The determination of optimal processing conditions for PLA and PLA/CaCO3 in twin screw extrusion using DoE and multivariate analysis

Biodegradable polymers, such as PLA (Polylactide), come from renewable resources like corn starch and if disposed of correctly, degrade and become harmless to the ecosystem making them attractive alternatives to petroleum based polymers. PLA in particular is used in a variety of applications including medical devices, food packaging and waste disposal packaging. However, the industry faces challenges in melt processing of PLA due to its poor thermal stability which is influenced by processing temperatures and shearing.
Identification and control of suitable processing conditions is extremely challenging, usually relying on trial and error, and often sensitive to batch to batch variations. Off-line assessment in a lab environment can result in high scrap rates, long lead times and lengthy and expensive process development. Scrap rates are typically in the region of 25-30% for medical grade PLA costing between €2000-€5000/kg.
Additives are used to enhance material properties such as mechanical properties and may also have a therapeutic role in the case of bioresorbable medical devices, for example the release of calcium from orthopaedic implants such as fixation screws promotes healing. Additives can also reduce the costs involved as less of the polymer resin is required.
This study investigates the scope for monitoring, modelling and optimising processing conditions for twin screw extrusion of PLA and PLA w/calcium carbonate to achieve desired material properties. A DAQ system has been constructed to gather data from a bespoke measurement die comprising melt temperature; pressure drop along the length of the die; and UV-Vis spectral data which is shown to correlate to filler dispersion. Trials were carried out under a range of processing conditions using a Design of Experiments approach and samples were tested for mechanical properties, degradation rate and the release rate of calcium. Relationships between recorded process data and material characterisation results are explored.

Pine wilt disease: global issues, trade and economic impact

Pine wilt disease (PWD) is perhaps the most serious threat to pine forests worldwide. Since it´s discovery in the early XXth century by Japanese forest researchers, and the relationship with its causative agent, the pinewood nematode (PWN) Bursaphelenchus xylophilus, in the 1970s, PWD has wreaked havoc wherever it appears. Firstly in the Far East (Japan, China and Korea) and now, more recently in 1999, in the EU (Portugal). The forest sector in Portugal plays a major role in the Portuguese economy with a 12% contribution to the industrial gross domestic product, 3.2% of the gross domestic product, 10% of foreign trade and 5% of national employment. Maritime pine (Pinus pinaster) is one of the most important pine productions, and industrial activity, such as the production of wood and resin, as well as coastal protection associated with sand dunes. Also, stone pine (Pinus pinea) plays an important role in the economy with a share derived from the exports of high-quality pineon seed. Thus, the tremendous economical and ecological impact of the introduction of a pest and pathogen such as the PWN, although as far as is known, the only species susceptible to the nematode is maritime pine. Immediately following detection, the research team involved (Univ. Évora, INIAP) informed the national plant quarantine and forest authorities, which relayed the information to Brussels and the appropriate EU authorities. A task force (GANP), followed by a national program (PROLUNP) was established. Since then, national surveys have been taking place, involving MADRP (Ministry of Agriculture), the University of Évora and several private corporations (e.g. UNAC). Forest growers in the area are particularly interested and involved since the area owned by the growers organizations totals 700 000 ha, largely affected by PWD. Detection of the disease has led to serious consequences and restrictions regarding exploration and commercialization of wood. A precautionary phytosanitary strip, 3 km-wide, has been recently (2007) established surrounding the affected area. The Portuguese government, through its national program PROLUNP, has been deeply involved since 1999, and in conjunction with the EU (Permanent Phytosanitary Committee, and FVO) and committed to controlling this nematode and the potential spread to the rest of the country and to the rest of the EU. The global impact of the presence of Bursaphelenchus xylophilus or the threat of its introduction and the resulting pine wilt disease in forested areas in different parts of the world is of increasing concern economically. The concern is exacerbated by the prevailing debate on climate change and the putative impact this could have on the vulnerability of the world’s pine forests to this disease. The scientific and regulatory approach taken in different jurisdictions to the threat of pine wilt disease varies from country to country depending on the perceived vulnerability of their pine forests to the disease and/or to the economic cost due to lost trade in wood products. Much of the research surrounding pine wilt disease has been located in the northern hemisphere, especially in southern Europe and in the warmer, coastal, Asian countries. However, there is an increased focus on this problem also in those countries in the southern hemisphere where plantations of susceptible pine have been established over the years. The forestry sector in Australia and New Zealand are on “high alert” for this disease and are practicing strict quarantine procedures at all ports of entry for wood products. As well, there is heightened awareness, as there is worldwide, for the need to monitor wood packaging materials for all imported goods. In carrying out the necessary monitoring and assessment of products for B. xylophilus and its vectors substantial costs are incurred especially when decisions have to be made rapidly and regardless of whether the outcome is positive or negative. Australia’s response recently to the appearance of some dying pines in a plantation illustrated the high sensitivity of some countries to this disease. Some $200,000 was spent on the assessment in order to save a potential loss of millions of dollars to the disease. This rapid, co-ordinated response to the report was for naught, because once identified it was found not to be B. xylophilus. This illustrates the particular importance of taking the responsibility at all levels of management to secure the site and the need of a rapid, reliable diagnostic method for small nematode samples for use in the field. Australia is particularly concerned about the vulnerability of its 1million hectares of planted forests, 80% of which are Pinus species, to attack from incursions of one or more species of the insect vector. Monochamus alternatus incursions in wood pallets have been reported from Brisbane, Queensland. The climate of this part of Australia is such that the Pinus plantations are particularly vulnerable to the potential outcome of such incursions, and the state of Queensland is developing a risk management strategy and a proactive breeding programme in response to this putative threat. New Zealand has 1.6 million hectares of planted forests and 89% of the commercial forest is Pinus radiata. Although the climate where these forests are located tends to be somewhat cooler than that in Australia the potential for establishment and development of the disease in that country is believed to be high. The passage alone of 200,000 m³/year of wood packaging through New Zealand ports is itself sufficient to require response. The potential incursion of insect vectors of pinewood nematode through the port system is regarded as high and is monitored carefully. The enormous expansion of global trade and the continued use of unprocessed/inadequately-processed wood for packaging purposes is a challenge for all trading nations as such wood packaging material often harbours disease or pest species. The extent of this problem is readily illustrated by the expanding economies and exports of countries in south-east Asia. China. Japan and Korea have significant areas of forestland infested with B. xylophilus. These countries too are among the largest exporting countries of manufactured goods. Despite the attempts of authorities to ensure that only properly treated wood is used in the crating and packaging of goods B. xylophilus and/or its insect vector infested materials is being recorded at ports worldwide. This reminds us, therefore, of the ease with which this nematode pest can gain access to forest lands in new geographic locations through inappropriate use, treatment or monitoring of wood products. It especially highlights the necessity to find an alternative to using low-grade lumber for packaging purposes. Lest we should believe that all wood products are always carriers of B. xylophilus and its vectors, it should be remembered that international trade of all kinds has occurred for thousands of years and that lumber-born pests and diseases do not have worldwide distribution. Other physico-biological factors have a significant role in the occurrence, establishment and sustainability of a disease. The question is often raised as to why the whole of southern Europe doesn’t already have B. xylophilus and pine wilt disease. European countries have traded with countries that are infested with B. xylophilus for hundreds of years. Turkey is an example of a country that appears to be highly vulnerable to pine wilt disease due to its extensive forests in the warm, southern region where the vector, Monochamus galloprovincialis, occurs. However, there is no record of the presence of B. xylophilus occurring there despite the importation of substantial quantities of wood from several countries In many respects, Portugal illustrates both the challenge and the dilemma. In recent times B. xylophilus was discovered there in the warm coastal region. The research, administrative and quarantine authorities responded rapidly and B. xylophilus appears to have been confined to the region in which it was found. The rapid response would seem to have “saved the day” for Portugal. Nevertheless, it raises again the long-standing questions, how long had B. xylophilus been in Portugal before it was found? If Lisbon was the port of entry, which seems very likely, why had B. xylophilus not entered Lisbon many years earlier and established populations and the pine wilt disease? Will the infestation in Portugal be sustainable and will it spread or will it die out within a few years? We still do not have sufficient understanding of the biology of this pest to know the answers to these questions.

Konstruktion och design av två glassförpackningar i kartongkvaliteten Frövi Light

This degree project was made in cooperation with AssiDomän Frövi and Charlotte Andersson and the main objectivehas been to create to ice cream pacbges from 250 gsm Frövi Light board. The paekages are intended to be easilyresealable while decreasing in size together with the ice cream. The project also describes the food packaging labelsand symbols currently present in the European common market.Both capsules utilize a separate lid for resealing. One of the paekages (Capsuie A) is indended to be cut along withthe ice cream and thereby decrease in size. The other one (Capsuie B) uses a series of flaps for contracting and expandingwhich enab1es adjusting of the size without cutting the package up.The design for Capsuie A is created both as a series of flavours with a super-hero theme intended for children andwith a colfee flavour for a maturer audience. For Capsule B, a design was created for a sorbet.

Como criar possibilidades de financiamento para a agricultura familiar adotando o Plano ABC Nacional?

Ao longo dos últimos anos, através do aprimoramento das políticas agrícolas, observaram-se aumentos consistentes dos recursos orçamentários destinados à Agricultura Familiar, através do Pronaf. O incremento dos recursos efetivamente aplicados e o número cada vez maior de contratos também são realidade e podem ser vistos em todas as regiões do País. De acordo com os dados divulgados pelo Banco Central do Brasil, através do Anuário Estatístico do Crédito Rural (2014), foram aplicados no Brasil em 2004 aproximadamente R$ 4,39 bilhões, já em 2012 foram pouco mais de R$ 16,35 bilhões, ou seja, incremento de 272% no intervalo analisado. Em relação ao número de contratos, o crescimento foi em torno de 35,5% no mesmo período. A importância da Agricultura Familiar no contexto atual é corroborada no âmbito internacional pela Resolução 66/222, de 28.03.2012, da Assembleia-Geral, que conferiu à Organização das Nações Unidas para Alimentação e Agricultura (FAO) o mandato de implementar o Ano Internacional da Agricultura Familiar (AIAF) neste ano de 2014, em parceria com os governos dos países membros bem como com outros organismos internacionais e organizações não-governamentais atuantes no tema da agricultura e da segurança alimentar. Concomitantemente, diante da crescente preocupação com as questões ambientais, o Plano Setorial de Mitigação e de Adaptação às Mudanças Climáticas para a Consolidação de uma Economia de Baixa Emissão de Carbono na Agricultura - Plano ABC - é uma importante parte do compromisso voluntário assumido pelo Brasil em 2009, na 15ª Conferência das Partes – COP15 ocorrida em Copenhague, na redução da emissão de gases de efeito estufa até 2020. Parte desse compromisso assumido precisa ser atendido pela agricultura familiar, o que aumenta a responsabilidade da mesma para questões que vão além do fornecimento de alimentos, matérias primas e geração de energia etc. O Programa ABC, instrumento pelo qual os agricultores brasileiros podem acessar crédito para implementar tecnologias de baixas emissões de carbono, já está integrado nas ações previstas na Política de Crédito Agropecuário Brasileiro. Porém, ainda se observam vários desafios no Programa ABC, como aumentar o repasse desses recursos, não obstante ao aumento das operações contratadas pelos produtores nos últimos anos. O objetivo do estudo é investigar como a agricultura familiar pode contribuir com o Plano ABC e nos compromissos voluntários assumidos pelo País para a redução de emissão dos gases de efeito estufa no setor agropecuário. Para atingir esse objetivo, realizou-se uma revisão da bibliografia e das linhas de crédito disponíveis pelos bancos públicos e privados relacionadas ao Programa ABC e ao Pronaf. Conclui-se que há sinergias entre algumas linhas de crédito do Pronaf e também do Fundo Constitucional de Financiamento do Nordeste - FNE - Sudene com as tecnologias previstas no Plano ABC. Nesse sentido, o Plano ABC prevê a aplicação de tecnologias de redução de emissões em cerca de 4,97 milhões de ha ocupados pela agricultura familiar, sendo recursos do Pronaf previstos para fomentar tal aplicação, através das linhas Pronaf Eco e Pronaf Floresta. Contudo, verificou-se que tais linhas do Pronaf contemplam o uso de recursos para diversas outras atividades não relacionadas diretamente àquelas previstas no Plano ABC ou capazes de reduzir emissões de gases de efeito estufa. Dessa forma, não há como assegurar que a aplicação de recursos nessas linhas seja direcionada para tecnologias e ações que reduzam emissões, nem tão pouco há como monitorar o volume de recursos do Pronaf aplicados de fato em atividades aderentes ao Plano ABC. Portanto, sugere-se a criação/incorporação de novas linhas de crédito ao Pronaf, como por exemplo, Pronaf ABC Eco e o Pronaf ABC Floresta. Além disso, apresentou-se estudo de caso para o município de Bragança Paulista (SP), onde verificou-se que a utilização dos recursos do Programa ABC poderia ser usada para recomposição de áreas de preservação permanente ou de reserva legal, importantes na preservação das nascentes e rios da região. Essa possibilidade é de elevada importância no contexto e nas discussões atuais sobre a escassez dos recursos hídricos que abastecem grandes cidades, a exemplo do que vem ocorrendo na região metropolitana do Estado de São Paulo. Como conclusão, identifica-se alguns gargalos e apresenta-se algumas sugestões de melhorias para aumentar a utilização e eficácia do Programa ABC, como promover com mais ênfase apoio das assistências técnicas junto aos produtores, priorizar as ações previstas no Plano ABC em algumas regiões do País e aumentar a atuação mais direcionada do Ministério do Desenvolvimento Agrário (MDA) para difusão e incorporação das tecnologias de uma agricultura de baixa emissão de carbono no segmento da agricultura familiar.

Determinação de parâmetros de qualidade para formas farmacêuticas homeopáticas

All medicine, whether allopathic or homeopathic, must go through strict quality control, which must ratify their characteristics throughout the period of validity. During the time of preparation and storage, solutions of the drugs are in permanent contact with packaging materials that can release undesirable substances to the solution. Several factors may influence the release of packing materials, and factorial design (FD) is a useful tool for analyzing the phenomenon. The aim of this study was the determination of quality parameters for Homeopathic solid (globules) and liquid (drops) dosage forms. It was carried out analysis in homeopathic globules for weight variation, mechanical strength, and moisture content uniformity. For liquid preparations, standard solutions were prepared from natural rubber bulbs, which were subjected to exhaustive extraction with two ethanol solutions (30 and 70%) in the ultrasonic bath for 20 minutes at 25°C and 50°C in three successive cycles. Studies of transfer have been made within five days, by spectrophotometric analysis in the UV region at 312 nm with λmáx and 323 nm for samples in 70% ethanol and 30% respectively. PH values were analyzed. We also conducted two FD studies, where the first, the three-level variables were solvent (chloroform, ethanol and nhexane), sample mass (30, 60 and 90mg), particle size (large disk, small disk and powder sample). In the second study, the solvent level variables were different ethanolic degrees (EtOH 30%, 70% and pure). The percentage of lending in the solutions was 5.5%, 12.4%, 24.2% and 41% of the total estimated in the reference solution. The values of rate constants of transfer were determined in the order of 0.0134 days-1 and 0.0232 days-1 in absorbance values, the solutions in ethanol at 30% and 70% respectively. These results suggest that the speed of transfer of materials from rubber is affected both by the nature of the vehicle as by the temperature

Análise Microbiológica de Embalagens para o Acondicionamento de Medicamentos e Cosméticos

Microbiological Control of Packaging Materials for Medicines and Cosmetics. Several consumers and official agencies, associated with the necessity of more efficient, safety and good microbiological quality packaging materials, conducted to the challenge of having packages which assure both the integrity of products and consumer's health. However, the packaging material can be an important source of microorganisms when does not fulfill the microbiological quality requirements. The objective of this work was to study the microbiological quality of different types of packaging materials for medicines and cosmetics. The microbial quality studies were conducted by analyzing representative samples by bioassay. The packing materials were analyzed for microbiological quality to verify presence of viable microorganisms. They showed the analyzed packaging materials for medicines are in agreement with RDC # 481 on 23/9/1999 of ANVISA. However, the packages to store cosmetic material are not fulfilling this RDC. The microbiological quality control of packing materials has fundamental importance for public health.

Postharvest conservation of the tuberous roots of Pachyrhizus Ahipa (Wedd) Parodi

O objetivo deste trabalho foi avaliar o período de armazenamento em diferentes temperaturas e embalagens na conservação das raízes de Pachyrhizus ahipa. As raízes foram colhidas, lavadas e armazenadas em bandejas de isopor, no refrigerador, câmara fria e à temperatura ambiente. As embalagens utilizadas foram PVC, saco plástico e sem embalagem (controle). As bandejas foram retiradas do seu ambiente de armazenamento e analisadas quanto a acidez total titulável, sólidos solúveis totais, pH, teores de cinzas, lipídios, carboidrato total e proteínas em base seca. A menor perda de massa das raízes foi em câmara fria e em saco plástico. A ATT manteve-se maior nas raízes armazenadas em câmara fria e na embalagem de PVC; os menores teores de SST foram observados em câmara fria não variando entre as embalagens. em todos os tratamentos a porcentagem média de carboidratos foi 84,9%. A porcentagem de lipídios foi maior nas raízes armazenadas em temperatura ambiente, entretanto, o teor de proteína e cinzas foram maiores nas armazenadas na geladeira. A melhor condição para o armazenamento das raízes é em câmara fria e embaladas com saco plástico, onde as raízes mantiveram a qualidade apropriada para comercialização durante até 30 dias de armazenamento.

New strategies in the preparation of exfoliated thermoplastic starch-montmorillonite nanocomposites

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

Influence of cerium (IV) ions on the inorganic and organic phase for preparation of a siloxane-PMMA based film on tin plate substrate

Tinplate is one of the most widely used food canning materials, however, there are significant problems related to the use of tinplate cans, such as alterations in sensory features affecting food quality and corrosion phenomena of the canning material. To avoid corrosion problems different methods have been used for the passivation of tinplate such protective lacquers or different kinds of corrosion inhibitors (chromate and dichromate). However, chromates and dichromates are extremely harmful to the environment and can cause carcinogenic tumors to humans. An option, protective coatings obtained by the sol-gel process, act as a physical barrier, which isolates the surface of metal protecting from the corrosive agents. The aim of this work is to study the influence of addition of cerium (IV) ions in the inorganic and organic part of sol-gel processing in the formation of hybrid coatings based on siloxane-PMMA on tin plate. The coatings were obtained by dip-coating technique and evaluated by open circuit and impedance measurements, linear polarization and polarization curves obtained in 3.5% NaCl solution. The results have clearly shown the improvement on the protective properties of the Ce 4+ modified film when added into the organic phase, which can be due to the formation of a more uniform and densely reticulated siloxane-PMMA film. © 2009 by NACE International.

New developments for lignocellulosics-nanocomposites with low carbon footprint

Cellulose nanofibrils have been evaluated as reinforcement material in polymeric matrixes due to their potential to improve the mechanical, optical, and dielectric properties of these matrixes as well as its environmental positive footprint. This work describes how banana nanocellulose can be used to replace others not so friendly materials in many applications including, biomaterials, automotive industries and packaging by proved with their mechanical properties. The process used is very mild to the environment and consists of a high pressure fibrillation followed by a chemical purification which affects the fiber morphology. Many fibers characterization processes were used including microscopy techniques and X-ray diffraction to study the structure and properties of the prepared nanofibers and composites. Microscopy studies showed that the used individualization processes lead to a unique morphology of interconnected web-like structure of the fibers. © 2012 Materials Research Society.

Optically transparent membrane based on bacterial cellulose/ polycaprolactone

Optically transparent membranes from bacterial cellulose (BC)/polycaprolactone (PCL) have been prepared by impregnation of PCL acetone solution into dried BC membranes. UV-Vis measurements showed an increase on transparency in BC/PCL membrane when compared with pristine BC. The good transparency of the BC/PCL can be related to the presence of BC nanofibers associated with deposit of PCL nano-sized spherulites which are smaller than the wavelength of visible light and practically free of light scattering. XRD results show that cellulose type I structure is preserved inside the BC/PCL membrane, while the mechanical properties suggested indicated that PCL acts as a plasticizer for the BC membrane. The novel BC/PCL membrane could be used for preparation of fully biocompatible flexible display and biodegradable food packaging.

Nanocompósitos com atividade antioxidante de amido de milho/isolado proteico de soro de leite/ óleo essencial de alecrim obtidos por extrusão termoplástica

In order to improve the quality and safety of food, the active packaging emerges as a new technology based on the release of composites beneficial to food products. Thus, biodegradable films incorporated with active substances have the function of acting as a barrier to external elements, protecting the product and increasing its shelf life. They are formulated from proteins, polysaccharides, lipids or from the combination of these compounds. However, there is a need to improve the performance properties of these packages. Nanotechnologies, then, emerges with the study of many nanoparticles as additives to modify the performance of biodegradable polymers. With this, we aimed at developing and active antioxidant film of corn starch blenders and whey protein isolate with rosemary essential oil or microcapsules of rosemary essential oil reinforced with sodium montmorillonite (MMTNa + ) nanoparticles by extrusion. The films were developed and characterized in a first stage for the selection of the best polymeric blender using the following analyses: water vapor permeability (WVP), machanical properties; optical, thermogravimetry (TG), differential scanning calorimetry (DSC), x-ray diffraction (XRD) and scanning electron microscopy (SEM). In the second stage, montmorillonite clay nanoparticles and rosemary essential oil were added as reinforcement to evaluate its antioxidant effect. In a third stage, we studied the addition of microcapsules of rosemary essential oil (MR) as a form of protecting the active agent and its antioxidant potential in the films. The results indicate that the development of p olymeric blender with 30% of corn starch substitution is the most indicated for future work. The addition of rosemary essential oil or microcapsule of rosemary essential oil allowed for the obtaining of nanocomposites with antioxidant potential for application in food packages.

Desenvolvimento e validação de método analítico para determinação de caprolactama em simulantes de alimentos: estudo de migração e efeito da irradiação

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Idosos e embalagens alimentares: avaliação do design ergonómico de informação

The packaging often presents faults that difficult the communication between product and consumer. The aim of this research is to study the interaction between a group of elderly people with five food packagings, that being illinterpreted, can bring them health problems. The results of this study evidence the importance of ergonomics in graphic design for food packaging.

High-Speed Laser Processing of Thin Single and Multi-Layer Films

Theoretical models are developed for the continuous-wave and pulsed laser incision and cut of thin single and multi-layer films. A one-dimensional steady-state model establishes the theoretical foundations of the problem by combining a power-balance integral with heat flow in the direction of laser motion. In this approach, classical modelling methods for laser processing are extended by introducing multi-layer optical absorption and thermal properties. The calculation domain is consequently divided in correspondence with the progressive removal of individual layers. A second, time-domain numerical model for the short-pulse laser ablation of metals accounts for changes in optical and thermal properties during a single laser pulse. With sufficient fluence, the target surface is heated towards its critical temperature and homogeneous boiling or "phase explosion" takes place. Improvements are seen over previous works with the more accurate calculation of optical absorption and shielding of the incident beam by the ablation products. A third, general time-domain numerical laser processing model combines ablation depth and energy absorption data from the short-pulse model with two-dimensional heat flow in an arbitrary multi-layer structure. Layer removal is the result of both progressive short-pulse ablation and classical vaporisation due to long-term heating of the sample. At low velocity, pulsed laser exposure of multi-layer films comprising aluminium-plastic and aluminium-paper are found to be characterised by short-pulse ablation of the metallic layer and vaporisation or degradation of the others due to thermal conduction from the former. At high velocity, all layers of the two films are ultimately removed by vaporisation or degradation as the average beam power is increased to achieve a complete cut. The transition velocity between the two characteristic removal types is shown to be a function of the pulse repetition rate. An experimental investigation validates the simulation results and provides new laser processing data for some typical packaging materials.