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.

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.

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.

Stabilisation and characterisation of peroxide-crosslinked high density polyethylene

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

Step and flash imprint lithography: Fabrication of patterned media for extremely high density magnetic data storage devices

Currently the data storage industry is facing huge challenges with respect to the conventional method of recording data known as longitudinal magnetic recording. This technology is fast approaching a fundamental physical limit, known as the superparamagnetic limit. A unique way of deferring the superparamagnetic limit incorporates the patterning of magnetic media. This method exploits the use of lithography tools to predetermine the areal density. Various nanofabrication schemes are employed to pattern the magnetic material are Focus Ion Beam (FIB), E-beam Lithography (EBL), UV-Optical Lithography (UVL), Self-assembled Media Synthesis and Nanoimprint Lithography (NIL). Although there are many challenges to manufacturing patterned media, the large potential gains offered in terms of areal density make it one of the most promising new technologies on the horizon for future hard disk drives. Thus, this dissertation contributes to the development of future alternative data storage devices and deferring the superparamagnetic limit by designing and characterizing patterned magnetic media using a novel nanoimprint replication process called "Step and Flash Imprint lithography". As opposed to hot embossing and other high temperature-low pressure processes, SFIL can be performed at low pressure and room temperature. Initial experiments carried out, consisted of process flow design for the patterned structures on sputtered Ni-Fe thin films. The main one being the defectivity analysis for the SFIL process conducted by fabricating and testing devices of varying feature sizes (50 nm to 1 μm) and inspecting them optically as well as testing them electrically. Once the SFIL process was optimized, a number of Ni-Fe coated wafers were imprinted with a template having the patterned topography. A minimum feature size of 40 nm was obtained with varying pitch (1:1, 1:1.5, 1:2, and 1:3). The Characterization steps involved extensive SEM study at each processing step as well as Atomic Force Microscopy (AFM) and Magnetic Force Microscopy (MFM) analysis.

Comprehensive process maps for synthesizing high density aluminum oxide-carbon nanotube coatings by plasma spraying for improved mechanical and wear properties

Plasma sprayed aluminum oxide ceramic coating is widely used due to its outstanding wear, corrosion, and thermal shock resistance. But porosity is the integral feature in the plasma sprayed coating which exponentially degrades its properties. In this study, process maps were developed to obtain Al2O3-CNT composite coatings with the highest density (i.e. lowest porosity) and improved mechanical and wear properties. Process map is defined as a set of relationships that correlates large number of plasma processing parameters to the coating properties. Carbon nanotubes (CNTs) were added as reinforcement to Al2O 3 coating to improve the fracture toughness and wear resistance. Two novel powder processing approaches viz spray drying and chemical vapor growth were adopted to disperse CNTs in Al2O3 powder. The degree of CNT dispersion via chemical vapor deposition (CVD) was superior to spray drying but CVD could not synthesize powder in large amount. Hence optimization of plasma processing parameters and process map development was limited to spray dried Al2O3 powder containing 0, 4 and 8 wt. % CNTs. An empirical model using Pareto diagram was developed to link plasma processing parameters with the porosity of coating. Splat morphology as a function of plasma processing parameter was also studied to understand its effect on mechanical properties. Addition of a mere 1.5 wt. % CNTs via CVD technique showed ∼27% and ∼24% increase in the elastic modulus and fracture toughness respectively. Improved toughness was attributed to combined effect of lower porosity and uniform dispersion of CNTs which promoted the toughening by CNT bridging, crack deflection and strong CNT/Al2O3 interface. Al2O 3-8 wt. % CNT coating synthesized using spray dried powder showed 73% improvement in the fracture toughness when porosity reduced from 4.7% to 3.0%. Wear resistance of all coatings at room and elevated temperatures (573 K, 873 K) showed improvement with CNT addition and decreased porosity. Such behavior was due to improved mechanical properties, protective film formation due to tribochemical reaction, and CNT bridging between the splats. Finally, process maps correlating porosity content, CNT content, mechanical properties, and wear properties were developed.

Developing a high density platinum/alumina hermetic feedthrough

Typically, hermetic feedthroughs for implantable devices, such as pacemakers, use a alumina ceramic insulator brazed to a platinum wire pin. This combination of material has a long history in implantable devices and has been approved by the FDA for implantable hermetic feedthroughs. The growing demand for increased input/output (I/O) hermetic feedthroughs for implantable neural stimulator applications could be addressed by developing a new, cofired platinum/alumina multilayer ceramic technology in a configuration that supports 300 plus I/Os, which is not commercially available. Seven platinum powders with different particle sizes were used to develop different conductive cofire inks to control the densification mismatch between platinum and alumina. Firing profile (ramp rate, burn- out and holding times) and firing atmosphere and concentrations (hydrogen (wet/dry), air, neutral, vacuum) were also optimized. Platinum and alumina exhibit the alloy formation reaction in a reduced atmosphere. Formation of any compound can increase the bonding of the metal/ceramic interface, resulting in enhanced hermeticity. The feedthrough fabricated in a reduced atmosphere demonstrated significantly superior performance than that of other atmospheres. A composite structure of tungsten/platinum ratios graded thru the via structure (pure W, 50/50 W/Pt, 80/20 Pt/W and pure Pt) exhibited the best performance in comparison to the performance of other materials used for ink metallization. Studies on the high temperature reaction of platinum and alumina, previously unreported, showed that, at low temperatures in reduced atmosphere, Pt 3Al or Pt8Al21 with a tetragonal structure would be formed. Cubic Pt3Al is formed upon heating the sample to temperatures above 1350 °C. This cubic structure is the equilibrium state of Pt-Al alloy at high temperatures. The alumina dissolves into the platinum ink and is redeposited as a surface coating. This was observed on both cofired samples and pure platinum thin films coated on a 99.6 Wt% alumina and fired at 1550 °C. Different mechanisms are proposed to describe this behavior based on the size of the platinum particle

Crustal-scale shear zones and heterogeneous structure beneath the North Anatolian Fault Zone, Turkey, revealed by a high-density seismometer array

Peer reviewed

Crustal-scale shear zones and heterogeneous structure beneath the North Anatolian Fault Zone, Turkey, revealed by a high-density seismometer array

Peer reviewed

Effect of early release from intense competition within high density natural regeneration on the properties of the juvenile and mature wood of 40-year-old Sitka spruce (Picea sitchensis (Bong.) Carr.)

Peer reviewed

Resist-substrate interface tailoring for generating high density arrays of Ge and Bi2Se3 nanowires by electron beam lithography

The authors report a chemical process to remove the native oxide on Ge and Bi2Se3 crystals, thus facilitating high-resolution electron beam lithography (EBL) on their surfaces using a hydrogen silsesquioxane (HSQ) resist. HSQ offers the highest resolution of all the commercially available EBL resists. However, aqueous HSQ developers such as NaOH and tetramethylammonium hydroxide have thus far prevented the fabrication of high-resolution structures via the direct application of HSQ to Ge and Bi2Se3, due to the solubility of components of their respective native oxides in these strong aqueous bases. Here we provide a route to the generation of ordered, high-resolution, high-density Ge and Bi2Se3 nanostructures with potential applications in microelectronics, thermoelectric, and photonics devices.                         

Theory and Practice in Sustainability Science: Influence of Urban Form on the Urban Heat Island and Implications for Urban Systems

As the world population continues to grow past seven billion people and global challenges continue to persist including resource availability, biodiversity loss, climate change and human well-being, a new science is required that can address the integrated nature of these challenges and the multiple scales on which they are manifest. Sustainability science has emerged to fill this role. In the fifteen years since it was first called for in the pages of Science, it has rapidly matured, however its place in the history of science and the way it is practiced today must be continually evaluated. In Part I, two chapters address this theoretical and practical grounding. Part II transitions to the applied practice of sustainability science in addressing the urban heat island (UHI) challenge wherein the climate of urban areas are warmer than their surrounding rural environs. The UHI has become increasingly important within the study of earth sciences given the increased focus on climate change and as the balance of humans now live in urban areas.

In Chapter 2 a novel contribution to the historical context of sustainability is argued. Sustainability as a concept characterizing the relationship between humans and nature emerged in the mid to late 20th century as a response to findings used to also characterize the Anthropocene. Emerging from the human-nature relationships that came before it, evidence is provided that suggests Sustainability was enabled by technology and a reorientation of world-view and is unique in its global boundary, systematic approach and ambition for both well being and the continued availability of resources and Earth system function. Sustainability is further an ambition that has wide appeal, making it one of the first normative concepts of the Anthropocene.

Despite its widespread emergence and adoption, sustainability science continues to suffer from definitional ambiguity within the academe. In Chapter 3, a review of efforts to provide direction and structure to the science reveals a continuum of approaches anchored at either end by differing visions of how the science interfaces with practice (solutions). At one end, basic science of societally defined problems informs decisions about possible solutions and their application. At the other end, applied research directly affects the options available to decision makers. While clear from the literature, survey data further suggests that the dichotomy does not appear to be as apparent in the minds of practitioners.

In Chapter 4, the UHI is first addressed at the synoptic, mesoscale. Urban climate is the most immediate manifestation of the warming global climate for the majority of people on earth. Nearly half of those people live in small to medium sized cities, an understudied scale in urban climate research. Widespread characterization would be useful to decision makers in planning and design. Using a multi-method approach, the mesoscale UHI in the study region is characterized and the secular trend over the last sixty years evaluated. Under isolated ideal conditions the findings indicate a UHI of 5.3 ± 0.97 °C to be present in the study area, the magnitude of which is growing over time.

Although urban heat islands (UHI) are well studied, there remain no panaceas for local scale mitigation and adaptation methods, therefore continued attention to characterization of the phenomenon in urban centers of different scales around the globe is required. In Chapter 5, a local scale analysis of the canopy layer and surface UHI in a medium sized city in North Carolina, USA is conducted using multiple methods including stationary urban sensors, mobile transects and remote sensing. Focusing on the ideal conditions for UHI development during an anticyclonic summer heat event, the study observes a range of UHI intensity depending on the method of observation: 8.7 °C from the stationary urban sensors; 6.9 °C from mobile transects; and, 2.2 °C from remote sensing. Additional attention is paid to the diurnal dynamics of the UHI and its correlation with vegetation indices, dewpoint and albedo. Evapotranspiration is shown to drive dynamics in the study region.

Finally, recognizing that a bridge must be established between the physical science community studying the Urban Heat Island (UHI) effect, and the planning community and decision makers implementing urban form and development policies, Chapter 6 evaluates multiple urban form characterization methods. Methods evaluated include local climate zones (LCZ), national land cover database (NCLD) classes and urban cluster analysis (UCA) to determine their utility in describing the distribution of the UHI based on three standard observation types 1) fixed urban temperature sensors, 2) mobile transects and, 3) remote sensing. Bivariate, regression and ANOVA tests are used to conduct the analyses. Findings indicate that the NLCD classes are best correlated to the UHI intensity and distribution in the study area. Further, while the UCA method is not useful directly, the variables included in the method are predictive based on regression analysis so the potential for better model design exists. Land cover variables including albedo, impervious surface fraction and pervious surface fraction are found to dominate the distribution of the UHI in the study area regardless of observation method.

Chapter 7 provides a summary of findings, and offers a brief analysis of their implications for both the scientific discourse generally, and the study area specifically. In general, the work undertaken does not achieve the full ambition of sustainability science, additional work is required to translate findings to practice and more fully evaluate adoption. The implications for planning and development in the local region are addressed in the context of a major light-rail infrastructure project including several systems level considerations like human health and development. Finally, several avenues for future work are outlined. Within the theoretical development of sustainability science, these pathways include more robust evaluations of the theoretical and actual practice. Within the UHI context, these include development of an integrated urban form characterization model, application of study methodology in other geographic areas and at different scales, and use of novel experimental methods including distributed sensor networks and citizen science.

Multiphase modeling of melting / solidification with high density variations using XFEM

La modélisation de la cryolite, utilisée dans la fabrication de l’aluminium, implique plusieurs défis, notament la présence de discontinuités dans la solution et l’inclusion de la difference de densité entre les phases solide et liquide. Pour surmonter ces défis, plusieurs éléments novateurs ont été développés dans cette thèse. En premier lieu, le problème du changement de phase, communément appelé problème de Stefan, a été résolu en deux dimensions en utilisant la méthode des éléments finis étendue. Une formulation utilisant un multiplicateur de Lagrange stable spécialement développée et une interpolation enrichie a été utilisée pour imposer la température de fusion à l’interface. La vitesse de l’interface est déterminée par le saut dans le flux de chaleur à travers l’interface et a été calculée en utilisant la solution du multiplicateur de Lagrange. En second lieu, les effets convectifs ont été inclus par la résolution des équations de Stokes dans la phase liquide en utilisant la méthode des éléments finis étendue aussi. Troisièmement, le changement de densité entre les phases solide et liquide, généralement négligé dans la littérature, a été pris en compte par l’ajout d’une condition aux limites de vitesse non nulle à l’interface solide-liquide pour respecter la conservation de la masse dans le système. Des problèmes analytiques et numériques ont été résolus pour valider les divers composants du modèle et le système d’équations couplés. Les solutions aux problèmes numériques ont été comparées aux solutions obtenues avec l’algorithme de déplacement de maillage de Comsol. Ces comparaisons démontrent que le modèle par éléments finis étendue reproduit correctement le problème de changement phase avec densités variables.