Biocomposites of non-crosslinked natural and synthetic polymers

Biocomposite films comprising a non-crosslinked, natural polymer (collagen) and a synthetic polymer, poly(var epsilon-caprolactone) (PCL), have been produced by impregnation of lyophilised collagen mats with a solution of PCL in dichloromethane followed by solvent evaporation. This approach avoids the toxicity problems associated with chemical crosslinking. Distinct changes in film morphology, from continuous surface coating to open porous format, were achieved by variation of processing parameters such as collagen:PCL ratio and the weight of the starting lyophilised collagen mat. Collagenase digestion indicated that the collagen content of 1:4 and 1:8 collagen:PCL biocomposites was almost totally accessible for enzymatic digestion indicating a high degree of collagen exposure for interaction with other ECM proteins or cells contacting the biomaterial surface. Much reduced collagen exposure (around 50%) was measured for the 1:20 collagen:PCL materials. These findings were consistent with the SEM examination of collagen:PCL biocomposites which revealed a highly porous morphology for the 1:4 and 1:8 blends but virtually complete coverage of the collagen component by PCL in the1:20 samples. Investigations of the attachment and spreading characteristics of human osteoblast (HOB) cells on PCL films and collagen:PCL materials respectively, indicated that HOB cells poorly recognised PCL but attachment and spreading were much improved on the biocomposites. The non-chemically crosslinked, collagen:PCL biocomposites described are expected to provide a useful addition to the range of biomaterials and matrix systems for tissue engineering.

Wear and corrosion of mechanical seals

Mechanical seals are used extensively to seal machinery such as pumps, mixers and agitators in the oil, petrochemical and chemical industries. The performance of such machinery is critically dependent on these devices. Seal failures may result in the escape of dangerous chemicals, possibly causing injury or loss of life. Seal performance is limited by the choice of face materials available. These range from cast iron and stellited stainless steel to cemented and silicon carbides. The main factors that affect seal performance are the wear and corrosion of seal faces. This research investigated the feasibility of applying surface coating/treatments to seal materials, in order to provide improved seal performance. Various surface coating/treatment methods were considered; these included electroless nickel plating, ion plating, plasma nitriding, thermal spraying and high temperature diffusion processes. The best wear resistance, as evaluated by the Pin-on-Disc wear test method, was conferred by the sprayed tungsten carbide/nickel/tungsten-chromium carbide deposit, produced by the high energy plasma spraying (Jet-Kote) process. In general, no correlation was found between hardness and wear resistance or surface finish and friction. This is due primarily to the complexity of the wear and frictional oxidation, plastic deformation, ploughing, fracture and delamination. Corrosion resistance was evaluated by Tafel extrapolation, linear polarisation and anodic potentiodynamic polarisation techniques. The best corrosion performance was exhibited by an electroless nickel/titanium nitride duplex coating due to the passivity of the titanium nitride layer in the acidified salt solution. The surface coating/treatments were ranked using a systematic method, which also considered other properties such as adhesion, internal stress and resistance to thermal cracking. The sealing behaviour of surface coated/treated seals was investigated on an industrial seal testing rig. The best sealing performances were exhibited by the Jet-Kote and electroless nickel silicon carbide composite coated seals. The failure of the electroless nickel and electroless nickel/titanium nitride duplex coated seals was due to inadequate adhesion of the deposits to the substrate. Abrasion of the seal faces was the principal wear mechanism. For operation in an environment similar to the experimental system employed (acidified salt solution) the Jet-Kote deposit appears to be the best compromise.

Ocular response to silicone-hydrogel contact lenses

The thesis investigates the ocular response to silicone-hydrogel (SiH) contact lens wear, a relatively new contact lens material that has a higher modulus of rigidity and different surface coating than used in conventional hydrogel materials. The properties of SiH materials differ significantly from conventional hydrogels and, using subjective and objective means of assessment, the thesis examines how these properties affect reflection and biometry, ocular physiology, tear film characteristics, symptomatology, adverse events and complications. A range of standard and newly designed investigative techniques were employed, and latter involving novel imaging techniques, for the objective assessment of physiological changes which occur with contact lens wear. The study is the first to combine these techniques with biochemical analyses of the tear film composition. Forty-seven subjects were fitted with SiH lenses and randomly allocated to one of the two materials currently on the market (Lotrafilcon A or Balafilcon A) on an either daily or continuous wear basis. An additional control group of 14 age-matched non-contact lens wearers were monitored over the same period. Measurements were taken before and 1, 3, 6, 12 and 18 months after initial fitting. The findings reported in this thesis will enable contact lens practitioners and manufacturers to understand further the optical, physiological and biochemical nature of the ocular response to SiH contact lenses and hence facilitate the development of this important generation of contact lens material.

Polycaprolactone fibres as a potential delivery system for collagen to support bone regeneration

Poly(e-caprolactone) (PCL) is biocompatible, non-immunogenic and non-toxic, and slowly degrades, allowing sufficient time for tissue regeneration. PCL has the potential for application in bone and cartilage repair as it may provide the essential structure required for bone regeneration, however, an ideal scaffold system is still undeveloped. PCL fibres were prepared using the gravity spinning technique, in which collagen was either incorporated into or coated onto the 'as-spun' fibres, in order to develop novel biodegradable polymer fibres which will effectively deliver collagen and support the attachment and proliferation of human osteoblast (HOB) cells for bone regeneration. The physical and mechanical characteristics and cell fibre interactions were analysed. The PCL fibres were found to be highly flexible and inclusion of collagen did not alter the mechanical properties of PCL fibres. Overall, HOB cells were shown to effectively adhere and proliferate on all fibre platforms tested, although proliferation rates were enhanced by surface coating PCL fibres with collagen compared to PCL fibres incorporating collagen and PCL-only fibres. These findings highlight the potential of using gravity spun PCL fibres as a delivery platform for extracellular matrix proteins, such as collagen, in order to enhance cell adherence and proliferation for tissue repair.

Effects of fibre reinforcement on the mechanical properties of brushite cement

In this study the effect of structure and amount of polyglactin fibre incorporation into a brushite forming calcium phosphate cement system and the effect of mechanical compaction on the fibre modified system were investigated. In comparison the effect of resorbable polycaprolactone surface coating of cement specimens was investigated. The results showed that, apart from the mechanical properties of the reinforcing material, the structure of the incorporated fibres, regular or random, is crucial for the resulting flexural strength and modulus of elasticity. Fibre reinforcement could also be combined with mechanical compaction of the cement/fibre composite paste leading to a possible 7-fold increase in flexural strength or an almost 5-fold increase in modulus of elasticity. Reinforcement of the tensile surface of cement grafts may ultimately improve strength where required, especially in conjunction with bone fixation devices. © 2005 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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

Advanced Aerogel Composites for Oil Remediation and Recovery

Oil spills in marine environments often damage marine and coastal life if not remediated rapidly and efficiently. In spite of the strict enforcement of environmental legislations (i.e., Oil Pollution Act 1990) following the Exxon Valdez oil spill (June 1989; the second biggest oil spill in U.S. history), the Macondo well blowout disaster (April 2010) released 18 times more oil. Strikingly, the response methods used to contain and capture spilled oil after both accidents were nearly identical, note that more than two decades separate Exxon Valdez (1989) and Macondo well (2010) accidents.

The goal of this dissertation was to investigate new advanced materials (mechanically strong aerogel composite blankets-Cabot® Thermal Wrap™ (TW) and Aspen Aerogels® Spaceloft® (SL)), and their applications for oil capture and recovery to overcome the current material limitations in oil spill response methods. First, uptake of different solvents and oils were studied to answer the following question: do these blanket aerogel composites have competitive oil uptake compared to state-of-the-art oil sorbents (i.e., polyurethane foam-PUF)? In addition to their competitive mechanical strength (766, 380, 92 kPa for Spaceloft, Thermal Wrap, and PUF, respectively), our results showed that aerogel composites have three critical advantages over PUF: rapid (3-5 min.) and high (more than two times of PUF’s uptake) oil uptake, reusability (over 10 cycles), and oil recoverability (up to 60%) via mechanical extraction. Chemical-specific sorption experiments showed that the dominant uptake mechanism of aerogels is adsorption to the internal surface, with some contribution of absorption into the pore space.

Second, we investigated the potential environmental impacts (energy and chemical burdens) associated with manufacturing, use, and disposal of SL aerogel and PUF to remove the oil (i.e., 1 m3 oil) from a location (i.e., Macondo well). Different use (single and multiple use) and end of life (landfill, incinerator, and waste-to-energy) scenarios were assessed, and our results demonstrated that multiple use, and waste-to-energy choices minimize the energy and material use of SL aerogel. Nevertheless, using SL once and disposing via landfill still offers environmental and cost savings benefits relative to PUF, and so these benefits are preserved irrespective of the oil-spill-response operator choices.

To inform future aerogel manufacture, we investigated the different laboratory-scale aerogel fabrication technologies (rapid supercritical extraction (RSCE), CO2 supercritical extraction (CSCE), alcohol supercritical extraction (ASCE)). Our results from anticipatory LCA for laboratory-scaled aerogel fabrication demonstrated that RSCE method offers lower cumulative energy and ecotoxicity impacts compared to conventional aerogel fabrication methods (CSCE and ASCE).

The final objective of this study was to investigate different surface coating techniques to enhance oil recovery by modifying the existing aerogel surface chemistries to develop chemically responsive materials (switchable hydrophobicity in response to a CO2 stimulus). Our results showed that studied surface coating methods (drop casting, dip coating, and physical vapor deposition) were partially successful to modify surface with CO2 switchable chemical (tributylpentanamidine), likely because of the heterogeneous fiber structure of the aerogel blankets. A possible solution to these non-uniform coatings would be to include switchable chemical as a precursor during the gel preparation to chemically attach the switchable chemical to the pores of the aerogel.

Taken as a whole, the implications of this work are that mechanical deployment and recovery of aerogel composite blankets is a viable oil spill response strategy that can be deployed today. This will ultimately enable better oil uptake without the uptake of water, potential reuse of the collected oil, reduced material and energy burdens compared to competitive sorbents (e.g., PUF), and reduced occupational exposure to oiled sorbents. In addition, sorbent blankets and booms could be deployed in coastal and open-ocean settings, respectively, which was previously impossible.

Adequação bioclimática para os espaços urbanos abertos do centro de Fortaleza, CE

This research presents a study investigating the correlation between the environmental-physycal charcateristics of cities and the formation of its micro-climates. The study was conducted in the central area of Fortaleza characterized as a stable and consolidated area, where the city originated and currently faces serious problems in its urban dynamics. The points of measurements were determined by the elaboration and analysis of topography maps, height of buildings, land use, type of surface coating and vegetation, following the methodology of Katzschner (1997). A zoning map was then determined, according to common morphological characteristics of the 12 measurement points, which were based on a set of Romero s (2001) bioclimatic criteria. Air measurements, temperature, humidity, intensity and direction of winds were made in transect form in two different circuits in the study area, with six points of data collection in each area, in three different times: 6:00 am, 1:00pm and 7:00pm, during two periods of the year: August 2008 and March 2009. The results verified the influence of different environmental-physical types in the behavior of the climatic variables that were collected. A verticalização tão condenada em algumas situações se bem equilibrada e controlada pode reduzir as temperaturas do ar através do sombreamento dos espaços urbanos e possibilidade de maior permeabilidade a ventilação natural. The highest average air temperature and lower humidity were recorded at the point I at all times. This situation may have been in result of the high density, poor vegetation and extended paving of the ground. According to the results, it s clear the positive influence vegetation has on easing air temperature. Another indicator observed that areas with a greater variation in building heights tend to present decreased average air temperature. High rise structure, planned in accordance to urban air quality parameters, can reduce air temperatures by the shading of urban spaces and the possibility of greater penetration of natural ventilation

Are iron oxide nanoparticles safe? Current knowledge and future perspectives

Due to their unique physicochemical properties, including superparamagnetism, iron oxide nanoparticles (ION) have a number of interesting applications, especially in the biomedical field, that make them one of the most fascinating nanomaterials. They are used as contrast agents for magnetic resonance imaging, in targeted drug delivery, and for induced hyperthermia cancer treatments. Together with these valuable uses, concerns regarding the onset of unexpected adverse health effects following exposure have been also raised. Nevertheless, despite the numerous ION purposes being explored, currently available information on their potential toxicity is still scarce and controversial data have been reported. Although ION have traditionally been considered as biocompatible - mainly on the basis of viability tests results - influence of nanoparticle surface coating, size, or dose, and of other experimental factors such as treatment time or cell type, has been demonstrated to be important for ION in vitro toxicity manifestation. In vivo studies have shown distribution of ION to different tissues and organs, including brain after passing the blood-brain barrier; nevertheless results from acute toxicity, genotoxicity, immunotoxicity, neurotoxicity and reproductive toxicity investigations in different animal models do not provide a clear overview on ION safety yet, and epidemiological studies are almost inexistent. Much work has still to be done to fully understand how these nanomaterials interact with cellular systems and what, if any, potential adverse health consequences can derive from ION exposure.

Efeito do revestimento nas propriedades das rolhas de cortiça

A utilização de revestimentos poliméricos em rolhas de cortiça natural é uma prática recorrente na indústria de produção de rolhas. A sua aplicação tem como principal objetivo a melhoria da qualidade visual das rolhas. Contudo, este tratamento altera também as suas caraterísticas de molhabilidade, pelo que é importante otimizar os processos de revestimento de superfície. O presente trabalho teve como objetivo principal a averiguação da influência de um revestimento colorido e de diferentes tratamentos de superfície no comportamento da rolha em garrafa. Foram utilizadas amostras, cedidas pela Cork Supply Portugal, provenientes de quatro branqueamentos distintos (LVL, CSP, CPI e SIL). Foram estudadas amostras com e sem revestimento colorido e, todas elas, tratadas superficialmente com quatro tipos de tratamento (TS1, TS2, TS3 e TS4), sendo as quantidades de parafina e silicone administradas todas diferentes. Para observar o efeito do revestimento colorido e dos tratamentos de superfície nas rolhas de cortiça, procedeu-se a testes para determinação de capilaridade, inserções e forças de extração, simulando as condições de engarrafamento/extração do cliente, de forma a verificar a conformidade dos resultados. Todos estes testes procederam-se nas instalações da CSP. Foram também efetuados testes de molhabilidade pela determinação de ângulos de contacto para três diferentes solventes, nomeadamente água, formamida e diiodometano, e obtidos os Wetting Envelopes, pelo método de OWRK, de forma a prever a molhabilidade das várias amostras. Os procedimentos experimentais descritos efetuaram-se nos laboratórios da Universidade de Aveiro. Aliando as análises aos vários testes efetuados, concluiu-se que o revestimento colorido tem um possível efeito favorecedor nas propriedades mecânicas das rolhas de cortiça, possui maior recetividade aos agentes lubrificantes e maior molhabilidade. Relativamente aos tratamentos de superfície, o melhor, tendo em conta os fatores de molhabilidade, foi o TS4, proporcionando melhor vedação ao vinho. Já a respeito da lubrificação, verificou-se melhores resultados para os tratamentos TS1 e TS2. A lavação SIL apresenta menor afinidade aos agentes vedantes e a CSP possui maior recetibilidade aos agentes lubrificantes.

Caracterização do cromo presente no lodo de galvanoplastia: avaliação técnica e econômica de processos de remoção

Dissertação (Mestrado em Tecnologia Nuclear)

Adequação bioclimática para os espaços urbanos abertos do centro de Fortaleza, CE

This research presents a study investigating the correlation between the environmental-physycal charcateristics of cities and the formation of its micro-climates. The study was conducted in the central area of Fortaleza characterized as a stable and consolidated area, where the city originated and currently faces serious problems in its urban dynamics. The points of measurements were determined by the elaboration and analysis of topography maps, height of buildings, land use, type of surface coating and vegetation, following the methodology of Katzschner (1997). A zoning map was then determined, according to common morphological characteristics of the 12 measurement points, which were based on a set of Romero s (2001) bioclimatic criteria. Air measurements, temperature, humidity, intensity and direction of winds were made in transect form in two different circuits in the study area, with six points of data collection in each area, in three different times: 6:00 am, 1:00pm and 7:00pm, during two periods of the year: August 2008 and March 2009. The results verified the influence of different environmental-physical types in the behavior of the climatic variables that were collected. A verticalização tão condenada em algumas situações se bem equilibrada e controlada pode reduzir as temperaturas do ar através do sombreamento dos espaços urbanos e possibilidade de maior permeabilidade a ventilação natural. The highest average air temperature and lower humidity were recorded at the point I at all times. This situation may have been in result of the high density, poor vegetation and extended paving of the ground. According to the results, it s clear the positive influence vegetation has on easing air temperature. Another indicator observed that areas with a greater variation in building heights tend to present decreased average air temperature. High rise structure, planned in accordance to urban air quality parameters, can reduce air temperatures by the shading of urban spaces and the possibility of greater penetration of natural ventilation

Construção de um aparato experimental para monitoramento in situ da deposição de filmes finos de titânio por magnetron sputtering

The technique of surface coating using magnetron sputtering is one of the most widely used in the surface engineering, for its versatility in obtaining different films as well as in the micro / nanometric thickness control. Among the various process parameters, those related to the active species of the plasma are of the most fundamental importance in the mechanism and kinetics of deposition. In order to identify the active species of the plasma, parameters such as gas flow, pressure and density of electric power were varied during titanium coating on glass substrate. By flowing argon gas of 10, 20, 30, 40 and 50 sccm (cubic centimeters per minute) for each gas flow a sequential scan of the electric current of 0.10, 0.20, 0.30, 0.40 , 0.50 A. The maximum value of 0.50 A was chosen based both on literature data and on limitations of the equipment. The monitoring of plasma species present during the deposition was carried out in situ by the technique of optical emission spectroscopy (OES) through the spectrometer Ocean Optics USB2000 Series. For this purpose, an apparatus was developed to adapt the OES inside the plasma reactor to stay positioned closest to the target. The radiations emitted by the species were detected by an optical fiber placed behind the glass substrate and their intensities as a function of wavelength were, displayed on a monitor screen. The acquisition time for each condition of the plain parameters was related to the minima of spectral lines intensities due to the film formed on the substrate. The intensities of different emission lines of argon and titanium were then analyzed as a function of time, to determine the active species and estimate the thickness of the deposited films. After the deposition, the coated glasses thin films were characterized by optical transmittance through an infrared laser. It was found that the thickness and deposition rate determined by in situ analysis were consistent with the results obtained by laser transmittance

Electrical conductivity of single walled and multiwalled carbon nanotube containing wool fibers

The main purpose of this study was producing conductive wool fabric applying carbon nanotubes. Raw and oxidized wool samples were treated with carbon nanotubes in the impregnating bath in the presence of citric acid as a crosslinking agent and sodium hypophosphite as a catalyst while sonicating them in the ultrasonic bath. Electrical resistance, washing durability, and color variation of treated samples were assessed. Through SEM images, the surface morphology of treated samples was studied confirming the surface coating through carbon nanotubes. According to the results, the electrical resistance of treated wool with carbon nanotubes reduced substantially. However, the single-walled carbon nanotubes are more useful to increase the conductivity. In addition, the wool color changed into gray after the treatment.