Characterisation of a cavity transfer mixer as a chemical reactor

This research project examined the feasibility of using a cavity transfer mixer (CTM) as a continuous reactor to perform reactions between either solid or liquid reagents and polymer melt; reactions which have previously been typically carried out in batch reactor systems. Equipment has been developed to allow uniform and reproducible introduction of reagents into the polymer melt. Reactions have also been performed using batch processing equipment to enable comparison with the performance of the CTM. It was concluded that: a) there are certain reactions which cannot be carried out in a CTM, but which can be performed in a batch system such as a mill or a sigma blade mixer. This was found to be the case for some neutralisation reactions where the product was quasi crosslinked. b) the reactions that can be carried out in a CTM are performed more efficiently in a CTM than on a batch process. For example, when monomers were to be grafted onto polymers, this was more safely and efficiently performed in the CTM than in a mill or a sigma blade mixer. Residence time distributions (RTDs) for three CTMs were studied in order to gain an insight into the effect of CTM geometry on RTD, polymer melt flow pattern and reactor performance. A mathematical model has been developed to predict the influence of process parameters on RTD and the results compared with experimentally observed trends. The comparison was good. A programme of research has been drawn up to form the basis of an industrially based sponsored development project of the CTM reactor. This work programme was successfully marketed to companies with commercial interest in modified rubber and plastics as an integral part of the research programme of this thesis and the sponsored research programme has paralleled the work reported here.

Simultaneous clock recovery and data regeneration using a nonlinear optical loop mirror as an all-optical mixer

High-speed optical clock recovery, demultiplexing and data regeneration will be integral parts of any future photonic network based on high bit-rate OTDM. Much research has been conducted on devices that perform these functions, however to date each process has been demonstrated independently. A very promising method of all-optical switching is that of a semiconductor optical amplifier-based nonlinear optical loop mirror (SOA-NOLM). This has various advantages compared with the standard fiber NOLM, most notably low switching power, compact size and stability. We use the SOA-NOLM as an all-optical mixer in a classical phase-locked loop arrangement to achieve optical clock recovery, while at the same time achieving data regeneration in a single compact device

Metallocene ethylene-1-octene copolymers:influence of comonomer content on thermo-mechanical, rheological, and thermo-oxidative behaviours before and after melt processing in an internal mixer

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.

Sugar and coffee: A history of settler agriculture in nineteenth-century Liberia

This dissertation is about commercial agriculture in nineteenth-century Liberia. Based primarily on the archives of the American Colonization Society (founder of Liberia), it examines the impact of environmental and demographic constraints on an agrarian settler society from 1822 to the 1890s. Contrary to the standard interpretation, which linked the poor state of commercial agriculture to the settlers' disdain for cultivation, this dissertation argues that the scarcity of labor and capital impeded the growth of commercial agriculture. The causes of the scarcity were high mortality, low immigration and the poverty of the American “Negroes” who began to settle Liberia in 1822. ^ Emigration to Liberia meant almost certain death and affliction for many immigrants because they encountered a new set of diseases. Mortality was particularly high during the early decades of colonization. From 1822 to 1843, about 48 percent of all immigrants died of various causes, usually within their first year. The bulk of the deaths is attributed to malaria. There was no natural increase in the population for this early period and because American “Negroes” were unenthusiastic about relocation to Liberia, immigration remained sparse throughout the century. Low immigration, combined with the high death rate, deprived the fledgling colony of its potential human resource, especially for the cultivation of labor-intensive crops, like sugar cane and coffee. Moreover, even though females constituted approximately half of the settlers, they seldom performed agricultural labor. ^ The problem of labor was compounded by the scarcity of draft animals. Liberia is in the region where trypanosomiasis occurs. The disease is fatal to large livestock. Therefore, animal-drawn plows, common in the United States, were never successfully transplanted in Liberia. Besides, the dearth of livestock obstructed the development of the sugar industry since many planters depended on oxen-powered mills because they could not afford to buy the more expensive steam engine mills. ^ Finally, nearly half of the immigrants were newly emancipated slaves. Usually these former bondsmen arrived in Liberia penniless. Consequently, they lacked the capital to invest in large-scale plantations. The other categories of immigrants (e.g., those who purchased their freedom), were hardly better off than the emancipated slaves. ^

On decentring ethnicity in buildings research : the settler homestead as assemblage

Peer reviewed

A Decade-Bandwidth Low-Noise Mixer RFIC with a Distortion-Canceling Output Amplifier

This paper presents a 1-10 GHz low-noise downconvert mixer RFIC suitable for wideband receivers. A switched transconductor mixing core is adopted to reduce noise at high frequencies. By adding a series inductor to the RF transconductor, a flat 4-5 dB noise figure (NF) and a high gain of 26.5 dB can be achieved over a broad bandwidth out to 10 GHz. A CMOS output amplifier is also integrated on-chip, employing derivative superposition (DS) for high linearity and an OIP3 of 16.5 dBm. The circuit consumes less than 20 mW of dc power and occupies an active chip area of less than 0.2 mm2.

Decolonizing Pedagogies: Interrupting the Settler Colonial Narrative of Landownership in Ontario Social Science and History Curriculum

Drawing upon Ontario Social Science and History curriculum documents and textbook imagery and language, this paper examines how narratives of settler landownership strategically present Indigenous and non-Indigenous peoples within the Canadian grand narrative. The curriculum and text material educators and learners are guided by ignore ongoing colonial violence towards Indigenous peoples and perpetuate the ideology of inevitable ‘peaceful’ interrelationships in national contexts. Learners develop identities in relation to land and how land is acquired. They come to understand themselves as part of a just nation in the particular sequence of Canadian Social Science and History teaching and learning. To go beyond simply adding content about Indigenous peoples in the classroom, educators and learners must adapt a decolonial approach to instead learn from Indigenous perspectives. Such a methodology would require the opening of a “third space” where the transmission of western curricular knowledge is interrupted. Educators and learners must create a space for problematizing the source itself and deconstruct the national grand narrative using inquiry, questioning and reflection, rather than repetition and regurgitation. This analysis reveals that particular placements of Indigenous peoples and settler Canadians in curriculum and classroom text material must be challenged by educators and learners to disrupt colonial narratives and to seek ongoing reconciliatory opportunities in and beyond the school walls.

Stitching Settler Identities: Canadian Quilts and Their Makers, 1800-1880

Stitching Settler Identities: Canadian Quilts and their Makers, 1800-1880 explores the making, use, and circulation of handmade settler quilts as representation of nineteenth-century women’s social, cultural and economic histories in Canada. An important part of Canadian settlement history is the making and use of handmade quilts in the settler homestead. Handmade coverlets that provided both physical and emotional warmth in the home were a measure of a settler-woman’s careful management of resources and a display of her innovation and creativity. Few settler women recorded their daily experiences; however, most women could sew and quilts offered a method of expression that allowed them to reflect and portray their identities. Thus far, the few studies of quilts have been limited to exhibition catalogues or research that considers a quilt’s aesthetics or its historic significance. While several scholars have called for a reclassification of textile production and needle arts to advance the way in which settler women were viewed as social beings – creating, producing, communicating, and circulating cultural values, most studies on quilts have overlooked a coverlet’s materiality. This study aims to expand the research on quilts as material culture within the context of art history by also considering a quilt’s materiality and when possible, its maker's biography.

A mixer design for the pigtail braid

The stirring of a body of viscous fluid using multiple stirring rods is known to be particularly effective when the rods trace out a path corresponding to a nontrivial mathematical braid. The optimal braid is the so-called "pigtail braid", in which three stirring rods execute the usual "over-under" motion associated with braiding plaiting) hair. We show how to achieve this optimal braiding motion straightforwardly: one stirring rod is driven in a figure-of-eight motion, while the other two rods are baffles, which rotate episodically about their common centre. We also explore the extent to which the physical baffles may be replaced by flow structures (such as periodic islands).

Sperimentazione di un EGR HP Mixer e di un Oil Cooler con Bypass in un motore V6 Diesel con l’obiettivo di ridurre la CO2

Lo scopo di questa tesi è stato sperimentare componenti prototipali su un motore V6 Diesel all’interno di un banco dinamico con il fine di valutarne la riduzione di CO2 in cicli di omologazione NEDC e WLTC. In particolare si sono studiati un nuovo EGR HP Mixer e un Oil Cooler dotato di Bypass: il primo componente per migliorare l’EGR distribution da cilindro a cilindro, mentre il secondo componente per ottenere un’ottimizzazione energetica della pompa dell’olio sfruttando il nuovo bypass del cooler. L’Oil Cooler è dotato di due cartucce intercambiabili che cambiano le fasi di bypass a seconda della temperatura dell’olio: la prima cartuccia, a 2 stadi, parte dalla condizione di bypass e chiude a una certa temperatura per proteggere il motore; la seconda, a 3 stadi, sfrutta il bypass solo in un range di temperatura ottimizzato con il calcolo CFD. La riduzione di consumi di gasolio è stata valutata confrontando i diversi consumi a pari emissioni di NOx; in questo modo si è registrata una riduzione di consumi con l’EGR HP Mixer dell’1.7% nel ciclo NEDC e dello 0.5% nel ciclo WLTC. Con lo stesso metodo si è registrato che l’Oil Cooler Bypass determina nel ciclo NEDC una riduzione dello 0.6 % con la valvola a 3 Stadi e una riduzione dello 0.37 % con la valvola a 2 Stadi. Nel ciclo WLTC si è invece ottenuta una riduzione dello 0.1 % con la valvola a 3 Stadi e un aumento dello 0.33 % con la valvola a 2 Stadi. Di ogni componente è stato fatto uno studio stazionario per indagarne a fondo i comportamenti.

Caracterização reológica das diferentes fases de extrato de inulina de raízes de chicória, obtidas por abaixamento de temperatura

Inulin is a functional food ingredient, generally employed as sugar or fat substitute in food systems. This ingredient can be found in several vegetal products, including chicory roots. As the solubility of inulin is susceptible to temperature changes, the product suffers a fractionalization resulting in two phases when cooled, originating a precipitated phase, more viscose, and a liquid phase, of lesser viscosity. The study of rheological properties of different phases of inulin extract is important for equipment designing, such as mixer and bombs. In this work, rheological behavior at three different temperatures (25; 40 and 50 ºC) was determined for liquid and precipitated phases of inulin liquid extract, extracted from chicory roots by hot water diffusion and cooled at two different temperatures (8 and -10 ºC), suffering phases separation. The precipitated phase was analyzed in two conditions: pure and with the addition of microencapsulating agents (maltodextrin and hydrolized starch). All of them presented a linear behavior, similar to that of the Plastics of Bingham. Some of them, however, were not an adequate fit to this model.

Thermoplastic starch modified during melt processing with organic acids: The effect of molar mass on thermal and mechanical properties

Thermoplastic starch (TPS) was modified with ascorbic acid and citric acid by melt processing of native starch with glycerol as plasticizer in an intensive batch mixer at 160 degrees C. It was found that the molar mass decreases with acid content and processing time causing the reduction in melting temperature (T(m)). As observed by the results of X-ray diffraction and DSC measurements, crystallinity was not changed by the reaction with organic acids. T(m) depression with falling molar mass was interpreted on the basis of the effect of concentration of end-chain units, which act as diluents. FTIR did not show any appreciable change in starch chemical compositions, leading to the conclusion that the main changes observed were produced by the variation in molar mass of the material. We demonstrated that it is possible to decrease melt viscosity without the need for more plasticizer thus avoiding side-effects such as an increase in water affinity or relevant changes in the dynamic mechanical properties. (C) 2010 Elsevier B.V. All rights reserved.

Compatible Ternary Blends of Chitosan/poly(vinyl alcohol)/poly(lactic acid) Produced by Oil-in-Water Emulsion Processing

Ternary compatible blends of chitosan, poly(vinyl alcohol), and poly(lactic acid) were prepared by an oil-in-water (O/W) emulsion process. Solutions of chitosan in aqueous acetic acid, poly(vinyl alcohol) (PVA) in water, and poly(lactic acid) (PLA) in chloroform were blended with a high shear mixer. PVA was used as an emulsifier to stabilize the emulsion and to reduce the interfacial tension between the solid polymers in the blends-produced. It proved to work very well because the emulsions were stable for periods of days or weeks and compatible blends were obtained When PVA was added. This effect was attributed to a synergistic effect of PVA and chitosan because the binary blends PVA/PLA and chitosan/PLA were completely incompatible; The blends were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal mechanical analysis (TMA), stress strain tests, and Fourier transform infrared spectroscopy (FTIR). The results indicated that despite the fact that the system contained distinct phases some degree of molecular miscibility occurred when the three components were present in the blend.

DEVELOPMENT OF STATIC MIXERS FOR MISCIBLE FLUIDS IN LAMINAR FLOW WITH THE USE OF COMPUTATIONAL FLUID DYNAMICS (CFD)

Static mixers with improved performance were developed from CFD simulations in a stepwise approach. The relevant geometric features of simple mixer designs and the corresponding mixing mechanisms-laminar shear, elongational flow, and distributive mixing-were identified first. This information was used to formulate guidelines for the development of new geometries. The solid elements of the static mixer should: (a) provide restrictions to the flow; (b) deflect the flow; (c) be sequentially rotated around the flow direction to provide symmetry; (d) extend from the center of the pipe to the vicinity of the walls to avoid short-circuiting; and (e) distribute and remix the flow. Based on these guidelines, two improved mixer designs were developed: the DS A-I mixer has a good mixing efficiency and an acceptable pressure drop; the Fins 35 degrees mixer is more efficient and compact, but requires a larger pressure drop. Their performance indicates that their use is possible on industrial applications.

Vortex configuration flow cell based on low temperature cofired ceramics as a compact chemiluminescence microsystern

The integration of optical detection methods in continuous flow microsystems can highly extend their range of application, as long as some negative effects derived from their scaling down can be minimized. Downsizing affects to a greater extent the sensitivity of systems based on absorbance measurements than the sensitivity of those based on emission ones. However, a careful design of the instrumental setup is needed to maintain the analytical features in both cases. In this work, we present the construction and evaluation of a simple miniaturized optical system, which integrates a novel flow cell configuration to carry out chemiluminescence (CL) measurements using a simple photodiode. It consists of a micro-mixer based on a vortex structure, which has been constructed by means of the low-temperature cofired ceramics (LTCC) technology. This mixer not only efficiently promotes the CL reaction due to the generated high turbulence but also allows the detection to be carried out in the same area, avoiding intensity signal losses. As a demonstration, a flow injection system has been designed and optimized for the detection of cobalt(H) in water samples. It shows a linear response between 2 and 20 mu M with a correlation of r > 0.993, a limit of detection of 1.1 mu M, a repeatability of RSD = 12.4 %, and an analysis time of 17 s. These results demonstrate the suitability of the proposal to the determination of compounds involved in CL reactions by means of an easily constructed versatile device based on low-cost instrumentation.