Natural Wax-Based Water Vapour Barrier Coatings on PLA for MAP Food Packaging

PLA is a bio-based polymer that is obtained from renewable resources and it is very promising for a sustainable packaging manufacturing. However, its gas and vapour barrier properties are not enough to comply with the requirements of MAP packaging of fresh foods, which need specific concentration of water and oxygen to avoid spoilage and to keep the organoleptic properties unaltered throughout their shelf-life. The use of waxes from natural renewable sources such as plants (e.g., candelilla wax, carnauba wax, rice bran wax, sunflower wax) or animals (e.g., beeswax) could tackle down the permeation of water vapour through the packaging without affecting its bio-based content. The core of this work is developing wax-based coatings with enhanced thermo-mechanical properties so that they can undergo thermoforming and a proper adhesion to the PLA substrate can be ensured. Chemical modifications and crosslinking of waxes are performed to produce wax-based alkyd resins. The synthesised materials are characterised both by DSC and FTIR. Films of the wax-based alkyds are produced in order to assess their water vapour permeability.

Sisal organosolv pulp as reinforcement for cement based composites

The present work describes non-conventional sisal (Agave sisalana) chemical (organosolv) pulp from residues of cordage as reinforcement to cement based materials. Sisal organosolv pulp was produced in a 1:1 ethanol/water mixture and post chemically and physically characterized in order to compare its properties with sisal kraft pulp. Cement based composites reinforced with organosolv or kraft pulps and combined with polypropylene (PP) fibres were produced by the slurry de-watering and pressing method as a crude simulation of the Hatschek process. Composites were evaluated at 28 days of age, after exposition to accelerated carbonation and after 100 soak/dry cycles. Composites containing organosolv pulp presented lower mechanical strength, water absorption and apparent porosity than composites reinforced with kraft pulp. The best mechanical performance after ageing was also achieved by samples reinforced with kraft pulp. The addition of PP fibres favoured the maintenance of toughness after ageing. Accelerated carbonation promoted the densification of the composites reinforced with sisal organosolv + PP fibres.

Eucalyptus pulp fibres as alternative reinforcement to engineered cement-based composites

This paper evaluates the advantages of using hardwood short fibre pulp (eucalyptus) as alternative to softwood long fibre pulp (pinus) and polymer fibres, traditionally used in reinforcement of cement-based materials. The effects of cellulose fibre length on microstructure and on mechanical performance of fibre-cement composites were evaluated before and after accelerated ageing cycles. Hardwood pulp fibres were better dispersed in the cement matrix and provided higher number of fibres per unitary weight or volume, in relation to softwood long fibre pulp. The short reinforcing elements lead to an effective crack bridging of the fragile matrix, which contributes to the improvement of the mechanical performance of the composite after ageing. These promising results show the potential of eucalyptus short fibres for reducing costs by both the partial replacement of expensive synthetic fibres in air curing process and the energy savings during pulp refining. (C) 2009 Elsevier B.V. All rights reserved.

Anomalous water absorption in porous materials

The absorption of fluid by unsaturated, rigid porous materials may be characterized by the sorptivity. This is a simple parameter to determine and is increasingly being used as a measure of a material's resistance to exposure to fluids (especially moisture and reactive solutes) in aggressive environments. The complete isothermal absorption process is described by a nonlinear diffusion equation, with the hydraulic diffusivity being a strongly nonlinear function of the degree of saturation of the material. This diffusivity can be estimated from the sorptivity test. In a typical test the cumulative absorption is proportional to the square root of time. However, a number of researchers have observed deviation from this behaviour when the infiltrating fluid is water and there is some potential for chemo-mechanical interaction with the material. In that case the current interpretation of the test and estimation of the hydraulic diffusivity is no longer appropriate. Kuntz and Lavallee (2001) discuss the anomalous behaviour and propose a non-Darcian model as a more appropriate physical description. We present an alternative Darcian explanation and theory that retrieves the earlier advantages of the simple sorptivity test in providing parametric information about the material's hydraulic properties and allowing simple predictive formulae for the wetting profile to be generated.

Coupling Mechanical and Electrical Behavior in the Multi-scale Simulation of Polymer-based CNT Nanocomposites

A numeric model has been proposed to investigate the mechanical and electrical properties of a polymeric/carbon nanotube (CNT) composite material subjected to a deformation force. The reinforcing phase affects the behavior of the polymeric matrix and depends on the nanofiber aspect ratio and preferential orientation. The simulations show that the mechanical behavior of a computer generated material (CGM) depends on fiber length and initial orientation in the polymeric matrix. It is also shown how the conductivity of the polymer/CNT composite can be calculated for each time step of applied stress, effectively providing the ability to simulate and predict strain-dependent electrical behavior of CNT nanocomposites.

Síntese e caracterização de redes metalo-orgânicas de fármacos

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Utilização de colas naturais para placas de derivados de madeira – uma síntese

Resumo: Nos últimos anos tem-se verificado um interesse crescente pela área das colas naturais, em particular na produção de placas de derivados de madeira para utilização no interior das construções. Estas colas parecem ser uma boa alternativa às colas sintéticas, derivadas do petróleo, pois, ao contribuírem para uma melhor qualidade do ar interior associada a uma menor incorporação de energia no produto final, apresentam vantagens interessantes em termos ambientais e de saúde. Nesse sentido fez-se uma revisão da bibliografia sobre a utilização laboratorial e mesmo semi-industrial de colas naturais em placas de derivados de madeira. São apresentados e discutidos alguns exemplos de materiais que estas colas aglutinam, bem como as suas características finais com vista a futuros desenvolvimentos experimentais de placas fabricadas a partir de resíduos agrícolas comuns. Abstract: An increased interest for bio-based adhesives for wood-based panels for building purposes has been arising. This type of adhesives could be a good alternative for petroleum based synthetic adhesives as bio-based adhesives can contribute for healthier indoor environments and, simultaneously, present lower embodied energy. For the previous reasons a bibliographic review was conducted, on the use of bio-based adhesives for the production of wood-based building panels. Some examples of the adhesives, the type of applications and the characterization of the resulting products are presented and compared, bearing in mind contributing for a future increase of research in this area.

Biofunctionalization of titanium surfaces for dental implants: osteogenic, anti-microbial and tribocorrosion resistant surfaces

PhD thesis in Biomedical Engineering

In silico constraint-based strain optimization methods: the quest for optimal cell factories

Shifting from chemical to biotechnological processes is one of the cornerstones of 21st century industry. The production of a great range of chemicals via biotechnological means is a key challenge on the way toward a bio-based economy. However, this shift is occurring at a pace slower than initially expected. The development of efficient cell factories that allow for competitive production yields is of paramount importance for this leap to happen. Constraint-based models of metabolism, together with in silico strain design algorithms, promise to reveal insights into the best genetic design strategies, a step further toward achieving that goal. In this work, a thorough analysis of the main in silico constraint-based strain design strategies and algorithms is presented, their application in real-world case studies is analyzed, and a path for the future is discussed.

Bacterial cellulose-lactoferrin as an antimicrobial edible packaging

Bacterial cellulose (BC) films from two distinct sources (obtained by static culture with Gluconacetobacter xylinus ATCC 53582 (BC1) and from a commercial source (BC2)) were modified by bovine lactoferrin (bLF) adsorption. The functionalized films (BC+bLF) were assessed as edible antimicrobial packaging, for use in direct contact with highly perishable foods, specifically fresh sausage as a model of meat products. BC+bLF films and sausage casings were characterized regarding their water vapour permeability (WVP), mechanical properties, and bactericidal efficiency against two food pathogens, Escherichia coli and Staphylococcus aureus. Considering their edibility, an in vitro gastrointestinal tract model was used to study the changes occurring in the BC films during passage through the gastrointestinal tract. Moreover, the cytotoxicity of the BC films against 3T3 mouse embryo fibroblasts was evaluated. BC1 and BC2 showed equivalent density, WVP and maximum tensile strength. The percentage of bactericidal efficiency of BC1 and BC2 with adsorbed bLF (BC1+bLF and BC2+bLF, respectively) in the standalone films and in inoculated fresh sausages, was similar against E. coli (mean reduction 69 % in the films per se versus 94 % in the sausages) and S. aureus (mean reduction 97 % in the films per se versus 36 % in the case sausages). Moreover, the BC1+bLF and BC2+bLF films significantly hindered the specific growth rate of both bacteria. Finally, no relevant cytotoxicity against 3T3 fibroblasts was found for the films before and after the simulated digestion. BC films with adsorbed bLF may constitute an approach in the development of bio-based edible antimicrobial packaging systems.

Development of a biorefinery–based bioprocess for pigment and lipid production by oleaginous yeasts

Dissertação de mestrado em Bioengenharia

Biopohjaiset polymeerit dispersiopäällystyksessä

Työn aiheena oli tehdä muotoiltavissa oleva rasvankestävä pakkauskartonki. Polymeeridispersiopäällystettyjä pakkauskartonkeja käytetään kertakäyttöisissä tuotteissa kuten vuoissa, kupeissa ja lautasissa. Tuotteiden on kestettävä rasvaa niiden lopputarkoituksen mukaisesti. Pakkausala jatkaa vuosittaista kasvuaan vauhdilla. Uusia kierrätettäviä biopohjaisia ja luonnolle ystävällisempiä pakkaustuotteita on kehitettävä kasvun tyydyttämiseksi. Biopohjaiset pakkaustuotteet ovat mahdollisia ratkaisuja ympäristöön kohdistuvien ongelmien vähentämiseksi ja öljypohjaisten raaka-aineiden korvaajiksi. Diplomityön teoriaosuudessa keskityttiin dispersiopäällystyksessä käytettyihin biopolymeereihin ja niiden toimivuuteen suojaavina kalvoina. Teoriaosuudessa käsiteltiin myös rasvankestoa ja rasvankestävien tuotteiden materiaaliominaisuuksia. Kirjallisuuden perusteella havaittiin luonnonpolymeerien alhaisen kuiva-ainepitoisuuden ja korkean päällystemäärätarpeen muodostamat haasteet dispersiopäällystyksessä. Pohjakartongin karheudella ja tiiveydellä sekä suojaavan polymeerin kalvon rakenteella huomattiin olevan suuri merkitys rasvankeston saavuttamiseksi. Kokeellinen osa jakautui kolmeen osakokonaisuuteen: laboratoriokokeisiin, esipilotointiin ja varsinaiseen pilot-koeajoon. Esikokeiden perusteella suojaavat kalvot, joiden raaka-aineena käytettiin biopohjaisia dispersiopolymeerejä, antoivat riittäviä rasvankesto-ominaisuuksia, mutta eivät kestäneet konvertointia. Pienellä synteettisten polymeerien lisäyksellä pystyttiin parantamaan päällystettyjen kartonkien rasvankestoa sekä konvertoitavuutta. Pilot-koeajonäytteiden testaustulokset tukivat esikokeissa tehtyjä havaintoja. Tämän työn perusteella kohtuullinen lisäysmäärä synteettistä polymeeriä voi parantaa merkittävästi biopohjaisen suojaavan kalvon antamaa rasvankestoa sekä päällystetyn kartongin konvertoitavuutta.

Low k thin films based on rf plasma-polymerized aniline

Thermally stable materials with low dielectric constant (k < 3.9) are being hotly pursued. They are essential as interlayer dielectrics/intermetal dielectrics in integrated circuit technology, which reduces parasitic capacitance and decreases the RC time constant. Most of the currently employed materials are based on silicon. Low k films based on organic polymers are supposed to be a viable alternative as they are easily processable and can be synthesized with simpler techniques. It is known that the employment of ac/rf plasma polymerization yields good quality organic thin films, which are homogenous, pinhole free and thermally stable. These polymer thin films are potential candidates for fabricating Schottky devices, storage batteries, LEDs, sensors, super capacitors and for EMI shielding. Recently, great efforts have been made in finding alternative methods to prepare low dielectric constant thin films in place of silicon-based materials. Polyaniline thin films were prepared by employing an rf plasma polymerization technique. Capacitance, dielectric loss, dielectric constant and ac conductivity were evaluated in the frequency range 100 Hz– 1 MHz. Capacitance and dielectric loss decrease with increase of frequency and increase with increase of temperature. This type of behaviour was found to be in good agreement with an existing model. The ac conductivity was calculated from the observed dielectric constant and is explained based on the Austin–Mott model for hopping conduction. These films exhibit low dielectric constant values, which are stable over a wide range of frequencies and are probable candidates for low k applications.

Ag dopedWO(3)-based powder sensor for the detection of NO gas in air

WO3-based materials as sensors for the monitor of environmental gases such as NO2 (NO + NO2) have been rapidly developed for various potential applications (stationary and mobile uses). It has been reported that these materials are highly sensitive to NOx with the sensitivity further enhanced by adding precious group metals (PGM such as Pt, Pd, Au, etc.). However, there has been limited work in revealing the sensing mechanism for these gases over the WO3-based sensors. In particular, the role of promoter is not yet clear though speculations on their catalytic, electronic and structural effects have been made in the past. In parallel to these PGM promoters here we report,for the first time, that Ag promotion can also enhance WO3 sensitivity significantly. In addition, this promotion decreases the optimum sensor temperature of 300 degreesC for Most WO3-based sensors, to below 200 degreesC. Characterizations (XRD, TEM, and impedance measurement) reveal that there is no significant bulk structure change nor particle size alteration in the WO3 phases during the NO exposure. However, it is found that the Ag doping creates a high concentration of oxygen vacancies in form of coordinated crystallographic shear (CS) planes onto the underneath WO3. It is thus proposed that the Ag particle facilitates the oxidative conversion of NO to NO2 followed by a subsequent NO2 adsorption on the defective WO, sites created at the Ag-WO3 interface; hence, accounting for the high molecular sensitivity. (C) 2002 Elsevier Science B.V. All rights reserved.

Mechanical effects of plant cell wall enzymes on xyloglucan/cellulose composites

Xyloglucan-acting enzymes are believed to have effects on type I primary plant cell wall mechanical properties. In order to get a better understanding of these effects, a range of enzymes with different in vitro modes of action were tested against cell wall analogues (bio-composite materials based on Acetobacter xylinus cellulose and xyloglucan). Tomato pericarp xyloglucan endo transglycosylase (tXET) and nasturtium seed xyloglucanase (nXGase) were produced heterologously in Pichia pastoris. Their action against the cell wall analogues was compared with that of a commercial preparation of Trichoderma endo-glucanase (EndoGase). Both 'hydrolytic' enzymes (nXGase and EndoGase) were able to depolymerise not only the cross-link xyloglucan fraction but also the surface-bound fraction. Consequent major changes in cellulose fibril architecture were observed. In mechanical terms, removal of xyloglucan cross-links from composites resulted in increased stiffness (at high strain) and decreased visco-elasticity with similar extensibility. On the other hand, true transglycosylase activity (tXET) did not affect the cellulose/xyloglucan ratio. No change in composite stiffness or extensibility resulted, but a significant increase in creep behaviour was observed in the presence of active tXET. These results provide direct in vitro evidence for the involvement of cell wall xyloglucan-specific enzymes in mechanical changes underlying plant cell wall re-modelling and growth processes. Mechanical consequences of tXET action are shown to be complimentary to those of cucumber expansin.