Modelos de regressão lineares para estimativa de produtividade da soja no oeste do Paraná, utilizando dados espectrais

The main objective of this work was to evaluate the linear regression between spectral response and soybean yield in regional scale. In this study were monitored 36 municipalities from the west region of the states of Parana using five images of Landsat 5/TM during 2004/05 season. The spectral response was converted in physical values, apparent and surface reflectances, by radiometric transformation and atmospheric corrections and both used to calculate NDVI and GVI vegetation indices. Those ones were compared by multiple and simple regression with government official yield values (IBGE). Diagnostic processing method to identify influents values or collinearity was applied to the data too. The results showed that the mean surface reflectance value from all images was more correlated with yield than individual dates. Further, the multiple regressions using all dates and both vegetation indices gave better results than simple regression.

Influence of the rubbery phase on the crystallinity and thermomechanical properties of poly(3-hydroxybutyrate)/elastomer blends

Poly(3-hydroxybutyrate) (PHB) is a very promising biopolymer. In order to improve its processability and decrease its brittleness, PHB/elastomer blends can be prepared. In the work reported, the effect of the addition of a rubbery phase, i.e. ethylene - propylene-diene terpolymer (EPDM) or poly(vinyl butyral) (PVB), on the properties of PHB was studied. The effects of rubber type and of changing the PHB/elastomer blend processing method on the crystallinity and physical properties of the blends were also investigated. For blends based on PHB, the main role of EPDM is its nucleating effect evidenced by a decrease of crystallization temperature and an increase of crystallinity with increasing EPDM content regardless of the processing route. While EPDM has a weak effect on PHB glass transition temperature, PVB induces a marked decrease of this temperature thank to its plasticizer that swells the PHB amorphous phase. A promising solution to improve the mechanical properties of PHB seems to be the melt-processing of PHB with both plasticizer and EPDM. In fact, the plasticizer is more efficient than the elastomer in decreasing the PHB glass transition temperature and, because of the nucleating effect of EPDM, the decrease of the PHB modulus due to the plasticizer can be counterbalanced. (C) 2010 Society of Chemical Industry

Improving Alzheimer`s Disease Diagnosis with Machine Learning Techniques

There is not a specific test to diagnose Alzheimer`s disease (AD). Its diagnosis should be based upon clinical history, neuropsychological and laboratory tests, neuroimaging and electroencephalography (EEG). Therefore, new approaches are necessary to enable earlier and more accurate diagnosis and to follow treatment results. In this study we used a Machine Learning (ML) technique, named Support Vector Machine (SVM), to search patterns in EEG epochs to differentiate AD patients from controls. As a result, we developed a quantitative EEG (qEEG) processing method for automatic differentiation of patients with AD from normal individuals, as a complement to the diagnosis of probable dementia. We studied EEGs from 19 normal subjects (14 females/5 males, mean age 71.6 years) and 16 probable mild to moderate symptoms AD patients (14 females/2 males, mean age 73.4 years. The results obtained from analysis of EEG epochs were accuracy 79.9% and sensitivity 83.2%. The analysis considering the diagnosis of each individual patient reached 87.0% accuracy and 91.7% sensitivity.

Subcritical crack growth in porcelains, glass-ceramics, and glass-infiltrated alumina composite for dental restorations

The objective was to compare fracture toughness (K(Ic)), stress corrosion susceptibility coefficient (n), and stress intensity factor threshold for crack propagation (K(I0)) of two porcelains [VM7/Vita (V) and d.Sign/Ivoclar (D)], two glass-ceramics [Empress/Ivolcar (E1) and Empress2/Ivlocar (E2)] and a glass-infiltrated alumina composite [In-Ceram Alumina/Vita (IC)]. Disks were constructed according to each manufacturer`s processing method, and polished before induction of cracks by a Vickers indenter. Crack lengths were measured under optical microscopy at times between 0.1 and 100 h. Specimens were stored in artificial saliva at 37A degrees C during the whole experiment. K(Ic) and n were determined using indentation fracture method. K(I0) was determined by plotting log crack velocity versus log K(I). Microstructure characterization was carried out under SEM, EDS, X-ray diffraction and X-ray fluorescence. IC and E2 presented higher K(Ic) and K(I0) compared to E1, V, and D. IC presented the highest n value, followed by E2, D, E1, and V in a decreasing order. V and D presented similar K(Ic), but porcelain V showed higher K(I0) and lower n compared to D. Microstructure features (volume fraction, size, aspect ratio of crystalline phases and chemical composition of glassy matrix) determined K(Ic). The increase of K(Ic) value favored the increases of n and K(I0).

Application to quantify fetal lung branching on rat explants

Recently, regulating mechanisms of branching morphogenesis of fetal lung rat explants have been an essential tool for molecular research. The development of accurate and reliable segmentation techniques may be essential to improve research outcomes. This work presents an image processing method to measure the perimeter and area of lung branches on fetal rat explants. The algorithm starts by reducing the noise corrupting the image with a pre-processing stage. The outcome is input to a watershed operation that automatically segments the image into primitive regions. Then, an image pixel is selected within the lung explant epithelial, allowing a region growing between neighbouring watershed regions. This growing process is controlled by a statistical distribution of each region. When compared with manual segmentation, the results show the same tendency for lung development. High similarities were harder to obtain in the last two days of culture, due to the increased number of peripheral airway buds and complexity of lung architecture. However, using semiautomatic measurements, the standard deviation was lower and the results between independent researchers were more coherent

Application to quantify fetal lung branching on rat explant

Recently, regulating mechanisms of branching morphogenesis of fetal lung rat explants have been an essential tool for molecular research. The development of accurate and reliable segmentation techniques may be essential to improve research outcomes. This work presents an image processing method to measure the perimeter and area of lung branches on fetal rat explants. The algorithm starts by reducing the noise corrupting the image with a pre-processing stage. The outcome is input to a watershed operation that automatically segments the image into primitive regions. Then, an image pixel is selected within the lung explant epithelial, allowing a region growing between neighbouring watershed regions. This growing process is controlled by a statistical distribution of each region. When compared with manual segmentation, the results show the same tendency for lung development. High similarities were harder to obtain in the last two days of culture, due to the increased number of peripheral airway buds and complexity of lung architecture. However, using semiautomatic measurements, the standard deviation was lower and the results between independent researchers were more coherent.

Femtosecond laser ablation of dentin

The surface morphology, structure and composition of human dentin treated with a femtosecond infrared laser (pulse duration 500 fs, wavelength 1030 nm, fluences ranging from 1 to 3 J cm(-2)) was studied by scanning electron microscopy, x-ray diffraction, x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The average dentin ablation threshold under these conditions was 0.6 +/- 0.2 J cm(-2) and the ablation rate achieved in the range 1 to 2 mu m/pulse for an average fluence of 3 J cm(-2). The ablation surfaces present an irregular and rugged appearance, with no significant traces of melting, deformation, cracking or carbonization. The smear layer was entirely removed by the laser treatment. For fluences only slightly higher than the ablation threshold the morphology of the laser-treated surfaces was very similar to the dentin fracture surfaces and the dentinal tubules remained open. For higher fluences, the surface was more porous and the dentin structure was partially concealed by ablation debris and a few resolidified droplets. Independently on the laser processing parameters and laser processing method used no sub-superficial cracking was observed. The dentin constitution and chemical composition was not significantly modified by the laser treatment in the processing parameter range used. In particular, the organic matter is not preferentially removed from the surface and no traces of high temperature phosphates, such as the beta-tricalcium phosphate, were observed. The achieved results are compatible with an electrostatic ablation mechanism. In conclusion, the high beam quality and short pulse duration of the ultrafast laser used should allow the accurate preparation of cavities, with negligible damage of the underlying material.

Engineering bio-based polymers using alternative solvents and processes

The work presented in this thesis explores novel routes for the processing of bio-based polymers, developing a sustainable approach based on the use of alternative solvents such as supercritical carbon dioxide (scCO2), ionic liquids (ILs) and deep eutectic solvents (DES). The feasibility to produce polymeric foams via supercritical fluid (SCF) foaming, combined with these solvents was assessed, in order to replace conventional foaming techniques that use toxic and harmful solvents. A polymer processing methodology is presented, based on SCF foaming and using scCO2 as a foaming agent. The SCF foaming of different starch based polymeric blends was performed, namely starch/poly(lactic acid) (SPLA) and starch/poly(ε-caprolactone) (SPCL). The foaming process is based on the fact that CO2 molecules can dissolve in the polymer, changing their mechanical properties and after suitable depressurization, are able to create a foamed (porous) material. In these polymer blends, CO2 presents limited solubility and in order to enhance the foaming effect, two different imidazolium based ILs (IBILs) were combined with this process, by doping the blends with IL. The use of ILs proved useful and improved the foaming effect in these starch-based polymer blends. Infrared spectroscopy (FTIR-ATR) proved the existence of interactions between the polymer blend SPLA and ILs, which in turn diminish the forces that hold the polymeric structure. This is directly related with the ability of ILs to dissolve more CO2. This is also clear from the sorption experiments results, where the obtained apparent sorption coefficients in presence of IL are higher compared to the ones of the blend SPLA without IL. The doping of SPCL with ILs was also performed. The foaming of the blend was achieved and resulted in porous materials with conductivity values close to the ones of pure ILs. This can open doors to applications as self-supported conductive materials. A different type of solvents were also used in the previously presented processing method. If different applications of the bio-based polymers are envisaged, replacing ILs must be considered, especially due to the poor sustainability of some ILs and the fact that there is not a well-established toxicity profile. In this work natural DES – NADES – were the solvents of choice. They present some advantages relatively to ILs since they are easy to produce, cheaper, biodegradable and often biocompatible, mainly due to the fact that they are composed of primary metabolites such as sugars, carboxylic acids and amino-acids. NADES were prepared and their physicochemical properties were assessed, namely the thermal behavior, conductivity, density, viscosity and polarity. With this study, it became clear that these properties can vary with the composition of NADES, as well as with their initial water content. The use of NADES in the SCF foaming of SPCL, acting as foaming agent, was also performed and proved successful. The SPCL structure obtained after SCF foaming presented enhanced characteristics (such as porosity) when compared with the ones obtained using ILs as foaming enhancers. DES constituted by therapeutic compounds (THEDES) were also prepared. The combination of choline chloride-mandelic acid, and menthol-ibuprofen, resulted in THEDES with thermal behavior very distinct from the one of their components. The foaming of SPCL with THEDES was successful, and the impregnation of THEDES in SPCL matrices via SCF foaming was successful, and a controlled release system was obtained in the case of menthol-ibuprofen THEDES.

Development of magnetoelectric CoFe2O4/poly(vinylidene fluoride) microspheres

Magnetoelectric microspheres based on piezoelectric poly(vinylidene fluoride) (PVDF) and magnetrostrictive CoFe2O4 (CFO), a novel morphology for polymer-based ME material, have been developed by an electrospray process. The CFO nanoparticles content in the (3-7 μm diameter) microspheres reaches values up to 27 wt.%, despite their concentration in the starting solution reaching values up to 70 wt.%. Additionally, the inclusion of magnetostrictive nanoparticles into the polymer spheres has no relevant effect on the piezoelectric β-phase content (≈60%), crystallinity (40%) and the onset degradation temperature (460º-465ºC) of the polymer matrix. The multiferroic microspeheres show a maximum piezoelectric reponse |d33|≈30 pC.N-1, leading to a magnetoelectric response of Δ|d33|≈5 pC.N-1 obtained when a 220 mT DC magnetic field was applied. It is also shown that the interface between CFO nanoparticles and PVDF (from 0 to 55%) has a strong influence on the ME response of the microspheres. The simplicity and the scalability of the processing method suggest a large application potential of this novel magnetoelectric geometry in areas such as tissue engineering, sensors and actuators.

Breast cancer and melanoma cell line identification by FTIR imaging after formalin-fixation and paraffin-embedding.

Over the past few decades, Fourier transform infrared (FTIR) spectroscopy coupled to microscopy has been recognized as an emerging and potentially powerful tool in cancer research and diagnosis. For this purpose, histological analyses performed by pathologists are mostly carried out on biopsied tissue that undergoes the formalin-fixation and paraffin-embedding (FFPE) procedure. This processing method ensures an optimal and permanent preservation of the samples, making FFPE-archived tissue an extremely valuable source for retrospective studies. Nevertheless, as highlighted by previous studies, this fixation procedure significantly changes the principal constituents of cells, resulting in important effects on their infrared (IR) spectrum. Despite the chemical and spectral influence of FFPE processing, some studies demonstrate that FTIR imaging allows precise identification of the different cell types present in biopsied tissue, indicating that the FFPE process preserves spectral differences between distinct cell types. In this study, we investigated whether this is also the case for closely related cell lines. We analyzed spectra from 8 cancerous epithelial cell lines: 4 breast cancer cell lines and 4 melanoma cell lines. For each cell line, we harvested cells at subconfluence and divided them into two sets. We first tested the "original" capability of FTIR imaging to identify these closely related cell lines on cells just dried on BaF2 slides. We then repeated the test after submitting the cells to the FFPE procedure. Our results show that the IR spectra of FFPE processed cancerous cell lines undergo small but significant changes due to the treatment. The spectral modifications were interpreted as a potential decrease in the phospholipid content and protein denaturation, in line with the scientific literature on the topic. Nevertheless, unsupervised analyses showed that spectral proximities and distances between closely related cell lines were mostly, but not entirely, conserved after FFPE processing. Finally, PLS-DA statistical analyses highlighted that closely related cell lines are still successfully identified and efficiently distinguished by FTIR spectroscopy after FFPE treatment. This last result paves the way towards identification and characterization of cellular subtypes on FFPE tissue sections by FTIR imaging, indicating that this analysis technique could become a potential useful tool in cancer research.

Towards desired crystalline product properties: In-situ monitoring of batch crystallization

The objective of industrial crystallization is to obtain a crystalline product which has the desired crystal size distribution, mean crystal size, crystal shape, purity, polymorphic and pseudopolymorphic form. Effective control of the product quality requires an understanding of the thermodynamics of the crystallizing system and the effects of operation parameters on the crystalline product properties. Therefore, obtaining reliable in-line information about crystal properties and supersaturation, which is the driving force of crystallization, would be very advantageous. Advanced techniques, such asRaman spectroscopy, attenuated total reflection Fourier transform infrared (ATR FTIR) spectroscopy, and in-line imaging techniques, offer great potential for obtaining reliable information during crystallization, and thus giving a better understanding of the fundamental mechanisms (nucleation and crystal growth) involved. In the present work, the relative stability of anhydrate and dihydrate carbamazepine in mixed solvents containing water and ethanol were investigated. The kinetics of the solvent mediated phase transformation of the anhydrate to hydrate in the mixed solvents was studied using an in-line Raman immersion probe. The effects of the operation parameters in terms of solvent composition, temperature and the use of certain additives on the phase transformation kineticswere explored. Comparison of the off-line measured solute concentration and the solid-phase composition measured by in-line Raman spectroscopy allowedthe identification of the fundamental processes during the phase transformation. The effects of thermodynamic and kinetic factors on the anhydrate/hydrate phase of carbamazepine crystals during cooling crystallization were also investigated. The effect of certain additives on the batch cooling crystallization of potassium dihydrogen phosphate (KDP) wasinvestigated. The crystal growth rate of a certain crystal face was determined from images taken with an in-line video microscope. An in-line image processing method was developed to characterize the size and shape of thecrystals. An ATR FTIR and a laser reflection particle size analyzer were used to study the effects of cooling modes and seeding parameters onthe final crystal size distribution of an organic compound C15. Based on the obtained results, an operation condition was proposed which gives improved product property in terms of increased mean crystal size and narrowersize distribution.

On-line –jatkojalostuksen integrointi mäntysahan tuotantoprosessiin

Diplomityön tavoitteena oli selvittää erilaisia jatkojalostusmahdollisuuksia, joilla voidaan nostaa suuren mäntysahan tuotteiston arvoa. Lisäksi tuli tarkastella jalostuksen integrointia sahan tuotantoprosessiin. Työn taustalla on toisaalta puutuotemarkkinoiden muuttuminen ja toisaalta raaka-aineen laadullinen huononeminen. Molemmat seikat vaikuttavat negatiivisesti perinteisen mäntysahan kannattavuuteen .Jatkojalostuksen integroinnilla sahatavaraprosessiin saavutetaan säästöjä tuotantokustannuksissa, kun tarkastellaan koko prosessia tukista jatkojalosteeksi. Myös raaka-aineen tuottavuutta voidaan nostaa integraation avulla. Jatkojalostus voidaan integroida sahatavaraprosessiin raaka-aineen valikoinnilla sahatavaraprosessin eri osissa, on-line –jalostuksella sekä taloudellisesti. Sahatavaraprosessissa tapahtuva raaka-aineen valikointi voidaan suorittaa tukeista ja sahatavarasta. Valikointikriteerinä voi olla puun ominaisuudet, sahatavaran mitat ja laatu. Valikointiin voidaan nykyteknologiasta hyödyntää röntgentekniikkaa sekä konenäköä. On-line –jalostus tarkoittaa kiinteästi sahatavaraprosessiin liittyvää jalostusta, jolloin ns. turhia prosessivaiheita jää pois ja syntyy säästöjä. On-line –jalostuksen edellytys on raaka-aineen jonkin asteinen valikointi, esim. pituus. Taloudellisesti integroitu jalostus tarkoittaa, että jalostuslaitoksella pyritään nollatulokseen ja jalostuksen lisäarvo palautetaan sahan toimittamaan raaka-aineen hintaan. Tällainen toiminta yhtiön sisällä poistaa turhaa keskustelua raaka-aineen siirtohinnoista ja siten vapauttaa osaltaan resursseja tuottavampaan toimintaan. Erilaisten jatkojalostusmuotojen ja puun ominaisuuksien hyödyntämisen seulonnan perusteella löytyi yksi jalostusmuoto, jolla voidaan kohottaa mäntysahan tuotteiston arvoa. Työn tuloksena syntyi investointiehdotus aihiotankotuotannosta ikkunateollisuuden tarpeisiin. Raaka-aineen hyödynnettäviä ominaisuuksia ovat männyn sydänpuun luonnollinen kestävyys sekä keskimääräinen oksaväli. Valikointi tehdään välitukeista, joiden sahaamisen kannattavuus on männyn rungon osista heikoin. Aihiotankoprosessissa hyödynnetään konenäköä ja sormijatkostekniikkaa. Jatkojalostuksen integrointi sahatavaraprosessiin toteutetaan rakentamalla on-line –jalostuslaitos sekä soveltamalla röntgentekniikkaa raaka-aineen valinnassa.

Ionic liquid mediated biomass deconstruction: from analysis challenges to fermentable sugars

Ionic liquids, ILs, have recently been studied with accelerating interest to be used for a deconstruction/fractionation, dissolution or pretreatment processing method of lignocellulosic biomass. ILs are usually utilized combined with heat. Regarding lignocellulosic recalcitrance toward fractionation and IL utilization, most of the studies concern IL utilization in the biomass fermentation process prior to the enzymatic hydrolysis step. It has been demonstrated that IL-pretreatment gives more efficient hydrolysis of the biomass polysaccharides than enzymatic hydrolysis alone. Both cellulose (especially cellulose) and lignin are very resistant towards fractionation and even dissolution methods. As an example, it can be mentioned that softwood, hardwood and grass-type plant species have different types of lignin structures leading to the fact that softwood lignin (guaiacyl lignin dominates) is the most difficult to solubilize or chemically disrupt. In addition to the known conventional biomass processing methods, several ILs have also been found to efficiently dissolve either cellulose and/or wood samples – different ILs are suitable for different purposes. An IL treatment of wood usually results in non-fibrous pulp, where lignin is not efficiently separated and wood components are selectively precipitated, as cellulose is not soluble or degradable in ionic liquids under mild conditions. Nevertheless, new ILs capable of rather good fractionation performance have recently emerged. The capability of the IL to dissolve or deconstruct wood or cellulose depends on several factors, (e.g. sample origin, the particle size of the biomass, mechanical treatments as pulverization, initial biomassto-IL ratio, water content of the biomass, possible impurities of IL, reaction conditions, temperature etc). The aim of this study was to obtain (fermentable) saccharides and other valuable chemicals from wood by a combined heat and IL-treatment. Thermal treatments alone contribute to the degradation of polysaccharides (e.g. 150 °C alone is said to cause the degradation of polysaccharides), thus temperatures below that should be used, if the research interest lies on the IL effectiveness. On the other hand, the efficiency of the IL-treatment can also be enhanced to combine other treatment methods, (e.g. microwave heating). The samples of spruce, pine and birch sawdust were treated with either 1-Ethyl-3-methylimidazolium chloride, Emim Cl, or 1-Ethyl-3-methylimidazolium acetate, Emim Ac, (or with ionized water for comparison) at various temperatures (where focus was between 80 and 120 °C). The samples were withdrawn at fixed time intervals (the main interest treatment time area lied between 0 and 100 hours). Double experiments were executed. The selected mono- and disaccharides, as well as their known degradation products, 5-hydroxymethylfurfural, 5-HMF, and furfural were analyzed with capillary electrophoresis, CE, and high-performance liquid chromatography, HPLC. Initially, even GC and GC-MS were utilized. Galactose, glucose, mannose and xylose were the main monosaccharides that were present in the wood samples exposed to ILs at elevated temperatures; in addition, furfural and 5-HMF were detected; moreover, the quantitative amount of the two latter ones were naturally increasing in line with the heating time or the IL:wood ratio.

Kartoitus Kaakkois-Suomen jätelietteistä, lietteen tuottajista ja käsittelymenetelmistä

In this thesis the sludge of Southeastern-Finland, the companies which produce sludge and the current methods and those still in development have been surveyed. 85 % of the waste sludge from industry comes from forest industries. The sludge from municipal waste water treatment plants is mostly used as a raw material for bioplants. The sludge from forest industry is mostly incinerated. New circulation methods increase the recycling value of the waste by creating new products but they still lack a full-scale plant. The political pressure from Europe and the politics driven by the government of Finland will drive circular economy forward and thus uplifting the processing options of waste slurries. This work is divided in two parts, first contains the survey and the second contains the experimental part and the operational methods based on the survey. In the experimental part wet hard sheet waste sludge was de-watered with shaking filter and the applications for waste sludge from cellulose factory were considered. The results are, that the wet hard sheet waste sludge can be dewatered to high enough total solids content for the inteded use. Also, the cellulose waste sludge has too high Cd content in almost all of the batches to be used as a land improment.

Real-time monitoring of laser scribing process utilizing high-speed camera

Currently, laser scribing is growing material processing method in the industry. Benefits of laser scribing technology are studied for example for improving an efficiency of solar cells. Due high-quality requirement of the fast scribing process, it is important to monitor the process in real time for detecting possible defects during the process. However, there is a lack of studies of laser scribing real time monitoring. Commonly used monitoring methods developed for other laser processes such a laser welding, are sufficient slow and existed applications cannot be implemented in fast laser scribing monitoring. The aim of this thesis is to find a method for laser scribing monitoring with a high-speed camera and evaluate reliability and performance of the developed monitoring system with experiments. The laser used in experiments is an IPG ytterbium pulsed fiber laser with 20 W maximum average power and Scan head optics used in the laser is Scanlab’s Hurryscan 14 II with an f100 tele-centric lens. The camera was connected to laser scanner using camera adapter to follow the laser process. A powerful fully programmable industrial computer was chosen for executing image processing and analysis. Algorithms for defect analysis, which are based on particle analysis, were developed using LabVIEW system design software. The performance of the algorithms was analyzed by analyzing a non-moving image from the scribing line with resolution 960x20 pixel. As a result, the maximum analysis speed was 560 frames per second. Reliability of the algorithm was evaluated by imaging scribing path with a variable number of defects 2000 mm/s when the laser was turned off and image analysis speed was 430 frames per second. The experiment was successful and as a result, the algorithms detected all defects from the scribing path. The final monitoring experiment was performed during a laser process. However, it was challenging to get active laser illumination work with the laser scanner due physical dimensions of the laser lens and the scanner. For reliable error detection, the illumination system is needed to be replaced.