Development of a prototype to access biodegradability of TPU shoe soles under controlled conditions

In the last years, the increasing problems posed by waste management have stimulated the interest in developing more sustainable and bio-based solutions for the footwear industry, including the use of biodegradable materials. As part of the NEWALK project, the objective of this work consisted in optimizing and implementing a respirometry system prototype. Besides evaluating different variables, two different approaches for measuring the evolved CO2 were assayed. Compared to manual titration, the use of conductivity offers the advantage of an automatic continuous monitoring.info:eu-repo/semantics/publishedVersio

The use of bio-based additives (lignin, starch and cellulose) in thermoplastic polyuretane formulations to enhance the biodegradability of footwear components

Thermoplastic polyurethanes (TPUs) are one of the most widely used polymeric materials. They can be used in an extensive range of applications, including automotive, footwear, interior design, adhesives, coatings, textile and biomedical. In what concerns the footwear sector, it is estimated that TPU based components represent about 60% of the whole European production of footwear components [1]. On the other hand, the use of a wide variety of additives in TPU formulations (e.g. pigments, coatings and fillers) limits the possibility of recycling. In such scenario, biodegradable polymers could offer an excellent solution to the environment hazard posed by the conventional materials [2]. Therefore, given the widespread use of TPUs and associated waste management problems, it makes sense to invest on the development of more biodegradable and environmental compatible solutions. For this purpose, the incorporation of bio-based and biodegradable additives is being studied in the last years [2-4]. The incorporation of a biodegradable compound, even at a low content in a TPU formulation, can promote biodegradation. It will constitute a preferential site for microorganisms’ attack thus favouring biodegradation initiation and progression. In this work, a base TPU used in the footwear industry was modified by compounding with three biobased additives (lignin, starch and cellulose). Biodegradability of the resulting materials was evaluated in agar plate tests against the fungi Aspergillus niger ATCC16404, the gram negative bacteria Pseudomonas aeruginosa ATCC9027 and an association of both (consortium). In a second phase soil tests have been also performed.info:eu-repo/semantics/publishedVersio

Incorporation of an acrylic fatty acid derivative as comonomer for oxidative cure in acrylic latex

An acrylic fatty acid derivative (AcFAD) was evaluated as comonomer for promotion of oxidative cure in waterborne latexes. AcFAD was polymerized by solvent homopolymerization and copolymerization and by emulsion copolymerization, and the final products characterized. In the two polymerization processes, NMR analyses confirmed that the reaction occurred involving both the terminal acrylic double bond and the conjugated double bonds of the aliphatic chain. Compared with a reference acrylic latex, the results obtained after AcFAD incorporation showed a time-dependent increase in gel content and in solvent resistance of dry films. These were ascribed to oxidative cure and consequent self-crosslinking of the acrylic polymer, involving the conjugated double bonds in AcFAD side chains. Oxidative cure was also confirmed by FTIR analyses. In addition, reduction in minimum film-forming temperature evidenced that AcFAD has an internal plasticization effect during film formation. Incorporation of this comonomer in acrylic paint binder formulations constitutes a promising alternative to the use of volatile coalescing agents

Screening of different microorganisms for their biodegradation capacity regarding polyester-based thermoplastic polyurethanes

and bio-based solutions in shoe manufacturing, including the use of biodegradable materials. As a first step towards the proposal of such solutions, in this work different microorganisms were screened for their intrinsic capacity to degrade a base TPU. The biodegradability was tested using the agar plate method against different bacteria, fungi and a consortium of both. The most promising results, corresponding to higher weight-loss percentages of the TPU sample, were obtained using the consortium of Pseudomonas aeruginosa and Aspergillus niger. These best conditions were thereafter applied to TPU samples compounded with biobased additives.info:eu-repo/semantics/publishedVersio

Clarifying changes in student empathy throughout medical school: a scoping review

Despite the increasing awareness of the relevance of empathy in patient care, some findings suggest that medical schools may be contributing to the deterioration of students' empathy. Therefore, it is important to clarify the magnitude and direction of changes in empathy during medical school. We employed a scoping review to elucidate trends in students' empathy changes/differences throughout medical school and examine potential bias associated with research design. The literature published in English, Spanish, Portuguese and French from 2009 to 2016 was searched. Two-hundred and nine potentially relevant citations were identified. Twenty articles met the inclusion criteria. Effect sizes of empathy scores variations were calculated to assess the practical significance of results. Our results demonstrate that scoped studies differed considerably in their design, measures used, sample sizes and results. Most studies (12 out of 20 studies) reported either positive or non-statistically significant changes/differences in empathy regardless of the measure used. The predominant trend in cross-sectional studies (ten out of 13 studies) was of significantly higher empathy scores in later years or of similar empathy scores across years, while most longitudinal studies presented either mixed-results or empathy declines. There was not a generalized international trend in changes in students' empathy throughout medical school. Although statistically significant changes/differences were detected in 13 out of 20 studies, the calculated effect sizes were small in all but two studies, suggesting little practical significance. At the present moment, the literature does not offer clear conclusions relative to changes in student empathy throughout medical school.info:eu-repo/semantics/publishedVersio

Combined effects of ultrasound and immobilization protocol on butyl acetate synthesis catalyzed by CALB

It is well established that the performance of lipase B from Candida antarctica (CALB) as catalyst for esterification reactions may be improved by the use of ultrasound technology or by its immobilization on styrene-divinylbenzene beads (MCI-CALB). The present research evaluated the synthesis of butyl acetate using MCI-CALB under ultrasonic energy, comparing the results against those obtained using the commercial preparation, Novozym 435. The optimal conditions were determined using response surface methodology (RSM) evaluating the following parameters: reaction temperature, substrate molar ratio, amount of biocatalyst, and added water. The optimal conditions for butyl acetate synthesis catalyzed by MCI-CALB were: Temperature, 48.8 °C; substrate molar ratio, 3.46:1 alcohol: Acid; amount of biocatalyst, 7.5%; and added water 0.28%, both as substrate mass. Under these conditions, 90% of conversion was reached in 1.5 h. In terms of operational stability, MCI-CALB was reused in seven cycles while keeping 70% of its initial activity under ultrasonic energy. The support pore size and resistance are key points for the enzyme activity and stability under mechanical stirring. The use of ultrasound improved both activity and stability because of better homogeneity and reduced mechanical stress to the immobilized system.This work was supported by grants from CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico), and CTQ2013-41507-R from Spanish MINECO. We would like to thank Novozymes Spain for its comprehensive support of this research, in special Ramiro Martínez (Novozymes, Spain) for kindly supplying the enzymes used in the work. We also thank CNPq (Brazil) for a fellowship to A.M. Silva and FAPERGS (Brazil) for a fellowship to J.S. Alves. A Ph D. fellowship from Spanish Goberment to Miss Garcia-Galan is also acknowledged The help and suggestions from Ángel Berenguer-Murcia (Instituto de Materiales, Universidad de Alicante) are gratefully recognized. We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI)Peer Reviewe

Materials, components and technology for the footwear of the future - Newalk project

At present, footwear is considered as one of the most internationalized sectors of the Portuguese industry with a significant importance for the national economy, as it is proved by the economic data of 2012: the average annual production was 74 million of shoe pares, being 90.0% of the production exported, which represents an average value of 1610 million euros [l].Financiai support from COMPETE, QREN and EU (project QREN SI J&D Copromoção 13850 NEWALK) and FCT and FEDER under Program COMPETE (PEst-C/EQB/LA0020/2011 strategic project).info:eu-repo/semantics/publishedVersio

NEWALK: novos materiais e componentes para calçado do futuro

A indústria do calçado é o núcleo de um importante cluster da economia nacional. A sua evolução refletiu-se no aumento da produtividade e no valor bruto da produção. Como resultado, o preço do calçado exportado em 2011 subiu para os 23,70 euros/par, tendo o valor global das exportações atingido 1548 milhões de euros (APICCAPS, 2012). Atualmente, este setor procura afirmar-se em nichos de mercado com maior exigência técnico-científica, de valor acrescentado e de padrões de qualidade elevados, resultando no investimento em investigação e desenvolvimento tecnológico. Neste contexto, o IPB tem participado em projetos de I&DT em parceria com o Centro Tecnológico do Calçado de Portugal (CTCP), estando presentemente em curso o projeto NEWALK