Nonsolvent induced phase separation preparation of poly(vinylidene fluoride-co-chlorotrifluoroethylene) membranes with tailored morphology, piezoelectric phase content and mechanical properties

Poly(vinylidene fluoride-co-chlorotrifluoroethylene) – P(VDF-CTFE) membranes are increasingly interesting for a wide range of applications, including battery separators, filtration membranes and biomedical applications. This work reports on the morphology, hydrophobicity, thermal and mechanical properties variation of P(VDF-CTFE) membranes processed by nonsolvent induced phase separation technique (NIPS) as a function of the main processing parameters. All membranes show a porous structure composed of large spherulites, (interconnected) micropores and/or microvoids depending on the processing conditions used that in turn affect their hydrophobicity and mechanical properties. The degree of crystallinity of the membranes remains approximately constant with a value of about 15 %, except for the membranes immediately immersed in ethanol, which is of about 23 %. In turn, the crystalline phases present in the copolymer is mainly affected by the temperature and nonsolvent characteristics of the coagulation bath, the β-phase content ranging from 33 to 100 %, depending on those processing parameters. It was show that the temperature of water-based coagulation bath plays an important role in order to produce structurally uniform and homogeneous porous membranes, which is particularly important from the point of view of technological applications.

Mechanical vs. electrical hysteresis of carbon nanotube/styrene-butadiene-styrene composites and their influence in the electromechanical response

The interesting properties of thermoplastics elastomers can be combined with carbon nanotubes (CNT) for the development of large strain piezoresistive composites for sensor applications. Piezoresistive properties of the composites depend on CNT content, with the gauge factor increasing for concentrations around the percolation threshold, mechanical and electrical hysteresis. The SBS copolymer composition (butadiene/styrene ratio) influences the mechanical and electrical hysteresis of composites and, therefore, the piezoresistive response. This work reports on the electrical and mechanical response of CNT/SBS composites with 4%wt nanofiller content, due to the larger electromechanical response. C401 and C540 SBS copolymers with 80% and 60% butadiene content, respectively have been selected. The copolymer with larger amount of soft phase (C401) shows a rubber-like mechanical behavior, with mechanical hysteresis increasing linearly with strain until 100% strain. The copolymer with the larger amount of hard phase (C540) just shows rubber-like behavior for low strains. The piezoresistive sensibility is similar for both composites for low strains, with a GF≈ 5 for 5% strain. The electrical hysteresis shows opposite behavior than the mechanical hysteresis, increasing with strain for both composites, but with higher increase for softer copolymer, C401. The GF increases with increasing strain, but this increase is larger for composites with lower amounts of soft phase due to the distinct initial modulus and deformation of the soft and hard phases of the copolymer. The soft phase shows larger strain under a given stress than the harder phase and the conductive pathway rearrangements in the composites are different for both phases, the harder copolymer (C540) showing higher piezoresistive sensibility, GF≈ 18, for 20% strain.

Effect of butadiene/styrene ratio, block structure and carbon nanotube content on the mechanical and electrical properties of thermoplastic elastomers after UV ageing

Thermoplastic elastomers based on a triblock copolymer styrene-butadiene-styrene (SBS) with different butadiene/styrene ratios, block structure and carbon nanotube (CNT) content were submitted to accelerated weathering in a Xenontest set up, in order to evaluate their stability to UV ageing. It was concluded that ageing mainly depends on butadiene/styrene ratio and block structure, with radial block structures exhibiting a faster ageing than linear block structures. Moreover, the presence of carbon nanotubes in the SBS copolymer slows down the ageing of the copolymer. The evaluation of the influence of ageing on the mechanical and electrical properties demonstrates that the mechanical degradation is higher for the C401 sample, which is the SBS sample with the largest butadiene content and a radial block structure. On the other hand, a copolymer derivate from SBS, the styrene-ethylene/butadiene-styrene (SEBS) sample, retains a maximum deformation of ~1000% after 80 h of accelerated ageing. The hydrophobicity of the samples decreases with increasing ageing time, the effect being larger for the samples with higher butadiene content. It is also verified that cytotoxicity increases with increasing UV ageing with the exception of SEBS, which remains not cytotoxic up to 80 h of accelerated ageing time, demonstrating its potential for applications involving exposition to environmental conditions.

Mechanical fatigue performance of PCL-chondroprogenitor constructs after cell culture under bioreactor mechanical stimulus

In tissue engineering of cartilage, polymeric scaffolds are implanted in the damaged tissue and subjected to repeated compression loading cycles. The possibility of failure due to mechanical fatigue has not been properly addressed in these scaffolds. Nevertheless, the macroporous scaffold is susceptible to failure after repeated loading-unloading cycles. This is related to inherent discontinuities in the material due to the micropore structure of the macro-pore walls that act as stress concentration points. In this work, chondrogenic precursor cells have been seeded in Poly-ε-caprolactone (PCL) scaffolds with fibrin and some were submitted to free swelling culture and others to cyclic loading in a bioreactor. After cell culture, all the samples were analyzed for fatigue behavior under repeated loading-unloading cycles. Moreover, some components of the extracellular matrix (ECM) were identified. No differences were observed between samples undergoing free swelling or bioreactor loading conditions, neither respect to matrix components nor to mechanical performance to fatigue. The ECM did not achieve the desired preponderance of collagen type II over collagen type I which is considered the main characteristic of hyaline cartilage ECM. However, prediction in PCL with ECM constructs was possible up to 600 cycles, an enhanced performance when compared to previous works. PCL after cell culture presents an improved fatigue resistance, despite the fact that the measured elastic modulus at the first cycle was similar to PCL with poly(vinyl alcohol) samples. This finding suggests that fatigue analysis in tissue engineering constructs can provide additional information missed with traditional mechanical measurements.

In vitro mechanical fatigue behavior of poly-ε-caprolactone macroporous scaffolds for cartilage tissue engineering: Influence of pore filling by a poly(vinyl alcohol) gel

Polymeric scaffolds used in regenerative therapies are implanted in the damaged tissue and subjected to repeated loading cycles. In the case of articular cartilage engineering, an implanted scaffold is typically subjected to long term dynamic compression. The evolution of the mechanical properties of the scaffold during bioresorption has been deeply studied in the past, but the possibility of failure due to mechanical fatigue has not been properly addressed. Nevertheless, the macroporous scaffold is susceptible to failure after repeated loading-unloading cycles. In this work fatigue studies of polycaprolactone scaffolds were carried by subjecting the scaffold to repeated compression cycles in conditions simulating the scaffold implanted in the articular cartilage. The behaviour of the polycaprolactone sponge with the pores filled with a poly(vinyl alcohol) gel simulating the new formed tissue within the pores was compared with that of the material immersed in water. Results were analyzed with Morrow’s criteria for failure and accurate fittings are obtained just up to 200 loading cycles. It is also shown that the presence of poly(vinyl alcohol) increases the elastic modulus of the scaffolds, the effect being more pronounced with increasing the number of freeze/thawing cycles.

Influence of design parameters on the mechanical behavior and porosity of braided fibrous stents

In spite of all innovations in stent design, commonly used metallic stents present several problems such as corrosion, infection and restenosis, leading to health complications or even death of patients. In this context, the present paper reports a systematic investigation on designing and development of 100% fiber based stents, which can eliminate or minimize the problems with existing metallic stents. For this purpose, braided stents were produced by varying different materials, structural and process parameters such as mono-filament type and diameter, braiding angle and mandrel diameter. The influence of these design parameters on mechanical behavior as well as stent's porosity was thoroughly investigated, and suitable parameters were selected for developing a stentwith mechanical characteristics and porosity matching with the commercial stents. According to the experimental results, the best performance was achieved with a polyester stent designed with 0.27 mm monofilament diameter, braiding angle of 35° and mandrel diameter of 6 mm, providing similar properties to commercial Nitinol stents.

Characterization of physical, mechanical and chemical properties of quiscal fibres : the influence of atmospheric DBD plasma treatment

This paper reports the first attempt of characterizing various physical, mechanical and chemical properties of Quiscal fibres, used by the native communities in Chile and investigating the influence of atmospheric dielectric barrier discharge plasma treatment on various properties such as diameter and linear density, fat, wax and impurity%, moisture regain, chemical elements and groups, thermal degradation, surface morphology, etc. According to the experimental observations, Quiscal fibre has lower tenacity than most of the technical grade natural fibres such as sisal, hemp, flax, etc., and plasma treatment at optimum dose improved its tenacity to the level of sisal fibres. Plasma treatment also reduced the amount of fat, wax and other foreign impurities present in Quiscal fibres as well as removed lignin and hemicellulose partially from the fibre structure. Plasma treatment led to functionalization of Quiscal fibre surface with chemical groups, as revealed from attenuated total reflection spectroscopy and also confirmed from the elemental analysis using energy dispersive Xray technique and pH and conductivity measurements of fibre aqueous extract. The wetting behavior of Quiscal fibre also improved considerably through plasma treatment. However, untreated and plasma treated Quiscal fibres showed similar thermal degradation behavior, except the final degradation stage, in which plasma treated fibres showed higher stability and incomplete degradation unlike the untreated fibres. The experimental results suggested that the plasma treated Quiscal fibres, like other technical grade natural fibres, can find potential application as reinforcement of composite materials for various industrial applications.

Microstructure and mechanical properties of carbon nanotube reinforced cementitious composites developed using a novel dispersion technique

The authors also acknowledge Centre for Textile Science and Technology (University of Minho) and FIBRENAMICS PLATFORMfor providing required conditions for this research. Sincere thanks are also due to Mr. Pedro Samuel Leite and Mr. Carlos Jesus for their kind help in sample preparation and testing.

Mechanical performance of natural fiber-reinforced composites for the strengthening of masonry

The growing concerns regarding the environmental impact generated by the use of inorganic materials in different fields of application increased the interest towards products based on materials with low environmental impact. In recent years, researchers have turned their attention towards the development of materials obtained from renewable sources, easily recoverable or biodegradable at the end of use. In the field of civil structures, a few attempts have been done to replace the most common composites (e.g. carbon and glass fibers) by materials less harmful to the environment, as natural fibers. This work presents a comprehensive experimental research on the mechanical performance of natural fibers for the strengthening of masonry constructions. Flax, hemp, jute, sisal and coir fibers have been investigated both from physical and mechanical points of view. The fibers with better performance were tested together with three different matrices (two of organic nature) in order to produce composites. These experimental results represent a useful database for understanding the potentialities of natural fibers as strengthening systems.

Design de superfície biomimética para aplicação em atividades desportivas

Tese de Doutoramento Engenharia Têxtil.

Mechanical, fatigue and wear properties of sintered Carbon Nanotube-based functionally graded materials

Tese de Doutoramento Engenharia Mecânica

Development of ductile cementitiuos composites using carbon nanotubes

Concrete is the primary construction material for civil infrastructures and generally consists of cement, coarse aggregates, sand, admixtures and water. Cementitious materials are characterized by quasi-brittle behaviour and susceptible to cracking [1]. The cracking process within concrete begins with isolated nano-cracks, which then conjoin to form micro-cracks and in turn macro-cracks. Formation and growth of cracks lead to loss of mechanical performance with time and also make concrete accessible to water and other degrading agents such as CO2, chlorides, sulfates, etc. leading to strength loss and corrosion of steel rebars. To improve brittleness of concrete, reinforcements such as polymeric as well as glass and carbon fibers have been used and microfibers improved the mechanical properties significantly by delaying (but could not stop) the transformation of micro-cracks into macro forms [2]. This fact encouraged the use of nano-sized fillers in concrete to prevent the growth of nano-cracks transforming in to micro and macro forms. Nanoparticles like SiO2, Fe2O3, and TiO2 led to considerable improvement in mechanical performance and moreover, nano-TiO2 helped to remove organic pollutants from concrete surfaces [3].

Narrative innovations predict symptom improvement: Studying innovative moments in narrative therapy of depression

Objective:Innovative moments (IMs) are moments in the therapeutic dialog that constitute exceptions toward the client's problems. These narrative markers of meaning transformation are associated with change in different models of therapy and diverse diagnoses. Our goal is to test if IMs precede symptoms change, or, on the contrary, are a mere consequence of symptomatic 15 change. Method: For this purpose, IMs and symptomatology (Outcome Questionnaire-10.2) were assessed at every session in a sample of 10 cases of narrative therapy for depression. Hierarchical linear modeling was conducted to explore whether (i) IMs in a given session predict patients' symptoms in the following session and/or (ii) symptoms in a given session predict IMs in the next session. Results: Results suggested that IMs are better predictors of symptoms than the reverse. Conclusions: These results are discussed considering the contribution of meanings and narrative processes' changes to symptomatic improvement.

Thin films composed of gold nanoparticles dispersed in a dielectric matrix: the influence of the host matrix on the optical and mechanical responses

Gold nanoparticles were dispersed in two different dielectric matrices, TiO2 and Al2O3, using magnetron sputtering and a post-deposition annealing treatment. The main goal of the present work was to study how the two different host dielectric matrices, and the resulting microstructure evolution (including both the nanoparticles and the host matrix itself) promoted by thermal annealing, influenced the physical properties of the films. In particular, the structure and morphology of the nanocomposites were correlated with the optical response of the thin films, namely their localized surface plasmon resonance (LSPR) characteristics. Furthermore, and in order to scan the future application of the two thin film system in different types of sensors (namely biological ones), their functional behaviour (hardness and Young's modulus change) was also evaluated. Despite the similar Au concentrations in both matrices (~ 11 at.%), very different microstructural features were observed, which were found to depend strongly on the annealing temperature. The main structural differences included: (i) the early crystallization of the TiO2 host matrix, while the Al2O3 one remained amorphous up to 800 °C; (ii) different grain size evolution behaviours with the annealing temperature, namely an almost linear increase for the Au:TiO2 system (from 3 to 11 nm), and the approximately constant values observed in the Au:Al2O3 system (4–5 nm). The results from the nanoparticle size distributions were also found to be quite sensitive to the surrounding matrix, suggesting different mechanisms for the nanoparticle growth (particle migration and coalescence dominating in TiO2 and Ostwald ripening in Al2O3). These different clustering behaviours induced different transmittance-LSPR responses and a good mechanical stability, which opens the possibility for future use of these nanocomposite thin film systems in some envisaged applications (e.g. LSPR-biosensors).

Mechanical ventilation for the treatment of severe excessive dynamic airway collapse

[Excerpt] We read with interest the case report by Ismael et al1 describing a patient with Sjo¨gren’s syndrome and cystic lung disease who could not be weaned from a ventilator due to severe central excessive dynamic airway collapse (EDAC) of the lower part of the trachea and proximal bronchi. EDAC corresponds to the expiratory bulging of the tracheobronchial wall without known airway structural abnormalities, leading to a decrease of at least 50% in internal diameter.2 It is a rare and underdiagnosed entity, commonly confused with other respiratory diseases such as asthma and COPD. Although noninvasive procedures such as cervicothoracic computed tomography scan on inspiration and expiration may suggest the disorder, the accepted standard method for diagnosis is bronchoscopy.3-7 (...).