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Soilless substrates, such as peat, pine bark, and coir, are widely used as growing media in containerized crops for their favorable characteristics, including low bulk density, balanced air exchange and water retention, disease resistance, and low pH and salinity. However, improper irrigation of these media can have negative outcomes such as root asphyxia, pathogen development, and reduced plant growth. Understanding pore size distributions, water dynamics, and gas diffusivity of these substrates is essential to promote plant growth. The effects of different particle sizes of soilless media on processes such as infiltration, hydraulic conductivity, and gas diffusivity are also not well understood. The characterization of these effects is important for the overall improvement of container crop production. This thesis presents three studies that aimed to characterize the physical and hydraulic properties of pine bark substrates, both unamended and amended with peat or coir. The first study looked at three substrate types: unamended, unscreened pine bark, peat-amended pine bark, and coir amended pine bark. Three methods were employed to quantify pore distributions: non-equilibrium infiltration measurements, equilibrium water retention characterization, and scanning electron microscopy. We characterized pore distributions during wetting and drainage for the three substrates. Coir-amended bark had the largest water-conducting porosity, highest hydraulic conductivity, and most water retention. Unamended pine bark had the highest microporosity, and the addition of peat and coir lowered macroporosity, with peat having the greater effect. The total porosity inferred from the infiltration method was significantly smaller than that inferred from drainage experiments due to assumptions related to pore shape. The second study focused on defining hydraulic conductivity and water retention for pine bark substrates of five different particle sizes, <1 mm, 1-2 mm, 2-4 mm, 4-6 mm, and an unscreened fraction. We utilized the same methods from the first study. The resulting data showed that the smallest particle sizes (i.e., <1 mm and 1-2 mm) had the highest hydraulic conductivity and greatest water retention. The three larger sizes had lower hydraulic conductivity and poor water retention, including the unscreened fraction, which more closely followed the results of the 2-4 mm size. The final study examined gas diffusivity of the five pine bark particle sizes at different moisture levels: 60% moisture content (initial conditions), saturated at the bottom of the sample, near-saturated at the sample bottom, and drained from saturation to container capacity. We used a one-chamber gas diffusion setup to find gas diffusion coefficients (Ds). The results displayed an inverse relationship between Ds values and substrate water content. In addition, the larger particle sizes were less sensitive to changes in water content due to their well-draining large pores. Proper balance of aeration and water retention is necessary for the success of soilless growing media. Overall, the smaller particle size fractions had the best water retention and hydraulic conductivity rates while the larger fractions had the largest Ds coefficients. This work contributes valuable knowledge on the physical and hydraulic properties of different size fractions of pine bark substrates, which can assist nursery growers in optimizing water usage for sustainable container crop production. / Master of Science / Since the 1950's soilless substrates have been an important resource for growing a variety of fruits, vegetables, flowers, and ornamental plants. Soilless growing media have become more popular choices for containerized plant production compared to natural soils due to improved air exchange, increased disease resistance, and more plants per acre. They are also favored because they help conserve resources, reduce agricultural waste, and minimize transportation requirements as compared to traditional cropping methods. The most popular types of soilless media include peat, coir, compost, and pine bark. In the U.S., pine bark is the main substrate used, as it is renewable and widely available. Growers still face many issues when using containerized crop production. For example, pine bark is susceptible to water runoff which can cause environmental problems and increase costs from this loss of water and fertilizer. Further characterizing of water and gas dynamics in of pine bark growing media is important for conserving water and fertilizer resources while optimizing plant growth in this container cropping industry. Pore characteristics, aeration, and water movement are key factors of substrates to be described to solve these challenges. This project aimed to apply soil physics strategies to soilless media, focusing on describing pore sizes, water movement, water holding capacity, and air movement in pine bark substrates. We utilized three methods throughout this study. For the first method, we took infiltration measurements to examine how water moved into the media, while the second utilized controlled drainage experiments to observe how water moved out of the media. The final method was characterizing gas movement through the substrates at different water contents and particle sizes. The results found showed that the smaller particle sizes and pine bark mixed with peat and coir had increased ability to retain water and allow water movement as compared to the larger particle sizes and unamended pine bark. In contrast, the larger particles had less water retention but improved gas movement. These results could be applied by stacking different particle sizes or mixes over one another could optimize water retention in the top of the container and drainage and gas movement in the bottom of the container. Overall, the application of this work is to create best management practices for growers to be able to balance water retention and gas movement in order to optimize plant growth.

Mesoporous materials constitute a promising class of nanomaterials for a number of applications due to their tunable pore structure. The synthesis of most mesoporous materials involves a surfactant liquid crystal structure to form the pores. As well as the many advantages associated with this method of synthesis, there are disadvantages such as high production costs and a substantial environmental impact which limit the possibilities for large scale production. Therefore there is a need for other synthesis routes. The aim of the work described herein was to contribute to this field by developing a synthesis route that does not rely on surfactants for pore formation. A mesoporous magnesium carbonate material was therefore formed by self-assemblage of the particles around carbon dioxide gas bubbles, which functioned as pore templates. It was also possible to vary the pore diameter between 3 and 20 nm. The biocompatibility of the formed magnesium carbonate material was evaluated in terms of in vitro cytotoxicity and hemocompatibility, in vivo skin irritation and acute systemic toxicity. The results from the in vitro cytotoxicity, in vivo skin irritation and acute systemic toxicity test using a polar extraction vehicle showed that the material was non-toxic. While signs of toxicity were observed in the acute systemic toxicity test using a non-polar solvent, this was attributed to injection of particles rather than toxic leachables. In the in vitro hemocompatibility test, no hemolytic activity was found with material concentrations of up to 1 mg/ml. It was further shown that the material had anticoagulant properties and induced moderate activation of the complement system. The anticoagulant properties were ascribed to uptake of Ca2+. Finally, the ability of the material to increase the dissolution rate of the poorly soluble drug itraconazole was analyzed.  Itraconazole was dissolved up to 23 times faster from the magnesium carbonate pores than when the free drug was used. The release rate from the delivery vehicle was dependent on the pore diameter. The work presented herein is expected to be useful for the development of alternative synthesis routes for mesoporous materials and also for encouraging the development of biomedical applications for these materials.

Liquid chromatography is an essential technique in manufacturing biopharmaceuticals where it is used on all scales from analytical applications in R&amp;D to full-scale production. In chromatography the target molecule, typically a protein, is separated and purified from other components and contaminants. Separation is based on different affinities of different molecules for the chromatographic medium and the physical and chemical properties of the latter determine the outcome. Controlling and designing those properties demand efficient analytical techniques. In this thesis the approach was to develop characterization methods based on nuclear magnetic resonance (NMR) spectroscopy for the assessment of various important physico-chemical properties. The rationale behind this strategy was that the versatility of NMR – with its chemical and isotopic specificity, high dynamic range, and direct proportionality between the integral intensity of the NMR signal and the concentration of spin-bearing atomic nuclei (e.g., 1H, 13C, 31P and 15N) – often renders it a very good choice for both qualitative and quantitative evaluations. These characteristics of NMR enabled us to develop two quantification methods for chromatography-media ligands, the functional groups that provide the specific interactions for the molecules being separated. Furthermore, a new method for measuring the distribution of macromolecules between the porous chromatographic beads and the surrounding liquid was established. The method, which we have named size-exclusion quantification (SEQ) NMR, utilizes the fact that it is possible to assess molecular size distribution from corresponding distribution of the molecular self-diffusion coefficient where the latter is accessible by NMR. SEQ-NMR results can also be interpreted in terms of pore-size distribution within suitable models. Finally, we studied self-diffusion of small molecules inside the pores of chromatographic beads. The results provided new insights into what affects the mass transport in such systems. The methods presented in this thesis are accurate, precise, and in many aspects better than conventional ones in terms of speed, sample consumption, and potential for automation. They are thus important tools that can assist a better understanding of the structure and function of chromatography media. In the long run, the results in this project may lead, via better chromatographic products, to better drugs and improved health. / Vätskekromatografi är en viktig teknik för tillverkning av biologiska läkemedel och används för alltifrån småskaliga analytiska applikationer till fullskalig produktion. I kromatografi separeras och renas målmolekylen (oftast ett protein), från andra komponenter och föroreningar genom att utnyttja molekylernas olika affinitet för det kromatografiska mediumet, vars fysikaliska och kemiska egenskaper har stor betydelse för hur separationen fungerar. För att kunna kontrollera och designa dessa egenskaper krävs effektiva analysmetoder. Strategin i den här avhandlingen var att utveckla metoder baserade på kärnmagnetisk resonans (NMR) spektroskopi för att karaktärisera flera viktiga fysikalisk-kemiska egenskaper. Anledningen till denna strategi är att mångsidigheten hos NMR – med dess kemiska och isotopiska specificitet, stora dynamiska omfång och direkta proportionalitet mellan NMR-signalens integralintensitet och koncentrationen av spinnbärande atomkärnor (t.ex. 1H, 13C, 31P och 15N) - ofta gör den till det bästa valet för både kvalitativa och kvantitativa tillämpningar. Dessa egenskaper hos NMR gjorde att vi kunde utveckla två kvantifieringsmetoder för kromatografimedia-ligander, dvs de funktionella grupperna som ger de specifika interaktioner som gör att molekylerna kan separeras. Dessutom har en ny metod för att mäta fördelningen av makromolekyler mellan de porösa kromatografiska pärlorna och den omgivande vätskan tagits fram. Metoden, som vi har valt att kalla size-exclusion quantification (SEQ) NMR, utnyttjar det faktum att det är möjligt att mäta molekylstorleksfördelningen genom att mäta motsvarande fördelning av självdiffusionskoefficienter, där den sistnämnda kan bestämmas med NMR. Resultaten från SEQ-NMR kan tolkas i termer av porstorleksfördelningar genom att använda lämpliga modeller. Slutligen studerade vi självdiffusion av små molekyler inuti porerna i kromatografiska pärlor. Resultaten gav nya insikter om vad som påverkar masstransporten i sådana system. De metoder som presenteras i denna avhandling är noggranna, precisa och på många sätt bättre än konventionella metoder när det gäller hastighet, låg provförbrukning och automatiseringspotential. De nya metoderna är därför viktiga verktyg som kan hjälpa till att ge en bättre förståelse av struktur och funktion hos kromatografimedia. I det långa loppet kan resultat från det här projektet kunna bidra till effektivare kromatografiska produkter, vilket i slutändan kan leda till bättre läkemedel och hälsa. / <p>QC 20170403</p>

Aerogel materials have had limited utility due to their fragility, geometrical limitations, fabrication costs and protracted fabrication times. The objective of this project was to eliminate these limitations. Native, cross-linked and hybrid aerogel monoliths have been fabricated using a newly developed one-pot method without the need for solvent exchange. The key to this technique is the use of an ethanol–water azeotrope mixture, which contains 4.4% water by volume, as both a gelation and supercritical drying solvent. The small water content allows for drying at temperatures close to the supercritical temperature of the dry solvent, where reactions such as silica dissolution and polymer degradation are negligible. This improvement on conventional fabrication processes is of particular importance since it decreases the total duration of aerogel fabrication from five days to one day. Cross-linked silica aerogel monoliths were fabricated using one-pot hydrolysis-condensation wet chemistry methods as well as a rapid photogelation method. Both native silica and cross-linked aerogel components were made with a minimum dimension of up to 3.6 cm and in customizable shapes. Fabrication of homogeneous aerogels using these methods required a maximum of one day, as demonstrated in this work. Finally, LEDs and Laser irradiation were both used to selectively embed cross-linked aerogel into a larger native silica component to provide reinforcement and/or a surface which can be used for labeling or affixing the aerogel component to another surface.

Lime has been used in construction for millennia, and its value, especially in the field of conservation architecture, has only recently been rediscovered. Lime mortars harden through carbonation, and this thesis is a study of that process. The research conducted has resulted in the development of two novel techniques for the measurement and detection of carbonation. The first technique is a method of thermogravimetric analysis which allows the carbonation profile to be measured within an acceptable time-frame. The second technique is the use of drilling resistance measurement to visualise the carbonation profile. The potential of elemental analysis to measure the carbonation profile has also been identified. It has been demonstrated that the lime/water ratio has less impact on the compressive strength of air lime mortars than had previously been supposed. The change in the pore size distribution of air lime mortars caused by carbonation has been studied, and a theory has been proposed to explain this phenomenon. Five different forms of air lime binder were studied. The impact of these on the structural performance of the resultant mortars has been assessed. It was concluded that mortars made with lime putties perform better than mortars made with dry lime hydrate. Mortars made with dispersed hydrated lime appear to perform as well as mortars made with lime putties, but at a slower rate of strength growth. The use of extra mature lime putty does not appear to confer structural performance benefits when compared with ordinary lime putty. It has been shown that the use of calcitic aggregates can produce air lime mortars which perform as well as moderately hydraulic lime mortars. It is theorised that this phenomenon is not directly related to carbonation, but rather to a complex interaction of the granulometry, mineralogy, chemistry and porosity of the aggregate with the binder.

The effect of steady shear stress on somatic embryos were investigated in a flow chamber and evaluated at different time intervals using microscopy technique. The development of meristematic cell clusters, i.e. the immature embryos, into a polarized somatic embryo, and the effect on the localization of the suspensor cells that form during development of the immature embryos, were studied as a function of shear stresses. With the distribution and growth rate of the meristematic and suspensor cells, the effect of stress on the embryo development was established. Furthermore, the effect of shear stress on the cells at molecular level, the reaction of integrin-like proteins, the production of reactive oxygen species and the pore size of the cell walls involved in the shear stress responses, were investigated with molecular techniques. In general, shear stress inhibits meristematic cells growth. Meristematic cells grow fastest at shear rate of 86 s-1 among all the tested shear stress conditions. By combining the results of meristematic cells growth and suspensor cells formation, it suggests that there is a critical shear rate between 86 and 140 s-1, at which no suspensor cells form. The unidirectional flow with different shear stresses helps the polarized growth and the unidirectional alignment of suspensor cells. Reactive oxygen species and integrin-like protein are detected in the stressed cells as cellular responses to shear stresses. By monitoring the pore size and uptake time of cells to macromolecules with solute-exclusive experiments, it suggests that the stressed cells expedite the response to plasmolyzing components that are used to induce maturation treatment thus affect the response to maturation stimuli.

Για τον προσδιορισμό της πορομετρικής καμπύλης των γεωυφασμάτων διατίθενται σήμερα τρία πρότυπα (ASTM D6767, EN ISO 12956 και ASTM D4751) που θεωρούνται “διεθνούς” αποδοχής. Το πιο πρόσφατο από αυτά (ASTM D6767) εγκρίθηκε το 2002, ορίζει μέθοδο με βάση τη ροή σε τριχοειδή και αποτελεί το κύριο αντικείμενο της παρούσας διατριβής. Ελέγχθηκαν 52 μη υφασμένα γεωυφάσματα κατασκευασμένα από ίνες πολυπροπυλενίου τόσο κατά ASTM D6767 όσο και κατά EN ISO 12956 (υγρό κοσκίνισμα) και ASTM D4751 (ξηρό κοσκίνισμα). Τα αποτελέσματα που προέκυψαν συγκρίθηκαν τόσο μεταξύ τους όσο και με φυσικές ιδιότητες των γεωυφασμάτων, με τιμές μεγεθών που παρέχουν οι κατασκευαστές αυτών των προϊόντων και με τιμές μεγεθών που υπολογίζονται θεωρητικά. Τα μεγέθη πόρων και οι πορομετρικές καμπύλες που προκύπτουν εργαστηριακά με εφαρμογή κάθε μίας από τις τρεις μεθόδους είναι διαφορετικά. Αυτό οφείλεται στις διαφορετικές παραδοχές ή υποθέσεις κάθε μεθόδου αλλά και στις διαδικασίες που προβλέπει η κάθε μέθοδος. Ειδικότερα, οι δύο βασικές υποθέσεις του προτύπου ASTM D6767 αφορούν τη γωνία επαφής, θ, μεταξύ ρευστού και στερεού (τίθεται ίση με μηδέν) και τη μορφή της διατομής των πόρων των γεωυφασμάτων (κυλινδρική). Λόγω της δομής των μη υφασμένων γεωυφασμάτων οι δύο παραπάνω υποθέσεις δεν είναι δυνατόν να επαληθευθούν. Για τον λόγο αυτό στην εξίσωση προσδιορισμού των μεγεθών πόρων του προτύπου ASTM D6767 εισάγεται διορθωτικός συντελεστής. Από την επεξεργασία των αποτελεσμάτων της παρούσας διατριβής προέκυψε ότι ο συντελεστής αυτός πρέπει να έχει τιμή ίση με 1/3 (για τη συγκεκριμένη συσκευή που χρησιμοποιήθηκε και τις διαδικασίες που εφαρμόστηκαν για την εκτέλεση των δοκιμών) ώστε τα αποτελέσματα να προσεγγίζουν ικανοποιητικά αυτά της δοκιμής κατά EN ISO 12956. / Three internationally accepted standards (ASTM D6767, EN ISO 12956 and ASTM D4751) are available today for determing the pore size distribution of geotextiles. The most recently approved standard (2002) is ASTM D6767 which defines a method based on capillary flow. Laboratory testing according to this standard is the main subject of this thesis. Fifty two nonwoven geotextiles, made of polypropylene fibers, were tested according to the three standardized methods (ASTM D6767, EN ISO 12956 – wet sieving and ASTM D4751 – dry sieving). Comparisons were made between the results obtained from each standardized method as well as between measured pore sizes and geotextile physical properties, manufacturer provided pore sizes and values obtained theoretically. Different pore sizes and pore size distribution curves are obtained when different laboratory standard methods are applied. This is due to the different assumptions on which each method is based and also due to the procedures that each method specifies. The two main assumptions of the Standard ASTM D6767 concern the contact angle, θ, between liquid and solid (equal to zero) and the pore shapes of the geotextiles (cylindrical). Due to the structure of the nonwoven geotextiles the effect of these assumptions is different to quantify. Accordingly, the computation of pore sizes according standard ASTM D6767 is based on the introduction of a correction coefficient in the pertinent equation. The results obtained during this correction coefficient should have a value equal to 1/3 for the particular device used and the procedures applied. Use of this correction coefficient fields results that approximate very well the results obtained from wet sieving tests according to Standard EN ISO 12956.

Made available in DSpace on 2014-06-11T19:33:39Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-01-20Bitstream added on 2014-06-13T21:06:47Z : No. of bitstreams: 1 beraldo_jmg_dr_jabo.pdf: 1719744 bytes, checksum: a27050b0770082469a896d7df06651eb (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O sistema de semeadura direta (SSD) proporciona melhores condições físicas do solo favorecendo o armazenamento de água no solo (ARM). A hipótese do trabalho foi que o Latossolo Vermelho argiloso, em sequências de culturas de verão e inverno sob SSD afeta o ARM em decorrência da modificação nos atributos físicos do solo e que o tensiômetro de punção digital (TDig) pode ser usado para medir o potencial mátrico da água no solo. Os objetivos foram avaliar o ARM e os atributos físicos do solo em sequências de culturas de verão e de inverno sob SSD e medir o potencial mátrico da água no solo por meio do tensiômetro de mercúrio e do TDig. O delineamento foi em blocos, com três repetições, no esquema em faixas. Os tratamentos foram constituídos por três sequências de culturas de verão (rotação soja/milho e monocultura de milho e soja) e sete culturas de inverno (milho, girassol, nabo forrageiro, milheto, guandu, sorgo e crotalária). Foram instalados tensiômetros nas camadas de 0,2; 0,4 e 0,6 m. Foi determinada a densidade do solo, a distribuição de poros por tamanho nas camadas de 0-0,1 e 0,1-0,2 m e a infiltração de água na superfície do solo. Os dados foram submetidos à análise de variância e as médias comparadas pelo teste de Tukey. O TDig pode ser usado para avaliar o potencial mátrico da água no solo. O ARM não diferiu entre as sequências de culturas de verão e nas culturas de inverno houve diferença, principalmente após período de menor disponibilidade hídrica. A densidade e a porosidade do solo não foram influenciadas pelas culturas de verão e inverno. O diâmetro de poros entre 0,075 - 0,05 e 0,03 - 0,0375 mm na camada de 0,0-0,1 m diferiu entre as sequências de verão. A distribuição de poros por tamanho não foi influenciada pelas sequências de culturas de inverno. A maior infiltração de água no solo ocorreu na parcela sob monocultura de soja / No tillage system provides soil physical properties improvements, and soil water storage. The hypothesis of this study was that a Red Latosol (Oxisol), in summer and winter crops sequences under no-tillage system, can have its soil water storage influenced by changes in soil physical properties and digital tensiometer can be used to measure soil water matric potential. This study aimed to measure the soil matric potential using both mercury and digital tensiometers and to evaluate the soil water storage and physical properties on summer and winter crops sequences under no-tillage system. A completely randomized block was designed with three replications on a strips plan. The treatments were the combination of three summer crops sequences (soybean/maize rotation, corn and soybean monocultures) and seven winter crops (maize, sunflower, oilseed radish, millet, pigeon pea, sorghum and sunn hemp). Tensiometers were installed at a depth of 0.20; 0.40; 0.60 meters. Bulk density and pores distribution curves were determined from layers 0-0.1 and 0.1-0.2 depth and water infiltration at the soil surface. The data were submitted to variance analysis and means were compared by the Tukey test. The hypothesis was confirmed, therefore digital tensiometer can be used to measure soil water matric potential. The results showed no difference regarding soil water storage in summer crops sequences, especially after a period associated with lower water availability. Soil porosity and bulk density were not influenced by summer and winter crops sequences. The results indicated that the pores with diameter between 0,075 - 0,05 e 0,03 - 0,0375 mm from layer 0-0.1 m differed on summer crops sequences. No difference was observed by pores distribution curves between summer and winter crops sequences. The largest water infiltration occurred under the soybean monocultures plot

Thermoporosimetry is a technique to determine small pore sizes based on melting and crystallization point depression. The temperature shift was measured by Differential Scanning Calorimetry (DSC). Development of thermoporosimetry was carried out on silica with a well-characterized narrow pore size distribution. Several parameters were studied, which a have a direct influence on melting and crystallization point depression (for example: a quality of the solvent, filling the pores with the solvent, time and frequency of centrifuging, superfluous solvent removal conditions, etc.). The optimum conditions for the thermoporosimetry method were developed using high porosity silica. The optimized experimental conditions found for silica were applied to polypropylene powder with much lower porosity. Several polypropylene powders were synthesized using different polymerization catalysts and their porosity determined. Polymer powder morphology and structure was characterized by standard methods. Powder porosity obtained by thermoporometry, gas sorption, and BET methods was compared.