Influence of electrospinning parameters on Poly(hydroxybutyrate) electrospun membranes fiber size and distribution

Poly(hydroxybutyrate) (PHB) obtained from sugar cane was dissolved in a blend of chloroform and dimethylformamide (DMF) and electrospun at 40 ºC. By adding DMF to the solution, the electrospinning process for the PHB polymer becomes more stable, allowing complete polymer crystallization during the jet travelling between the tip and the grounded collector. The influence of processing parameters on fiber size and distribution was systematically studied. It was observed that an increase of tip inner diameter promotes a decrease of the fiber average size and a broader distribution. On the other hand, an increase of the electric field and flow rate produces an increase of fiber diameter until a maximum of ~2.0 m, but for electric fields higher than 1.5 kV.cm-1, a decrease of the fiber diameter was observed. Polymer crystalline phase seems to be independent of the processing conditions and a crystallinity degree of 53 % was found. Moreover, thermal degradation of the as-spun membrane occurs in single step degradation with activation energy of 91 kJ/mol. Furthermore, MC-3T3-E1 cell adhesion was not inhibited by the fiber mats preparation, indicating their potential use for biomedical applications.

Thermomechanical environment characterisation in injection moulding and its relation to the mechanical properties of talc-filled polypropylene

This study is focused on the establishment of relationships between the injection moulding processing conditions, the applied thermomechanical environment (TME) and the tensile properties of talc-filled polypropylene,adopting a new extended concept of thermomechanical indices (TMI). In this approach, TMI are calculated from computational simulations of the moulding process that characterise the TME during processing, which are then related to the mechanical properties of the mouldings. In this study, this concept is extended to both the filling and the packing phases, with new TMI defined related to the morphology developed during these phases. A design of experiments approach based on Taguchi orthogonal arrays was adopted to vary the injection moulding parameters (injection flow rate, injection temperature, mould wall temperature and holding pressure), and thus, the TME. Results from analysis of variance for injection-moulded tensile specimens have shown that among the considered processing conditions, the flow rate is the most significant parameter for the Young’s modulus; the flow rate and melt temperature are the most significant for the strain at break; and the holding pressure and flow rate are the most significant for the stress at yield. The yield stress and Young’s modulus were found to be governed mostly by the thermostress index (TSI, related to the orientation of the skin layer), whilst the strain at break depends on both the TSI and the cooling index (CI, associated to the crystallinity degree of the core region). The proposed TMI approach provides predictive capabilities of the mechanical response of injection-moulded components, which is a valuable input during their design stage.

Mechanical Behavior of the Lamellar Structure in Semi-Crystalline Polymers

We have employed molecular dynamics simulations to study the behavior of virtual polymeric materials under an applied uniaxial tensile load. Through computer simulations, one can obtain experimentally inaccessible information about phenomena taking place at the molecular and microscopic levels. Not only can the global material response be monitored and characterized along time, but the response of macromolecular chains can be followed independently if desired. The computer-generated materials were created by emulating the step-wise polymerization, resulting in self-avoiding chains in 3D with controlled degree of orientation along a certain axis. These materials represent a simplified model of the lamellar structure of semi-crystalline polymers,being comprised of an amorphous region surrounded by two crystalline lamellar regions. For the simulations, a series of materials were created, varying i) the lamella thickness, ii) the amorphous region thickness, iii) the preferential chain orientation, and iv) the degree of packing of the amorphous region. Simulation results indicate that the lamella thickness has the strongest influence on the mechanical properties of the lamella-amorphous structure, which is in agreement with experimental data. The other morphological parameters also affect the mechanical response, but to a smaller degree. This research follows previous simulation work on the crack formation and propagation phenomena, deformation mechanisms at the nanoscale, and the influence of the loading conditions on the material response. Computer simulations can improve the fundamental understanding about the phenomena responsible for the behavior of polymeric materials, and will eventually lead to the design of knowledge-based materials with improved properties.

Effect of fiber alignment in gelled electrospun membranes based on poly(vinylidene fluoride) for battery applications

Battery separators based on electrospun membranes of poly(vinylidene fluoride) (PVDF) have been prepared in order to study the effect of fiber alignment on the performance and characteristics of the membrane. The prepared membranes show an average fiber diameter of 272 nm and a degree of porosity of 87 %. The gel polymer electrolytes are prepared by soaking the membranes in the electrolyte solution. The alignment of the fibers improves the mechanical properties for the electrospun membranes. Further, the microstructure of the membrane also plays an important role in the ionic conductivity, being higher for the random electrospun membrane due to the lower tortuosity value. Independently of the microstructure, both membranes show good electrochemical stability up to 5.0 V versus Li/Li+. These results show that electrospun membranes based on PVDF are appropriate for battery separators in lithium-ion battery applications, the random membranes showing a better overall performance.

Determining factors of environmental management practices in portuguese local entities

Purpose: The aim of this paper is to analyse the development of environmental management practices by Portuguese local entities and their determining factors. Design/methodology/approach: The data were collected by sending a postal questionnaire. In order to measure the degree of development of environmental management practices an index of environmental management practices (EMPI) was developed, which reflects the extent to which a set of 16 environmental management practices have been implemented by the entities included in the sample. Four variables are considered in this study as possible factors that drive the development of environmental management practices by local entities, namely type of entity, size, proactive environmental strategy and Local Agenda 21 Findings: Results indicate the degree of development of environmental management practices in Portuguese local entities is low. Additionally, entity size, the adoption of proactive environmental strategies and the implementation of Local Agenda 21 are explaining factors of the degree of development of such practices. Originality/value: This study adds to the international research on environmental management in public sector by providing empirical data from a country, Portugal, where empirical evidence is still relatively limited.

Determining factors of environmental management practices in portuguese local entities

Purpose – The purpose of this paper is to analyse the development of environmental management practices by Portuguese local entities and their determining factors. Design/methodology/approach – The data were collected by sending a postal questionnaire. In order to measure the degree of development of environmental management practices, an index of environmental management practices (EMPI) was developed, which reflects the extent to which a set of 16 environmental management practices have been implemented by the entities included in the sample. In total, four variables are considered in this study as possible factors that drive the development of environmental management practices by local entities: type of entity; size; proactive environmental strategy; and Local Agenda 21. Findings – Results indicate the degree of development of environmental management practices in Portuguese local entities is low. Additionally, entity size, the adoption of proactive environmental strategies and the implementation of Local Agenda 21 are explaining factors of the degree of development of such practices. Originality/value – The paper adds to the international research on environmental management in the public sector by providing empirical data from a country, Portugal, where empirical evidence is still relatively limited.

Factors Influencing the Implementation of the Balanced Scorecard in Portugal: Empirical Evidence From Privately Owned and Publicly Owned Organizations

In this paper we aim to identify and analyze a set of variables that can potentially influence the adoption and knowledge of the Balanced Scorecard (BSC) in Portugal. Hypotheses were tested using data obtained from a questionnaire sent to 591 publicly-owned organizations (local governments, municipal corporations and hospitals) and 549 privately-owned organizations (large companies and small and medium enterprises) in Portugal. The results allow us to conclude that although the majority of respondents claimed to know the BSC, its use in Portugal is still limited and very recent, particularly in the public sector organizations. However, it should be noted that its use has increased in Portugal in recent years. The study also reveals that in spite of the noticeable differences between public and private sector, the BSC is used in the public sector after a few adjustments to the traditional model. Using as theoretical framework the contingency and institutional theories, we found that decentralization, vertical differentiation and the degree of higher education are associated with the implementation of the BSC.

Carbon Nanofiber Type and Content Dependence of the Physical Properties of Carbon Nanofiber Reinforced Polypropylene Composites

The variation of the physical properties of four differ- ent carbon nanofibers (CNFs), based-polymer nano- composites incorporated in the same polypropylene (PP) matrix by twin-screw extrusion process was investigated. Nanocomposites fabricated with CNFs with highly graphitic outer layer revealed electrical isolation-to-conducting behaviors as function of CNF’s content. Nanocomposites fabricated with CNFs with an outer layer consisting on a disordered pyro- litically stripped layer, in contrast, revealed better mechanical performance and enhanced thermal sta- bility. Further, CNF’s incorporation into the polymer increased the thermal stability and the degree of crystallinity of the polymer, independently on the filler content and type. In addition, dispersion of the CNFs’ clusters in PP was analyzed by transmitted light opti- cal microscopy, and grayscale analysis (GSA). The results showed a correlation between the filler concentration and the variance, a parameter which measures quantitatively the dispersion, for all composites. This method indicated a value of 1.4 vol% above which large clusters of CNFs cannot be dispersed effectively and as a consequence only slight changes in mechanical performance are observed. Finally, this study establishes that for tailoring the physical properties of CNF based-polymer nanocomposites, both adequate CNFs structure and content have to be chosen.

Virtual simulation of the postsurgical cosmetic outcome in patientswith pectus excavatum

Pectus excavatum is the most common congenital deformity of the anterior chest wall, in which several ribs and the sternum grow abnormally. Nowadays, the surgical correction is carried out in children and adults through Nuss technic. This technic has been shown to be safe with major drivers as cosmesis and the prevention of psychological problems and social stress. Nowadays, no application is known to predict the cosmetic outcome of the pectus excavatum surgical correction. Such tool could be used to help the surgeon and the patient in the moment of deciding the need for surgery correction. This work is a first step to predict postsurgical outcome in pectus excavatum surgery correction. Facing this goal, it was firstly determined a point cloud of the skin surface along the thoracic wall using Computed Tomography (before surgical correction) and the Polhemus FastSCAN (after the surgical correction). Then, a surface mesh was reconstructed from the two point clouds using a Radial Basis Function algorithm for further affine registration between the meshes. After registration, one studied the surgical correction influence area (SCIA) of the thoracic wall. This SCIA was used to train, test and validate artificial neural networks in order to predict the surgical outcome of pectus excavatum correction and to determine the degree of convergence of SCIA in different patients. Often, ANN did not converge to a satisfactory solution (each patient had its own deformity characteristics), thus invalidating the creation of a mathematical model capable of estimating, with satisfactory results, the postsurgical outcome

The estimation of the return on firms’ investments – as to ISO 9001

The aim of this paper was to estimate the return on investment in QMS (quality management systems) certification undertaken in Portuguese firms, according to the ISO 9000 series. A total of 426 certified Portuguese firms were surveyed. The response rate was 61.03 percent. The different payback periods were validated through statistical analysis and the relationship between expected and perceived payback periods was discussed. This study suggests that a firm’s sector of activity, size and degree of internationalization are related to the length of the investment in QMS certification recovery period. Furthermore, our findings suggest, that the time taken to obtain the certification is not directly related to the economic component of the certification. The majority of Portuguese firms (58.9%) took up to three years to recoup their investment and 35.5% of companies said they had not yet recovered the initial investment made. The recoup of investment was measured by the increase in the number of customers and consequent volume of deliveries, improved profitability and productivity of the company, improvement of competitive position and performance (cost savings), reduction in the number of external complaints and internal defects/scrap, achievement of some important clientele, among others. We compared our work to similar studies undertaken in other countries. This paper provides a contribution to the research related to the return on investment for costs related to the certification QMS according to ISO 9000. This paper provides a valuable contribution to the field and is one of the first studies to undertake this type of analysis in Portugal.

Effect of fiber orientation in gelled poly (vinylience fluoride) electrospun membranes for Li-ion battery applications

Battery separators based on electrospun membranes of poly(vinylidene fluoride) (PVDF) have been prepared in order to study the effect of fiber alignment on the performance and characteristics of the membrane. The prepared membranes show an average fiber diameter of ~272 nm and a degree of porosity of ~87 %. The gel polymer electrolytes are prepared by soaking the membranes in the electrolyte solution. The alignment of the fibers improves the mechanical properties for the electrospun membranes. Further, the microstructure of the membrane also plays an important role in the ionic conductivity, being higher for the random electrospun membrane due to the lower tortuosity value. Independently of the microstructure, both membranes show good electrochemical stability up to 5.0 V versus Li/Li+. These results show that electrospun membranes based on PVDF are appropriate for battery separators in lithium-ion battery applications, the random membranes showing a better overall performance.

Determinant factors of the implementation of the balanced scorecard in Portugal: empirical evidence in public and private organizations

In this article we aim to identify and analyze a set of variables that can potentially influence the adoption of the Balanced Scorecard (BSC)in Portugal. Hypotheses were tested using data obtained from a questionnaire sent to 591 publicly-owned organizations (local governments, municipal corporations and hospitals) and 549 privately-owned organizations (large companies and small and medium enterprises) in Portugal, with an overall response rate of 31.3%. The results allow us to conclude that although the majority of respondents claimed to know the BSC, its use in Portugal is still limited and very recent, particularly in the public sector organizations. However, it should be noted that its use has increased in Portugal in recent years. Using as theoretical framework the contingency and institutional theories, we found that decentralization, vertical differentiation and the degree of higher education are associated with the implementation of the BSC.

Use of performance information by local politicians: a field study in the Portuguese context.

This paper seeks to investigate the use of performance information by politicians and whether the institutional reforms on performance management (PM) have been operationalized by local politicians. Differences on the policy field and the organizational context have been analyzed. Our goal is contribute to knowledge on PM in the political sphere and understand the different responses of politicians to government change initiatives (mainly coercive pressures). Our findings show that local politicians support the notion that greater attention should be devoted to the use of performance information on the evaluation process. Nevertheless they are very skeptic in relation to effective execution of government reforms. There is an internal culture where agencies are embedded, strongly influenced by the high degree of politicisation among senior managers, that lead politicians to be more concerned about personal opinions and informal performance information rather than to use more sophisticated information (output and outcome measures). The institutional approach helps us to identify political responses to institutional pressures and understand the reasons for a reduced use in the Portuguese context.