MRI pressure and stress measurement in novel homogeneous soft solids

This paper presents MRI measurements of a novel semi solid MR contrast agent to pressure. The agent is comprised of potassium chloride cross linked carageenan gum at a concentration of 2% w/v, with micron size lipid coated bubbles of air at a concentration of 3% v/v. The choice for an optimum suspending medium, the methods of production and the preliminary MRI results are presented herein. The carageenan gum is shown to be ideally elastic for compressions relating to volume changes less than 15%, in contrast to the inelastic gellan gum also tested. Although slightly lower than that of gellan gum, carageenan has a water diffusion coefficient of 1.72×10-9 m2.s-1 indicating its suitability to this purpose. RARE imaging is performed whilst simultaneously compressing test and control samples and a maximum sensitivity of 1.6% MR signal change per % volume change is found which is shown to be independent of proton density variations due to the presence of microbubbles and compression. This contrast agent could prove useful for numerous applications, and particularly in chemical engineering. More generally the method allows the user to non-invasively image with MRI any process that causes, within the solid, local changes either in bubble size or bubble shape. © 2008 American Institute of Physics.

Sistemas semissólidos à base de nanopartículas lipídicas

As nanopartículas lipídicas foram desenvolvidas no início dos anos 90 e, atendendo às vantagens que apresentam comparativamente a outros sistemas coloidais, têm-se demonstrado muito promissoras, tanto para uso cosmético como farmacêutico. No entanto, atualmente apenas existem comercializados produtos cosméticos à base de nanopartículas lipídicas, o que pode ser justificado pelas restrições regulamentares relacionadas com a introdução de medicamentos no mercado. Existem dois tipos de nanopartículas lipídicas, as nanopartículas de lípidos sólidos (Solid Lipid Nanoparticles, SLN) e os vetores lipídicos nanoestruturados (Nanostructured Lipid Carriers, NLC), consistindo ambos em dispersões aquosas de nanopartículas sólidas. A baixa viscosidade destes sistemas dificulta a sua aplicação tópica. Neste contexto, têm sido desenvolvidas várias formulações semissólidas à base de nanopartículas lipídicas para aplicação tópica, nomeadamente cutânea, ocular, nasal e vaginal. A primeira parte desta dissertação consiste na revisão bibliográfica relativa ao estado da arte dos sistemas semissólidos à base de nanopartículas lipídicas, para uso farmacêutico e cosmético, baseada nos estudos realizados por diversos autores, entre 2012 e 2016. Na segunda parte, são apresentados resultados do trabalho experimental relativo ao desenvolvimento e caraterização de uma formulação semissólida à base de nanopartículas lipídicas.

Ocorrência de bactérias diazotroficas e fungos micorrizicos arbusculares na cultura da mandioca.

Este trabalho teve como objetivo avaliar a ocorrencia, isolar e identificar fungos micorrízicos carbunculares associados a cultura da mandioca (Manihot esculenta). Amostras de solo rizosférico e de varias partes da planta (raízes, tubérculos, manivas e folhas) de locais nos Estados do Rio de Janeiro, São Paulo e Paraná, foram inoculadas nos meios LGI-P, NFb-malato e NFb-GOC, avaliando-se o numero mais provável de células e a atividade de redução de acetileno. Bactérias diazotróficas foram isoladas de todas as partes da planta, com exceção das folhas, sendo identificadas como Klebsiella sp., Azospirillum lipoferum e uma bactéria denominada "E", provavelmente pertencente ao gênero Burkholderia. A bactéria E acumulou de 7,63 mg a 14,84 mg de N/g de C em meio semi-solido, isento de N, e conseguiu manter a capacidade de fixação biológica de N, mesmo apos uma dezena de repicagens consecutivas. A colonização micorrízica variou de 31% a 69%, e a densidade de esporos de 10 a 384 esporos/100 mL de solo, predominando as espécies Entrophospora colombiana e Acaulospora scrobiculata no Rio de Janeiro, A. scrobiculata e Scutellospora heterogama no Paraná e em Piracicaba (São Paulo) e A. appendicula e S. pellucida em Campinas (São Paulo). This study was performed to evaluate the occurrence and to isolate and identify diazotrophic bacteria and arbuscular mycorrhizal fungi associated with the cassava (Manihot esculenta) crop. Samples from rhizosperical soil, roots, tubers, stems and leaves from several localities of the States of Rio de Janeiro, Sao Paulo and Parana, in Brazil, were inoculated in three media specific for diazotrophic associative bacteria, LG1-P, NFb-malate and NFb-GOC, evaluating the most probable number of cells and the acetylene-reducing activity. Diazotrophic bacteria were detected in all plant parts except for the leaves, and were identified as Klebsiella sp., Azospirillum lipoferum and a bacterium called "E", probably belonging to the Burkholderia genus. Bacterium E was able to accumulate, in the N-free semi-solid media, from 7.63 to 14.84 mg of N/g of C and to maintain N fixation capacity after ten consecutive transferences. Mycorrhizal root colonization varied from 31% to 69% and spore density from 10 to 384 spores/100 mL of soil, predominanting the species Entrophospora colombiana and Acaulospora scrobiculata in Rio de Janeiro, A. scrobiculata and Scutellospora heterogama in Parana and in Piracicaba (Sao Paulo), and A. appendicula and S. pellucida in Campinas (Sao Paulo).

Influence of spatial constraints in non-crystalline regions on the polymer dynamics in semi-crystalline polyethylene: a solid state NMR study

A broad variety of solid state NMR techniques were used to investigate the chain dynamics in several polyethylene (PE) samples, including ultrahigh molecular weight PEs (UHMW-PEs) and low molecular weight PEs (LMW-PEs). Via changing the processing history, i.e. melt/solution crystallization and drawing processes, these samples gain different morphologies, leading to different molecular dynamics. Due to the long chain nature, the molecular dynamics of polyethylene can be distinguished in local fluctuation and long range motion. With the help of NMR these different kinds of molecular dynamics can be monitored separately. In this work the local chain dynamics in non-crystalline regions of polyethylene samples was investigated via measuring 1H-13C heteronuclear dipolar coupling and 13C chemical shift anisotropy (CSA). By analyzing the motionally averaged 1H-13C heteronuclear dipolar coupling and 13C CSA, the information about the local anisotropy and geometry of motion was obtained. Taking advantage of the big difference of the 13C T1 relaxation time in crystalline and non-crystalline regions of PEs, the 1D 13C MAS exchange experiment was used to investigate the cooperative chain motion between these regions. The different chain organizations in non-crystalline regions were used to explain the relationship between the local fluctuation and the long range motion of the samples. In a simple manner the cooperative chain motion between crystalline and non-crystalline regions of PE results in the experimentally observed diffusive behavior of PE chain. The morphological influences on the diffusion motion have been discussed. The morphological factors include lamellar thickness, chain organization in non-crystalline regions and chain entanglements. Thermodynamics of the diffusion motion in melt and solution crystallized UHMW-PEs is discussed, revealing entropy-controlled features of the chain diffusion in PE. This thermodynamic consideration explains the counterintuitive relationship between the local fluctuation and the long range motion of the samples. Using the chain diffusion coefficient, the rates of jump motion in crystals of the melt crystallized PE have been calculated. A concept of "effective" jump motion has been proposed to explain the difference between the values derived from the chain diffusion coefficients and those in literatures. The observations of this thesis give a clear demonstration of the strong relationship between the sample morphology and chain dynamics. The sample morphologies governed by the processing history lead to different spatial constraints for the molecular chains, leading to different features of the local and long range chain dynamics. The knowledge of the morphological influence on the microscopic chain motion has many implications in our understanding of the alpha-relaxation process in PE and the related phenomena such as crystal thickening, drawability of PE, the easy creep of PE fiber, etc.

Development and implementation of strategies for the incorporation of reinforcing elements in aluminium alloys by solid state processing

Dissertação para obtenção do Grau de Mestre em Engenharia Mecânica

Fick's law adapted to cationic diffusion in a semi-infinite solid: application to spinel megacrystals

In alkaline lavas, the chemical zoning of megacrystals of spinel is due to the cationic exchange between the latter and the host lava. The application of Fick's law to cationic diffusion profiles allows to calculate the time these crystals have stayed in the lava. Those which are in a chemical equilibrium were in contact with the lava during 20 to 30 days, whereas megacrystals lacking this equilibrium were in contact only for 3 or 4 days. The duration of the rise of an ultrabasic nodule in the volcanic chimney was calculated by applying Stokes' law.

Downstream processing of pectinase produced by Aspergillus niger in solid state cultivation and its application to fruit juices clarification

In this work, a protocol for the formulation of an enzyme concentrated product to be applied in fruit juice treatment is described. Downstream processing conditions for the recovery and concentration of pectinases produced by the new strain Aspergillus niger LB-02-SF in solid state cultivation were assessed. The solid-liquid ratio in the extraction step of pectinases recovery from the cultivated media was evaluated and the highest activity was obtained with a solid-liquid ratio of 1:10. The crude extract was concentrated by ultrafiltration and the total pectinase (TP) activity was 73.6-fold concentrated in relation to the crude extract, and a final TP titer of 663 U mL–1 was obtained with 73.7% of recovery yield. KCl and different glycerol concentrations were added to the concentrated extract and the stability of pectinases during the storage at 5°C for 59 weeks was tested. The formulation with 50% w/w glycerol was applied to the treatment of apple and grape juices and the results of these tests were statistically comparable to those obtained with two high-quality commercial preparations.

A Study of Single Stage Semi‐Dry Anaerobic Digestion of Organic Fraction of Municipal Solid Waste

Solid waste generation is a natural consequence of human activity and is increasing along with population growth, urbanization and industrialization. Improper disposal of the huge amount of solid waste seriously affects the environment and contributes to climate change by the release of greenhouse gases. Practicing anaerobic digestion (AD) for the organic fraction of municipal solid waste (OFMSW) can reduce emissions to environment and thereby alleviate the environmental problems together with production of biogas, an energy source, and digestate, a soil amendment. The amenability of substrate for biogasification varies from substrate to substrate and different environmental and operating conditions such as pH, temperature, type and quality of substrate, mixing, retention time etc. Therefore, the purpose of this research work is to develop feasible semi-dry anaerobic digestion process for the treatment of OFMSW from Kerala, India for potential energy recovery and sustainable waste management. This study was carried out in three phases in order to reach the research purpose. In the first phase, batch study of anaerobic digestion of OFMSW was carried out for 100 days at 32°C (mesophilic digestion) for varying substrate concentrations. The aim of this study was to obtain the optimal conditions for biogas production using response surface methodology (RSM). The parameters studied were initial pH, substrate concentration and total organic carbon (TOC). The experimental results showed that the linear model terms of initial pH and substrate concentration and the quadratic model terms of the substrate concentration and TOC had significant individual effect (p < 0.05) on biogas yield. However, there was no interactive effect between these variables (p > 0.05). The optimum conditions for maximizing the biogas yield were a substrate concentration of 99 g/l, an initial pH of 6.5 and TOC of 20.32 g/l. AD of OFMSW with optimized substrate concentration of 99 g/l [Total Solid (TS)-10.5%] is a semi-dry digestion system .Under the optimized condition, the maximum biogas yield was 53.4 L/kg VS (volatile solid).. In the second phase, semi-dry anaerobic digestion of organic solid wastes was conducted for 45 days in a lab-scale batch experiment for substrate concentration of 100 g/l (TS-11.2%) for investigating the start-up performances under thermophilic condition (50°C). The performance of the reactor was evaluated by measuring the daily biogas production and calculating the degradation of total solids and the total volatile solids. The biogas yield at the end of the digestion was 52.9 L/kg VS for the substrate concentration of 100 g/l. About 66.7% of volatile solid degradation was obtained during the digestion. A first order model based on the availability of substrate as the limiting factor was used to perform the kinetic studies of batch anaerobic digestion system. The value of reaction rate constant, k, obtained was 0.0249 day-1. A laboratory bench scale reactor with a capacity of 36.8 litres was designed and fabricated to carry out the continuous anaerobic digestion of OFMSW in the third phase. The purpose of this study was to evaluate the performance of the digester at total solid concentration of 12% (semi-dry) under mesophlic condition (32°C). The digester was operated with different organic loading rates (OLRs) and constant retention time. The performance of the reactor was evaluated using parameters such as pH, volatile fatty acid (VFA), alkalinity, chemical oxygen demand (COD), TOC and ammonia-N as well as biogas yield. During the reactor’s start-up period, the process is stable and there is no inhibition occurred and the average biogas production was 14.7 L/day. The reactor was fed in continuous mode with different OLRs (3.1,4.2 and 5.65 kg VS/m3/d) at constant retention time of 30 days. The highest volatile solid degradation of 65.9%, with specific biogas production of 368 L/kg VS fed was achieved with OLR of 3.1 kg VS/m3/d. Modelling and simulation of anaerobic digestion of OFMSW in continuous operation is done using adapted Anaerobic Digestion Model No 1 (ADM1).The proposed model, which has 34 dynamic state variables, considers both biochemical and physicochemical processes and contains several inhibition factors including three gas components. The number of processes considered is 28. The model is implemented in Matlab® version 7.11.0.584(R2010b). The model based on adapted ADM1 was tested to simulate the behaviour of a bioreactor for the mesophilic anaerobic digestion of OFMSW at OLR of 3.1 kg VS/m3/d. ADM1 showed acceptable simulating results.

Impact of sward type, cutting date and conditioning temperature on mass and energy flows in the integrated generation of solid fuel and biogas from semi-natural grassland

Energy production from biomass and the conservation of ecologically valuable grassland habitats are two important issues of agriculture today. The combination of a bioenergy production, which minimises environmental impacts and competition with food production for land with a conversion of semi-natural grasslands through new utilization alternatives for the biomass, led to the development of the IFBB process. Its basic principle is the separation of biomass into a liquid fraction (press fluid, PF) for the production of electric and thermal energy after anaerobic digestion to biogas and a solid fraction (press cake, PC) for the production of thermal energy through combustion. This study was undertaken to explore mass and energy flows as well as quality aspects of energy carriers within the IFBB process and determine their dependency on biomass-related and technical parameters. Two experiments were conducted, in which biomass from semi-natural grassland was conserved as silage and subjected to a hydrothermal conditioning and a subsequent mechanical dehydration with a screw press. Methane yield of the PF and the untreated silage was determined in anaerobic digestion experiments in batch fermenters at 37°C with a fermentation time of 13-15 and 27-35 days for the PF and the silage, respectively. Concentrations of dry matter (DM), ash, crude protein (CP), crude fibre (CF), ether extract (EE), neutral detergent fibre (NDF), acid detergent fibre (ADF), acid detergent ligning (ADL) and elements (K, Mg, Ca, Cl, N, S, P, C, H, N) were determined in the untreated biomass and the PC. Higher heating value (HHV) and ash softening temperature (AST) were calculated based on elemental concentration. Chemical composition of the PF and mass flows of all plant compounds into the PF were calculated. In the first experiment, biomass from five different semi-natural grassland swards (Arrhenaterion I and II, Caricion fuscae, Filipendulion ulmariae, Polygono-Trisetion) was harvested at one late sampling (19 July or 31 August) and ensiled. Each silage was subjected to three different temperature treatments (5°C, 60°C, 80°C) during hydrothermal conditioning. Based on observed methane yields and HHV as energy output parameters as well as literature-based and observed energy input parameters, energy and green house gas (GHG) balances were calculated for IFBB and two reference conversion processes, whole-crop digestion of untreated silage (WCD) and combustion of hay (CH). In the second experiment, biomass from one single semi-natural grassland sward (Arrhenaterion) was harvested at eight consecutive dates (27/04, 02/05, 09/05, 16/05, 24/05, 31/05, 11/06, 21/06) and ensiled. Each silage was subjected to six different treatments (no hydrothermal conditioning and hydrothermal conditioning at 10°C, 30°C, 50°C, 70°C, 90°C). Energy balance was calculated for IFBB and WCD. Multiple regression models were developed to predict mass flows, concentrations of elements in the PC, concentration of organic compounds in the PF and energy conversion efficiency of the IFBB process from temperature of hydrothermal conditioning as well as NDF and DM concentration in the silage. Results showed a relative reduction of ash and all elements detrimental for combustion in the PC compared to the untreated biomass of 20-90%. Reduction was highest for K and Cl and lowest for N. HHV of PC and untreated biomass were in a comparable range (17.8-19.5 MJ kg-1 DM), but AST of PC was higher (1156-1254°C). Methane yields of PF were higher compared to those of WCD when the biomass was harvested late (end of May and later) and in a comparable range when the biomass was harvested early and ranged from 332 to 458 LN kg-1 VS. Regarding energy and GHG balances, IFBB, with a net energy yield of 11.9-14.1 MWh ha-1, a conversion efficiency of 0.43-0.51, and GHG mitigation of 3.6-4.4 t CO2eq ha-1, performed better than WCD, but worse than CH. WCD produces thermal and electric energy with low efficiency, CH produces only thermal energy with a low quality solid fuel with high efficiency, IFBB produces thermal and electric energy with a solid fuel of high quality with medium efficiency. Regression models were able to predict target parameters with high accuracy (R2=0.70-0.99). The influence of increasing temperature of hydrothermal conditioning was an increase of mass flows, a decrease of element concentrations in the PC and a differing effect on energy conversion efficiency. The influence of increasing NDF concentration of the silage was a differing effect on mass flows, a decrease of element concentrations in the PC and an increase of energy conversion efficiency. The influence of increasing DM concentration of the silage was a decrease of mass flows, an increase of element concentrations in the PC and an increase of energy conversion efficiency. Based on the models an optimised IFBB process would be obtained with a medium temperature of hydrothermal conditioning (50°C), high NDF concentrations in the silage and medium DM concentrations of the silage.

Effectiveness of high-throughput miniaturized sorbent- and solid phase microextraction techniques combined with gas chromatography–mass spectrometry analysis for a rapid screening of volatile and semi-volatile composition of wines: a comparative study

In this study the feasibility of different extraction procedures was evaluated in order to test their potential for the extraction of the volatile (VOCs) and semi-volatile constituents (SVOCs) from wines. In this sense, and before they could be analysed by gas chromatography–quadrupole first stage masss spectrometry (GC–qMS), three different high-throughput miniaturized (ad)sorptive extraction techniques, based on solid phase extraction (SPE), microextraction by packed sorbents (MEPS) and solid phase microextraction (SPME), were studied for the first time together, for the extraction step. To achieve the most complete volatile and semi-volatile signature, distinct SPE (LiChrolut EN, Poropak Q, Styrene-Divinylbenzene and Amberlite XAD-2) and MEPS (C2, C8, C18, Silica and M1 (mixed C8-SCX)) sorbent materials, and different SPME fibre coatings (PA, PDMS, PEG, DVB/CAR/PDMS, PDMS/DVB, and CAR/PDMS), were tested and compared. All the extraction techniques were followed by GC–qMS analysis, which allowed the identification of up to 103 VOCs and SVOCs, distributed by distinct chemical families: higher alcohols, esters, fatty acids, carbonyl compounds and furan compounds. Mass spectra, standard compounds and retention index were used for identification purposes. SPE technique, using LiChrolut EN as sorbent (SPELiChrolut EN), was the most efficient method allowing for the identification of 78 VOCs and SVOCs, 63 and 19 more than MEPS and SPME techniques, respectively. In MEPS technique the best results in terms of number of extractable/identified compounds and total peak areas of volatile and semi-volatile fraction, were obtained by using C8 resin whereas DVB/CAR/PDMS was revealed the most efficient SPME coating to extract VOCs and SVOCs from Bual wine. Diethyl malate (18.8 ± 3.2%) was the main component found in wine SPELiChrolut EN extracts followed by ethyl succinate (13.5 ± 5.3%), 3-methyl-1-butanol (13.2 ± 1.7%), and 2-phenylethanol (11.2 ± 9.9%), while in SPMEDVB/CAR/PDMS technique 3-methyl-1-butanol (43.3 ± 0.6%) followed by diethyl succinate (18.9 ± 1.6%), and 2-furfural (10.4 ± 0.4%), are the major compounds. The major VOCs and SVOCs isolated by MEPSC8 were 3-methyl-1-butanol (26.8 ± 0.6%, from wine total volatile fraction), diethyl succinate (24.9 ± 0.8%), and diethyl malate (16.3 ± 0.9%). Regardless of the extraction technique, the highest extraction efficiency corresponds to esters and higher alcohols and the lowest to fatty acids. Despite some drawbacks associated with the SPE procedure such as the use of organic solvents, the time-consuming and tedious sampling procedure, it was observed that SPELiChrolut EN, revealed to be the most effective technique allowing the extraction of a higher number of compounds (78) rather than the other extraction techniques studied.

Processing-structure-property relationships in solid-state shear pulverization: Parametric study of specific energy

Solid-state shear pulverization (SSSP) is a unique processing technique for mechanochemical modification of polymers, compatibilization of polymer blends, and exfoliation and dispersion of fillers in polymer nanocomposites. A systematic parametric study of the SSSP technique is conducted to elucidate the detailed mechanism of the process and establish the basis for a range of current and future operation scenarios. Using neat, single component polypropylene (PP) as the model material, we varied machine type, screw design, and feed rate to achieve a range of shear and compression applied to the material, which can be quantified through specific energy input (Ep). As a universal processing variable, Ep reflects the level of chain scission occurring in the material, which correlates well to the extent of the physical property changes of the processed PP. Additionally, we compared the operating cost estimates of SSSP and conventional twin screw extrusion to determine the practical viability of SSSP.

Processing-Structure-Property Relationships in Solid-State Shear Pulverization: Parametric Study of specific energy

Solid-state shear pulverization (SSSP) is a unique processing technique for mechanochemical modification of polymers, compatibilization of polymer blends, and exfoliation and dispersion of fillers in polymer nanocomposites. A systematic parametric study of the SSSP technique is conducted to elucidate the detailed mechanism of the process and establish the basis for a range of current and future operation scenarios. Using neat, single component polypropylene (PP) as the model material, we varied machine type, screw design, and feed rate to achieve a range of shear and compression applied to the material, which can be quantified through specific energy input (Ep). As a universal processing variable, Ep reflects the level of chain scission occurring in the material, which correlates well to the extent of the physical property changes of the processed PP. Additionally, we compared the operating cost estimates of SSSP and conventional twin screw extrusion to determine the practical viability of SSSP.

Investigation of Solid-State Shear Pulverization Processing Parameters for Polyethylene-Clay Nanocomposites

Investigates multiple processing parameters, includingpolymer type, filler type, processing technique, severity of SSSP (Solid-state shear pulverization)processing, and postprocessing, of SSSP. HDPE and LLDPE polymers with pristine clay and organo-clay samples are explored. Effects on crystallization, high-temperature behavior, mechanicalproperties, and gas barrier properties are examined. Thermal, mechanical, and morphological characterization is conducted to determine polymer/filler compatibility and superior processing methods for the polymer-clay nanocomposites.

Characterization of Biodegradable Polymer Nanocomposites Fabricated via Solid-State Processing

Biodegradable polymer/clay nanocomposites were prepared withpristine and organically modified montmorillonite in polylactic acid (PLA) and polycaprolactone (PCL) polymer matrices. Nanocomposites were fabricated using extrusion and SSSP to compare the effects of melt-state and solid-state processing on the morphology of the final nanocomposite. Characterization of various material properties was performed on prepared biodegradable polymer/clay nanocomposites to evaluate property enhancements from different clays and/or processing methods.