetic implantation, the surfaces were cleaned using Ar+ beam bombardment prior to implantation. The materials were then bombarded with N2+ beam and eight sets of successful experiments were performed on each sample, using a rastered N2+ ion beam of energy of 2, 3, 4 and 5 keV with current densities of 1 μA/cm2 and 5 μA/cm22 for each energy. The bombarded samples were examined by ARXPS. After each complete implantation, XPS depth profiles were created using Ar+ beam at energy 2 ke V and current density 2 μA/cm2 . As the current density was chosen as one of the parameters, accurate determination of current density was very important. In the case of glow discharge, two sets of successful experiments were performed in each case, by exposing the samples to nitrogen plasma for the two conditions: at low pressure and high voltage and high pressure and low voltage. These samples were then examined by ARXPS. On the theoretical side, the major problem was prediction of the number of ions of an element that can be implanted in a given matrix. Although the programme is essentially on experimental study, but an attempt is being made to understand the current theoretical models, such as SATVAL, SUSPRE and TRIM. The experimental results were compared with theoretical predictions, in order to gain a better understanding of the mechanisms responsible. From the experimental results, considering possible experimental uncertainties, there is no evidence of significant variation in nitrogen saturation concentration with ion energy or ion current density in the range of 2-5 ke V, however, the retention characteristics of implantant seem to strongly depend on the chemical reactivity between ion species and target material. The experimental data suggests the presence of at least one thermal process. The discrepancy between the theoretical and experimental results could be the inability of the codes to account for molecular ion impact and thermal processes.

Using organoclay to promote morphology refinement and co-continuity in high-density polyethylene/polyamide 6 blends - Effect of filler content and polymer matrix composition

We investigate the gradual changes of the microstructure of two blends of high-density polyethylene (HDPE) and polyamide 6 (PA6) at opposite composition filled with increasing amounts of an organomodified clay. The filler locates preferentially inside the polyamide phase, bringing about radical alterations in the micron-scale arrangement of the polymer phases. When the host polyamide represents the major constituent, a sudden reduction of the average sizes of the polyethylene droplets was observed upon addition of even low amounts of organoclay. A morphology refinement was also noticed at low filler contents when the particles distributes inside the minor phase. In this case, however, keep increasing the organoclay content eventually results in a high degree of PA6 phase continuity. Rheological analyses reveal that the filler loading at which the polyamide assembles in a continuous network corresponds to the critical threshold for its rheological transition from a liquid- to a gel-like behaviour, which is indicative of the structuring of the filler inside the host PA6. On the basis of this finding, a schematic mechanism is proposed in which the role of the filler in driving the space arrangement of the polymer phases is discussed. Finally, we show that the synergism between the reinforcing action of the filler and its ability to affect the blend microstructure can be exploited in order to enhance relevant technological properties of the materials, such as their high temperature structural integrity.

Fracture toughness of some high density PM steels

Tensile strengths, impact energies, and fracture toughness data are presented for pure Fe-0.5 C, Astaloy A with 0.2 and 0.6%C, and for Distaloy AB-0.6%C at relative densities of about 0.9, achieved by conventional pressing and sintering, and at close to 1.0, achieved by powder forging. At low relative density, properties are controlled by sizes of sinter necks; it is postulated that toughness scales as (x/a)4, x/a being the ratio of neck diameter to particle diameter. At high relative density, microvoid coalescence and good toughness is observed for low strength microstructures whereas cleavage and poor toughness is a concomitant of high strength.

Sequential pyrolysis of willow SRC at low and high heating rates:implications for selective pyrolysis

The main aim of the work is to investigate sequential pyrolysis of willow SRC using two different heating rates (25 and 1500 °C/min) between 320 and 520 °C. Thermogravimetric analysis (TGA) and pyrolysis - gas chromatography - mass spectroscopy (Py-GC-MS) have been used for this analysis. In addition, laboratory scale processing has been undertaken to compare product distribution from fast and slow pyrolysis at 500 °C. Fast pyrolysis was carried out using a 1 kg/h continuous bubbling fluidized bed reactor, and slow pyrolysis using a 100 g batch reactor. Findings from this study show that heating rate and pyrolysis temperatures have a significant influence on the chemical content of decomposition products. From the analytical sequential pyrolysis, an inverse relationship was seen between the total yield of furfural (at high heating rates) and 2-furanmethanol (at low heating rates). The total yield of 1,2-dihydroxybenzene (catechol) was found to be significant higher at low heating rates. The intermediates of catechol, 2-methoxy-4-(2-propenyl)phenol (eugenol); 2-methoxyphenol (guaiacol); 4-Hydroxy-3,5-dimethoxybenzaldehyde (syringaldehyde) and 4-hydroxy-3-methoxybenzaldehyde (vanillin), were found to be highest at high heating rates. It was also found that laboratory scale processing alters the pyrolysis bio-oil chemical composition, and the proportions of pyrolysis product yields. The GC-MS/FID analysis of fast and slow pyrolysis bio-oils reveals significant differences. © 2011 Elsevier Ltd. All rights reserved.

An assessment of the performance of high density polyethylene copolymers for natural gas distribution pipes

The total thermoplastics pipe market in west Europe is estimated at 900,000 metric tonnes for 1977 and is projected to grow to some 1.3 million tonnes of predominantly PVC and polyolefins pipe by 1985. By that time, polyethylene for gas distribution pipe and fittings will represent some 30% of the total polyethylene pipe market. The performance characteristics of a high density polyethylene are significantly influenced by both molecular weight and type of comonomer; the major influences being in the long-term hoop stress resistance and the environmental stress cracking resistance. Minor amounts of hexene-1 are more effective than comonomers lower in the homologous series, although there is some sacrifice of density related properties. A synergistic improvement is obtained by combining molecular weight increase with copolymerisation. The Long-term design strength of polyethylene copolymers can be determined from hoop stress measurement at elevated temperatures and by means of a separation factor of approximate value 22, extrapolation can be made to room temperature performance for a water environment. A polyethylene of black composition has a sufficiently improved performance over yellow pigmented pipe to cast doubts on the validity of internationally specifying yellow coded pipe for gas distribution service. The chemical environment (condensate formation) that can exist in natural gas distribution networks has a deleterious effect on the pipe performance the reduction amounting to at least two decades in log time. Desorption of such condensate is very slow and the influence of the more aggressive aromatic components is to lead to premature stress cracking. For natural gas distribution purposes, the design stress rating should be 39 Kg/cm2 for polyethylenes in the molecular weight range of 150 - 200,000 and 55 Kg/cm2 for higher molecular weight materials.

Stabilisation and characterisation of peroxide-crosslinked high density polyethylene

DUE TO COPYRIGHT RESTRICTIONS ONLY AVAILABLE FOR CONSULTATION AT ASTON UNIVERSITY LIBRARY WITH PRIOR ARRANGEMENT

Energy conversion assessment of vacuum, slow and fast pyrolysis processes for low and high ash paper waste sludge

The performance of vacuum, slow and fast pyrolysis processes to transfer energy from the paper waste sludge (PWS) to liquid and solid products was compared. Paper waste sludges with low and high ash content (8.5 and 46.7 wt.%) were converted under optimised conditions for temperature and pellet size to maximise both product yields and energy content. Comparison of the gross energy conversions, as a combination of the bio-oil/tarry phase and char (ECsum), revealed that the fast pyrolysis performance was between 18.5% and 20.1% higher for the low ash PWS, and 18.4% and 36.5% higher for high ash PWS, when compared to the slow and vacuum pyrolysis processes respectively. For both PWSs, this finding was mainly attributed to higher production of condensable organic compounds and lower water yields during FP. The low ash PWS chars, fast pyrolysis bio-oils and vacuum pyrolysis tarry phase products had high calorific values (∼18-23 MJ kg-1) making them promising for energy applications. Considering the low calorific values of the chars from alternative pyrolysis processes (∼4-7 MJ kg-1), the high ash PWS should rather be converted to fast pyrolysis bio-oil to maximise the recovery of usable energy products.

Expanding the biomass resource:sustainable oil production via fast pyrolysis of low input high diversity biomass and the potential integration of thermochemical and biological conversion routes

Waste biomass is generated during the conservation management of semi-natural habitats, and represents an unused resource and potential bioenergy feedstock that does not compete with food production. Thermogravimetric analysis was used to characterise a representative range of biomass generated during conservation management in Wales. Of the biomass types assessed, those dominated by rush (Juncus effuses) and bracken (Pteridium aquilinum) exhibited the highest and lowest volatile compositions respectively and were selected for bench scale conversion via fast pyrolysis. Each biomass type was ensiled and a sub-sample of silage was washed and pressed. Demineralization of conservation biomass through washing and pressing was associated with higher oil yields following fast pyrolysis. The oil yields were within the published range established for the dedicated energy crops miscanthus and willow. In order to examine the potential a multiple output energy system was developed with gross power production estimates following valorisation of the press fluid, char and oil. If used in multi fuel industrial burners the char and oil alone would displace 3.9 × 105 tonnes per year of No. 2 light oil using Welsh biomass from conservation management. Bioenergy and product development using these feedstocks could simultaneously support biodiversity management and displace fossil fuels, thereby reducing GHG emissions. Gross power generation predictions show good potential.

The study of ultra-low energy deposition of hydrogenated amorphous carbon thin films

This thesis is dedicated to the production and analysis of thin hydrogenated amorphous carbon films. A cascaded arc plasma source was used to produce a high density plasma of hydrocarbon radicals that deposited on a substrate at ultra low energies. The work was intended to create a better understanding of the mechanisms responsible for the film formation, by an extensive analysis on the properties of the films in correlation with the conditions used in the plasma cell. Two different precursors were used: methane and acetylene. They revealed a very different picture for the mechanism of film formation and properties. Methane was less successful, and the films formed were soft, with poor adhesion to the substrate and decomposing with time. Acetylene was the better option, and the films formed in this case were harder, with better adhesion to the substrate and stable over time. The plasma parameters could be varied to change the character of films, from polymer-like to diamond-like carbon. Films deposited from methane were grown at low deposition rates, which increased with the increase in process pressure and source power and decreased with the increase in substrate temperature and in hydrogen fraction in the carrier gas. The films had similar hydrogen content, sp3 fractions, average roughness (Ra) and low hardness. Above a deposition temperature of 350°C graphitization occurred - an increase in the sp2 fraction. A deposition mechanism was proposed, based upon the reaction product of the dissociative recombination of CH4+. There were small differences between the chemistries in the plasma at low and high precursor flow rates and low and high substrate temperatures; all experimental conditions led to formation of films that were either polymer-like, soft amorphous hydrogenated carbon or graphitic-like in structure. Films deposited from acetylene were grown at much higher deposition rates on different substrates (silicon, glass and plastics). The film quality increased noticeably with the increase of relative acetylene to argon flow rate, up to a certain value, where saturation occurred. With the increase in substrate temperature and the lowering of the acetylene injection ring position further improvements in film quality were achieved. The deposition process was scaled up to large area (5 x 5 cm) substrates in the later stages of the project. A deposition mechanism was proposed, based upon the reaction products of the dissociative recombination of C2H2 +. There were large differences between the chemistry in the plasma at low and medium/high precursor flow rates. This corresponded to large differences in film properties from low to medium flow rates, when films changed their character from polymer-like to diamond-like, whereas the differences between films deposited at medium and high precursor flow rates were small. Modelling of the film growth on silicon substrates was initiated and it explained the formation of sp2 and sp3 bonds at these very low energies. However, further improvements to the model are needed.

Systemic circulatory influences on retinal microvascular function in middle-age individuals with low to moderate cardiovascular risk

Purpose: To investigate the relationship between retinal microvascular reactivity, circulatory markers for CVD risk and systemic antioxidative defence capacity in healthy middle-aged individuals with low to moderate risk of CVD. Methods: Retinal vascular reactivity to flickering light was assessed in 102 healthy participants (46-60 years) by means of dynamic retinal vessel analysis (DVA). Other vascular assessments included carotid intima-media thickness (C-IMT) and blood pressure (BP) measurements. Total cholesterol (CHOL), high-density lipoprotein cholesterol (HDL-C), low-density lipoprotein cholesterol (LDL-C), triglycerides (TG) and blood glutathione levels in its reduced (GSH) and oxidized (GSSG) forms were also determined for each participant, along with Framingham risk scores (FRS). Results: Retinal arterial baseline diameter fluctuation (BDF) was independently, significantly and negatively influenced by LDL-C levels (β = -0.53, p = 0.027). Moreover, the arterial dilation slope (SlopeAD) was independently, significantly and positively associated with redox index (GSH: GSSG ratio, β = 0.28, p = 0.016), while the arterial constriction slope (SlopeAC) was significantly and negatively influenced by blood GSH levels (β = -0.20, p = 0.042), and positively associated with FRS (β = 0.25, p = 0.009). Venous BDF and dilation amplitude (DA) were also negatively influenced by plasma LDL-C levels (β = -0.83, p = 0.013; and β = -0.22, p = 0.028, respectively). Conclusions: In otherwise healthy individuals with low to moderate cardiovascular risk, retinal microvascular dilation and constriction responses to stress levels are influenced by systemic antioxidant capacity, and circulating markers for cardiovascular risk.