Enabling ultra high precision on hard steels using surface defect machining

This paper is an extension to an idea coined during the 13th EUSPEN Conference (P6.23) named "surface defect machining" (SDM). The objective of this work was to demonstrate how a conventional CNC turret lathe can be used to obtain ultra high precision machined surface finish on hard steels without recourse to a sophisticated ultra precision machine tool. An AISI 4340 hard steel (69 HRC) workpiece was machined using a CBN cutting tool with and without SDM. Post-machining measurements by a Form Talysurf and a Scanning Electron Microscope (FEI Quanta 3D) revealed that SDM culminates to several key advantages (i) provides better quality of the machined surface integrity and offers (ii) lowering feed rate to 5μm/rev to obtain a machined surface roughness of 30 nm (optical quality).

Insight of the interface of electroless Ni-P/SiC composite coating on aluminium alloy, LM24

Electroless nickel composite coatings with silicon carbide, SiC, as reinforcing particles deposited with Ni–P onto aluminium alloy, LM24, having zincating as under layer were subjected to heat treatment using air furnace. The changes at the interface were investigated using scanning electron microscope (SEM) and energy dispersive X-ray (EDX) to probe the chemistry changes upon heat treatment. Microhardness tester with various loads using both Knoop and Vickers indenters was used to study the load effect clubbed with the influence of second phase particles on the coating at the vicinity of the interface. It was observed that zinc was absent at the interface after elevated temperature heat treatment at 400–500 °C. Precipitation of copper and nickel with a distinct demarcation (copper rich belt) along the coating interface was seen with irregular thickness of the order of 1 μm. Migration of copper from the bulk aluminium alloy could have been the factor. Brittleness of the coating was confirmed on heat treatment when indented with Vickers. However, in composite coating the propagation of the microcrack was stopped by the embedded particles but the microcracks continue in the matrix when not interrupted by second phase particles (SiC).

Micro-scale abrasion behaviour of electroless Ni-P-SiC coating on aluminium alloy

Electroless nickel (EN) and electroless nickel composite (ENC) coatings were deposited on aluminium alloy substrate, LM24. The micro abrasion test was conducted to study the wear behaviour of the coatings with the effect of SiC concentration. Microhardness of the coatings was tested also. The wear scars were analysed using optical microscope and scanning electron microscope (SEM). The wear resistance was found to be improved in composite coating that has higher microhardness as compared to particles free and the bare aluminium substrate. In as-deposited condition for the composite coating, the wear volume increases on increase in SiC percentage in the coating but is found to be minimum for lower SiC percentage. The increase in hardness on heat treatment at 400°C is due to the hardening or grain coarsening with the formation Ni3P.

Factors influencing the compressive strengths of fly ash based geopolymers

Several factors affecting the reactivity of pulverised fuel ash (pfa) as a precursor for geopolymer concrete have been investigated. These include physical and chemical properties of various pfa sources, inclusion of ground granulated blast furnace slag (ggbs), chemical activator dosages and curing temperature. Alkali-activated pfa was found to require elevated curing temperatures and high alkali concentrations. A mixture of sodium hydroxide and sodium silicate was used and this was shown to result in high strengths, as high as 70 MPa at 28-days. The presence of silicates in solution was found to be a key factor. Detailed physical and chemical characterisation was carried out on thirteen pfa sources from the UK. The most important factor affecting the reactivity was found to be the particle size of pfa. The loss on ignition (LOI) and the amorphous content are also important parameters that need to be considered for the selection of pfa for use in geopolymer concrete. The partial replacement of pfa by ground granulated blast furnace slag (ggbs) was found to be beneficial in not only avoiding the need for elevated curing temperatures but also in improving compressive strengths. Microstructural characterisation with scanning electron microscope (SEM) coupled with energy dispersive X-ray spectroscopy (EDS) was performed on pfa/ggbs pastes. The reaction product of pfa and ggbs in these binary systems was calcium aluminium silicate hydrate gel (C-A-S-H) with inclusion of Na in the structure.

Ferroelectric : CNTs structures fabrication for advanced functional nano devices

This work is about the combination of functional ferroelectric oxides with Multiwall Carbon Nanotubes for microelectronic applications, as for example potential 3 Dimensional (3D) Non Volatile Ferroelectric Random Access Memories (NVFeRAM). Miniaturized electronics are ubiquitous now. The drive to downsize electronics has been spurred by needs of more performance into smaller packages at lower costs. But the trend of electronics miniaturization challenges board assembly materials, processes, and reliability. Semiconductor device and integrated circuit technology, coupled with its associated electronic packaging, forms the backbone of high-performance miniaturized electronic systems. However, as size decreases and functionalization increases in the modern electronics further size reduction is getting difficult; below a size limit the signal reliability and device performance deteriorate. Hence miniaturization of siliconbased electronics has limitations. On this background the Road Map for Semiconductor Industry (ITRS) suggests since 2011 alternative technologies, designated as More than Moore; being one of them based on carbon (carbon nanotubes (CNTs) and graphene) [1]. CNTs with their unique performance and three dimensionality at the nano-scale have been regarded as promising elements for miniaturized electronics [2]. CNTs are tubular in geometry and possess a unique set of properties, including ballistic electron transportation and a huge current caring capacity, which make them of great interest for future microelectronics [2]. Indeed CNTs might have a key role in the miniaturization of Non Volatile Ferroelectric Random Access Memories (NVFeRAM). Moving from a traditional two dimensional (2D) design (as is the case of thin films) to a 3D structure (based on a tridimensional arrangement of unidimensional structures) will result in the high reliability and sensing of the signals due to the large contribution from the bottom electrode. One way to achieve this 3D design is by using CNTs. Ferroelectrics (FE) are spontaneously polarized and can have high dielectric constants and interesting pyroelectric, piezoelectric, and electrooptic properties, being a key application of FE electronic memories. However, combining CNTs with FE functional oxides is challenging. It starts with materials compatibility, since crystallization temperature of FE and oxidation temperature of CNTs may overlap. In this case low temperature processing of FE is fundamental. Within this context in this work a systematic study on the fabrication of CNTs - FE structures using low cost low temperature methods was carried out. The FE under study are comprised of lead zirconate titanate (Pb1-xZrxTiO3, PZT), barium titanate (BaTiO3, BT) and bismuth ferrite (BiFeO3, BFO). The various aspects related to the fabrication, such as effect on thermal stability of MWCNTs, FE phase formation in presence of MWCNTs and interfaces between the CNTs/FE are addressed in this work. The ferroelectric response locally measured by Piezoresponse Force Microscopy (PFM) clearly evidenced that even at low processing temperatures FE on CNTs retain its ferroelectric nature. The work started by verifying the thermal decomposition behavior under different conditions of the multiwall CNTs (MWCNTs) used in this work. It was verified that purified MWCNTs are stable up to 420 ºC in air, as no weight loss occurs under non isothermal conditions, but morphology changes were observed for isothermal conditions at 400 ºC by Raman spectroscopy and Transmission Electron Microscopy (TEM). In oxygen-rich atmosphere MWCNTs started to oxidized at 200 ºC. However in argon-rich one and under a high heating rate MWCNTs remain stable up to 1300 ºC with a minimum sublimation. The activation energy for the decomposition of MWCNTs in air was calculated to lie between 80 and 108 kJ/mol. These results are relevant for the fabrication of MWCNTs – FE structures. Indeed we demonstrate that PZT can be deposited by sol gel at low temperatures on MWCNTs. And particularly interesting we prove that MWCNTs decrease the temperature and time for formation of PZT by ~100 ºC commensurate with a decrease in activation energy from 68±15 kJ/mol to 27±2 kJ/mol. As a consequence, monophasic PZT was obtained at 575 ºC for MWCNTs - PZT whereas for pure PZT traces of pyrochlore were still present at 650 ºC, where PZT phase formed due to homogeneous nucleation. The piezoelectric nature of MWCNTs - PZT synthesised at 500 ºC for 1 h was proved by PFM. In the continuation of this work we developed a low cost methodology of coating MWCNTs using a hybrid sol-gel / hydrothermal method. In this case the FE used as a proof of concept was BT. BT is a well-known lead free perovskite used in many microelectronic applications. However, synthesis by solid state reaction is typically performed around 1100 to 1300 ºC what jeopardizes the combination with MWCNTs. We also illustrate the ineffectiveness of conventional hydrothermal synthesis in this process due the formation of carbonates, namely BaCO3. The grown MWCNTs - BT structures are ferroelectric and exhibit an electromechanical response (15 pm/V). These results have broad implications since this strategy can also be extended to other compounds of materials with high crystallization temperatures. In addition the coverage of MWCNTs with FE can be optimized, in this case with non covalent functionalization of the tubes, namely with sodium dodecyl sulfate (SDS). MWCNTs were used as templates to grow, in this case single phase multiferroic BFO nanorods. This work shows that the use of nitric solvent results in severe damages of the MWCNTs layers that results in the early oxidation of the tubes during the annealing treatment. It was also observed that the use of nitric solvent results in the partial filling of MWCNTs with BFO due to the low surface tension (<119 mN/m) of the nitric solution. The opening of the caps and filling of the tubes occurs simultaneously during the refluxing step. Furthermore we verified that MWCNTs have a critical role in the fabrication of monophasic BFO; i.e. the oxidation of CNTs during the annealing process causes an oxygen deficient atmosphere that restrains the formation of Bi2O3 and monophasic BFO can be obtained. The morphology of the obtained BFO nano structures indicates that MWCNTs act as template to grow 1D structure of BFO. Magnetic measurements on these BFO nanostructures revealed a week ferromagnetic hysteresis loop with a coercive field of 956 Oe at 5 K. We also exploited the possible use of vertically-aligned multiwall carbon nanotubes (VA-MWCNTs) as bottom electrodes for microelectronics, for example for memory applications. As a proof of concept BiFeO3 (BFO) films were in-situ deposited on the surface of VA-MWCNTs by RF (Radio Frequency) magnetron sputtering. For in situ deposition temperature of 400 ºC and deposition time up to 2 h, BFO films cover the VA-MWCNTs and no damage occurs either in the film or MWCNTs. In spite of the macroscopic lossy polarization behaviour, the ferroelectric nature, domain structure and switching of these conformal BFO films was verified by PFM. A week ferromagnetic ordering loop was proved for BFO films on VA-MWCNTs having a coercive field of 700 Oe. Our systematic work is a significant step forward in the development of 3D memory cells; it clearly demonstrates that CNTs can be combined with FE oxides and can be used, for example, as the next 3D generation of FERAMs, not excluding however other different applications in microelectronics.

Test and development of microcapsules for rigid polyurethane foam

Tese de mestrado em Química Tecnológica, apresentada à Universidade de Lisboa, através da Faculdade de Ciências, 2016

Citotoxicidade do ácido peracético: avaliação metabólica, estrutural e de morte em fibroblastos L929

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Cutting forces and wear analysis of Si3N4 diamond coated tools in high speed machining

Si3N4 tools were coated with a thin diamond film using a Hot-Filament Chemical Vapour Deposition (HFCVD) reactor, in order to machining a grey cast iron. Wear behaviour of these tools in high speed machining was the main subject of this work. Turning tests were performed with a combination of cutting speeds of 500, 700 and 900 m min−1, and feed rates of 0.1, 0.25 and 0.4 mm rot−1, remaining constant the depth of cut of 1 mm. In order to evaluate the tool behaviour during the turning tests, cutting forces were analyzed being verified a significant increase with feed rate. Diamond film removal occurred for the most severe set of cutting parameters. It was also observed the adhesion of iron and manganese from the workpiece to the tool. Tests were performed on a CNC lathe provided with a 3-axis dynamometer. Results were collected and registered by homemade software. Tool wear analysis was achieved by a Scanning Electron Microscope (SEM) provided with an X-ray Energy Dispersive Spectroscopy (EDS) system. Surface analysis was performed by a profilometer.

Molecular mobility, composition and structure analysis in glycerol plasticised chitosan films

This study was developed with the purpose to investigate the effect of polysaccharide/plasticiser concentration on the microstructure and molecular dynamics of polymeric film systems, using transmission electron microscope imaging (TEM) and nuclear magnetic resonance (NMR) techniques. Experiments were carried out in chitosan/glycerol films prepared with solutions of different composition. The films obtained after drying and equilibration were characterised in terms of composition, thickness and water activity. Results show that glycerol quantities used in film forming solutions were responsible for films composition; while polymer/total plasticiser ratio in the solution determined the thickness (and thus structure) of the films. These results were confirmed by TEM. NMR allowed understanding the films molecular rearrangement. Two different behaviours for the two components analysed, water and glycerol were observed: the first is predominantly moving free in the matrix, while glycerol is mainly bounded to the chitosan chain. (C) 2013 Elsevier Ltd. All rights reserved.

Desenvolvimento de um biossensor para Ácido Glutâmico

A presente dissertação tem com objetivo o desenvolvimento de um biossensor com base nos polímeros de impressão molecular para a deteção de uma molécula alvo, o ácido glutâmico que é convertido em glutamina pela glutamina sintetase, recorrendo à potenciometria. Nas células neoplásicas a glutamina não é sintetizada podendo-se considerar que o ácido glutâmico é um potencial agente anti-cancro. A técnica de impressão molécular utilizada foi a polimerização em bulk, combinando a acrilamida e a bis acrilamida com o ácido glutâmico. Para se verificar se a resposta potenciométrica obtida era de facto da molécula alvo foram preparados em paralelo com os sensores, materiais de controlo, ou seja, moléculas sem impressão molécular (NIP). Para se controlar a constituíção química dos vários sensores nomeadamente, do NIP e do polímero de impressão molecular (MIP) antes e após a remoção bem como a molécula foram realizados estudos de Espetroscopia de Infravermelhos de Transformada de Fourier (FTIR), Scanning electron microscope (SEM) e Espetroscopia de Raios X por dispersão em energia (EDS). Os materiais desenvolvidos foram aplicados em várias membranas que diferiam umas das outras, sendo seletivas ao ião. A avaliação das características gerais das membranas baseou-se na análise das curvas de calibração, conseguidas em meios com pHs diferentes, comparando os vários elétrodos. O pH 5 foi o que apresentou melhor resultado, associado a uma membrana que continha um aditivo, o p-tetra-octilphenol, e com o sensor com percentagem de 3%. Posto isto, testou-se em material biológico, urina, com as melhores características quer em termos de sensibilidade (18,32mV/década) quer em termos de linearidade (1,6x10-6 a 1,48x10-3 mol/L). Verificou-se ainda que aplicando iões interferentes na solução, estes não interferem nesta, podendo ser aplicados na amostra sem que haja alteração na resposta potenciométrica. O elétrodo é capaz de distinguir o ácido glutâmico dos restantes iões presentes na solução.

New tools for old organelles

For hundreds of years biologists have studied the naturally occurring diversity in plant and animal species. The invention of the electron microscope in the rst half of the 1900's reveled that cells also can be incredible complex (and often stunningly beautiful). However, despite the fact that the eld of cell biology has existed for over 100 years we still lack a formal understanding of how cells evolve: It is unclear what the extents are in cell and organelle morphology, if and how diversity might be constrained, and how organelles change morphologically over time.(...)

Fabrication and characterization of silicon position sensitive particle detectors

Position sensitive particle detectors are needed in high energy physics research. This thesis describes the development of fabrication processes and characterization techniques of silicon microstrip detectors used in the work for searching elementary particles in the European center for nuclear research, CERN. The detectors give an electrical signal along the particles trajectory after a collision in the particle accelerator. The trajectories give information about the nature of the particle in the struggle to reveal the structure of the matter and the universe. Detectors made of semiconductors have a better position resolution than conventional wire chamber detectors. Silicon semiconductor is overwhelmingly used as a detector material because of its cheapness and standard usage in integrated circuit industry. After a short spread sheet analysis of the basic building block of radiation detectors, the pn junction, the operation of a silicon radiation detector is discussed in general. The microstrip detector is then introduced and the detailed structure of a double-sided ac-coupled strip detector revealed. The fabrication aspects of strip detectors are discussedstarting from the process development and general principles ending up to the description of the double-sided ac-coupled strip detector process. Recombination and generation lifetime measurements in radiation detectors are discussed shortly. The results of electrical tests, ie. measuring the leakage currents and bias resistors, are displayed. The beam test setups and the results, the signal to noise ratio and the position accuracy, are then described. It was found out in earlier research that a heavy irradiation changes the properties of radiation detectors dramatically. A scanning electron microscope method was developed to measure the electric potential and field inside irradiated detectorsto see how a high radiation fluence changes them. The method and the most important results are discussed shortly.

Host-parasite relationships in mycoparasite /

A mycoparasite, Piptocephalis virginiana ^ shows a resemblance to fungal parasites of higher plants in the fine structure of hyphae and haustoria. The morphology and fine structure of host and parasitic fungi have been described. The mode of penetration of the host cell, Choanephora cucurbitarum , probably involves mechanical forces. Although the presence of cell wall degrading enzyme was not detected by conventional techniques, its role in penetration can't be ruled out. A collar around the haustorial neck is formed as an extension of the host cell wall. No papilla was detected although appressorixim was seen during penetration. The young haustorium is enclosed in highly invaginating plasmalemma of the host cell and n\imerous cisternae of endoplasmic reticulum. Appearance of an electron—dense sheath around the mature haustorium seems to coincide with the disappearance of cisternae of endoplasmic reticulum from the host cystoplasm in the vicinity of the haustorium. The role of host cytoplasm particularly of endoplasmic reticulum in the development of the sheath is discussed. Extensive accumulation of spherosomes-like bodies, containing lipids, is found in haustorium, parasite and host hypha. Electron microscope revealed the parasiticculture spore has more lipid content than the axenic culture spore of P. virginiana . The biochemical and cytochemical tests also support these results. The mature spore of C. cucurbitarum possesses a thick three-layered cell wall, different from the hyphal wall. Its germination is accompanied by the formation of an elastic thin inner layer which surrounds the emerging germ tube and the growing hypha. High resolution autoradiography showed that H N-acetyl-glucosamine , a precursor of chitin, was incorporated preferentially in the thin inner layer of the spore wall and also in the cell wall of the growing hypha. When the label was fed to the infected cells, at different intervals after inoculation, grains were observed on the sheath which developed around the haustorium of P. virginiana , 30 hours after inoculation. The significance of these results in relation to the origin and composition of the sheath is discussed.

A biochemical predictor of performance during mesophilic anaerobic fermentation of starch wastewater

The aim of this study was to determine the potential of biochemical parameters, such as enzyme activity and adenosine triphosphate (ATP) levels, as monitors of process performance in the Upflow Anaerobic Sludge Blanket (UASB) reactor utilizing a starch wastewater. The acid and alkaline phosphatase activity and the ATP content of the UASB sludge were measured in response to changes in flow rate and nutrient loading. Conventional parameters of process performance, such as gas production, acetic acid production, COD, phosphorus, nitrogen and suspended solids loadings and % COD removal were also monitored. The response of both biochemical and conventional parameters to changing process conditions was then compared. Alkaline phosphatase activity exhibited the highest activity over the entire study perioda A high suspended solids loading was observed to upset the system in terms of gas production, acetic acid production and % COD removala The initial rate of increase in alkaline phosphatase activity following an increase in loading was four times as great during process upset than under conditions of good performance. The change in enzyme actiVity was also more sensitive to process upset than changes in acetic acid production. The change in ATP content of the sludge with time suggested that enzyme actiVity was changing independently of the actual viable biomass present. The bacterial composition of the anaerobic sludge granules was similar to that of other sludge bed systems, at the light and scanning electron microscope level. Isolated serum bottle cultures produced several acids involved in anaerobic carbohydrate metabolism. The overall performance of the UASB system indicated that higher loadings of soluble nutrients could have been tolerated by the system.

Microstructural and geochemical investigation of North American lower-middle Paleozoic trilobites and recent arthropods

Trilobites ¥tere collected from Ordovician and Devonian formations of Ontario} New York} Ohio} Oklahoma} and Indiana. Diversity was generally low} but 19..?telllS and Ph..~tY>ps ¥tere the most abundant species from the Ordovician and Devonian} respectively. Recent marine arthropods ¥tere collected from the Atlantic shore of the middle Florida Keys} and from the Pacific and lagoonal waters at Cape Beale} B. C. Fresh-water arthropods were collected along the shore of the Severn River in northcentral Ontario. Cuticles ¥tere analyzed for major} minor and trace elements, 180 and 13C isotopes, as ¥tell as examined by scanning electron micr?scope to identify original and diagenetic fabrics. Examination of trilobite cuticles by scanning electron microscope revealed several microstructures consistent with those observed in Recent arthropods. Microstructures} such as setae and tegumental gland duct openings} in like sized Lim/IllS and Isoteline trilobites may indicate common ancestral origins for these organisms, or simply parallel cuticle evolutions. The dendritic microstructure, originally' thought to be a diagenetic indicator, was found in Recent specimens and therefore its presence in trilobites may be suggestive of the delicate nature of diagenesis in trilobites. The absence of other primary microstructures in trilobites may indicate alteration, taxonomic control} or that there is some inherent feature of S EM examination which may' not allow detection of some features} while others are apparently visit·le onl~1 under SH.·1. The region of the cuticle sampled for examination is also a major influence in detecting pristine microstructures, as not all areas of trilobite and Recent arthropod cuticles will have microstructures identifiable in a SEM study. Subtleties in the process of alteration, however} ma~·· leave pristine microstructures in cuticles that are partial~/ silicified or do 10m itized, and degree and type of alteration may vary stratigraphically and longitudinally within a unit. The presence of fused matrices, angular calcite rhombs, and pyrite in the cuticle are thought to be indicative of altered cuticles, although pyritization may not affect the entire cuticle. t-~atural processes in Recent arthropods, such as molting, lead to variations in cuticle chemistries, and are thought to reflect the area of concentration of the elements during calcification. The level of sodium in Recent arthropods was found to be higher than that in trilobites, but highly mobile when sUbjected to the actions of VY'€'athering. Less saline water produced lovy'€'r magnesium and higher calcium values in Recent specimens .. and metal variations in pristine Ordovician trilobite cuticle appears to follow the constraints outlined for Recent arthropods, of regulation due to the chemislry of the surrounding medium. In diagenetic analysis, sodium, strontium and magnesium proved most beneficial in separating altered from least altered trilobites. Using this criterion, specimens from shale show the least amount of geochemical alteration, and have an original mineralogy of 1.7 - 2.4 mole % MgC03 (8000 t(> 9500 ppm magnesium) for both /s>..?/e/11S lJA'i.riff!11S and PseIAit'11J17ites I..itmirpin..itl/~ and 2.8 - 3.3 mole % MgC03 (5000 to 7000 ppm magnesium) for Ph.i{).?PS This is Slightly lower than the mineralogy of Recent marine arthropods (4.43 - 12.1 mole % MgC03), and slightly higher than that of fresh-water crayfish (0.96 - 1.82 mole % MgC03). Geochemically pristine trilobites were also found to possess primary microstructures. Stable isotope values and trends support the assertion that marine-meteoriclburial fluids were responsible for the alteration observed in a number of the trilobite specimens. The results of this stUdy suggest that fossil material has to be evaluated separately along taxonomic and lithological lines to arrive at sensible diagenetic and e nvironmenta I interpretations.