Phase morphology and crystallinity of poly(vinylidene fluoride)/poly(ethylene oxide) piezoelectric blend membranes

Polymer blends based on poly(vinylidene fluoride), PVDF and poly(ethylene oxide), PEO, with varying compositions have been prepared by solvent casting, the polymer blend films being obtained from solutions in dimethyl formamide at 70ºC. Under these conditions PVDF crystallizes from solution while PEO remains in the molten state. Then, PEO crystallizes from the melt confined by PVDF crystalls during cooling to room temperature. PVDF crystallized from DMF solutions adopt predominantly the electroactive β-phase (85%). Nevertheless when PEO is introduced in the polymer blend the β-phase content decreases slightly to 70%. The piezoelectric coefficient (d33) in pristine PVDF is -5 pC/N and decreases with increasing PEO content in the PVDF/PEO blends. Blend morphology, observed by electron and atomic force microscopy, shows the confinement of PEO between the already formed PVDF crystals. On the other hand the sample contraction when PEO is extracted from the blend with water (which is not a solvent for PVDF) allows proving the co-continuity of both phases in the blend. PEO crystallization kinetics have been characterized by DSC both in isothermal and cooling scans experiments showing important differences in crystalline fraction and crystallization rate with sample composition.

Effect of the degree of porosity on the performance of poly(vinylidene fluoride-trifluoroethylene)/poly(ethylene oxide) blend membranes for lithium-ion battery separators

Porous polymer membranes based on poly(vinylidene fluoride-trifluoroethylene)/poly(ethylene oxide) copolymers, P(VDF-TrFE)/PEO, are prepared through the, from partial to total, elimination of PEO, leading to interconnected micropores in the polymer blends. Electrolyte uptake, thermal and mechanical properties depend on the amount of PEO present in the polymer blend. Further, the degree of crystallinity of PEO and the elastic modulus (E´) of the polymer blend decrease with increasing PEO removal. Electrical properties of the polymer blend membranes are influenced by the porosity and are dominated by diffusion. The temperature dependence of ionic conductivity follows the Arrhenius behavior. It is the highest for the membranes with a volume fraction of pores of 44% (i.e, 90% PEO removal), reaching a value of 0.54 mS.cm-1 at room temperature. Battery performance was determined by assembling Li/C-LiFePO4 swagelok cells. The polymer blends with 90% PEO removal exhibit rate (124 mAhg-1 at C/5 and 47 mAhg-1 at 2C) and cycling capabilities suitable for lithium ion battery applications.

Design and validation of a biomechanical bioreactor for cartilage tissue culture

Specific tissues, such as cartilage undergo mechanical solicitation under their normal performance in human body. In this sense, it seems necessary that proper tissue engineering strategies of these tissues should incorporate mechanical solicitations during cell culture, in order to properly evaluate the influence of the mechanical stimulus. This work reports on a user-friendly bioreactor suitable for applying controlled mechanical stimulation - amplitude and frequency - to three dimensional scaffolds. Its design and main components are described, as well as its operation characteristics. The modular design allows easy cleaning and operating under laminar hood. Different protocols for the sterilization of the hermetic enclosure are tested and ensure lack of observable contaminations, complying with the requirements to be used for cell culture. The cell viability study was performed with KUM5 cells.

Thermal–mechanical behaviour of chitosan–cellulose derivative thermoreversible hydrogel films

CH, Chitosan; HPMC, (Hydroxypropyl)methyl cellulose; FT, Freeze-thaw; SC, Solvent casting; CH:HPMC (X:Y), pH Z, FT/SC, Chitosan and (hydroxypropyl)methyl cellulose hydrogel, at X and Y proportion (0-100), at Z pH (3.0-4.0) and prepared by freeze-thaw or solvent casting techniques; DSC, Differential scanning calorimetry; MDSC, Temperature modulated Differential scanning calorimetry; Tg, glass transition temperature; ΔH, enthalpy change; TGA, Thermogravimetric Analysis; TG, Thermogravimetry; DTG, Derivative or Differential thermogravimetry; σ, Tensile strength; ε, elongation at break; DMA, Dynamic mechanical analysis; X-Ray, X-radiation, FTIR-ATR, Attenuated total reflectance Fourier transform infrared spectroscopy; SEM, Scanning electron microscopy.

Erratum to: Thermal–mechanical behaviour of chitosan–cellulose derivative thermoreversible hydrogel films

CH, Chitosan; HPMC, (Hydroxypropyl)methyl cellulose; FT, Freeze-thaw; SC, Solvent casting; CH:HPMC (X:Y), pH Z, FT/SC, Chitosan and (hydroxypropyl)methyl cellulose hydrogel, at X and Y proportion (0-100), at Z pH (3.0-4.0) and prepared by freeze-thaw or solvent casting techniques; DSC, Differential scanning calorimetry; MDSC, Temperature modulated Differential scanning calorimetry; Tg, glass transition temperature; ΔH, enthalpy change; TGA, Thermogravimetric Analysis; TG, Thermogravimetry; DTG, Derivative or Differential thermogravimetry; σ, Tensile strength; ε, elongation at break; DMA, Dynamic mechanical analysis; X-Ray, X-radiation, FTIR-ATR, Attenuated total reflectance Fourier transform infrared spectroscopy; SEM, Scanning electron microscopy.

Influence of oxygen plasma treatment parameters on poly(vinylidene fluoride) electrospun fiber mats wettability

Electrospun poly(vinylidene fluoride) (PVDF) fiber mats find applications in an increasing number of areas, such as battery separators, filtration and detection membranes, due to their excellent properties. However, there are limitations due to the hydrophobic nature and low surface energy of PVDF. In this work, oxygen plasma treatment has been applied in order to modify the surface wettability of PVDF fiber mats and superhydrophilic PVDF electrospun membranes have been obtained. Further, plasma treatment does not significantly influences fiber average size (~400 ± 200 nm), morphology, electroactive -phase content (~80-85%) or the degree of crystallinity (Xc of 42 ± 2%), allowing to maintain the excellent physical-chemical characteristics of PVDF. Plasma treatment mainly induces surface chemistry modifications, such as the introduction of oxygen and release of fluorine atoms that significantly changes polymer membrane wettability by a reduction of the contact angle of the polymer fibers and an overall decrease of the surface tension of the membranes.

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.

Hydrophobic/hydrophilic P(VDF-TrFE)/PHEA polymer blend membranes

Polymer blend membranes have been obtained consisting of a hydrophilic and a hydrophobic polymers distributed in co-continuous phases. In order to obtain stable membranes in aqueous environments, the hydrophilic phase is formed by a poly(hydrohyethyl acrylate), PHEA, network while the hydrophobic phase is formed by poly(vinylidene fluoride-co-trifluoroethylene) P(VDF-TrFE). To obtain the composites, in a first stage, P(VDF-TrFE) is blended with poly(ethylene oxyde) (PEO), the latter used as sacrificial porogen. P(VDF-TrFE)/PEO blend membranes were prepared by solvent casting at 70° followed by cooling to room temperature. Then PEO is removed from the membrane by immersion in water obtaining a P(VDF-TrFE) porous membrane. After removing of the PEO polymer, a P(VDF-TrFE) membrane results in which pores are collapsed. Nevertheless the pores reopen when a mixture of hydroxethyl acrylate (HEA) monomer, ethyleneglycol dimethacrylate (as crosslinker) and ethanol (as diluent) is absorbed in the membrane and subsequent polymerization yields hybrid hydrophilic/hydrophobic membranes with controlled porosity. The membranes are thus suitable for lithium-ion battery separator membranes and/or biostable supports for cell culture in biomedical applications.

Erratum: Influence of oxygen plasma treatment parameters on poly(vinylidene fluoride) electrospun fiber mats wettability

Electrospun poly(vinylidene fluoride) (PVDF) fiber mats find applications in an increasing number of areas, such as battery separators, filtration and detection membranes, due to their excellent properties. However, there are limitations due to the hydrophobic nature and low surface energy of PVDF. In this work, oxygen plasma treatment has been applied in order to modify the surface wettability of PVDF fiber mats and superhydrophilic PVDF electrospun membranes have been obtained. Further, plasma treatment does not significantly influences fiber average size (~400 ± 200 nm), morphology, electroactive -phase content (~80-85%) or the degree of crystallinity (Xc of 42 ± 2%), allowing to maintain the excellent physical-chemical characteristics of PVDF. Plasma treatment mainly induces surface chemistry modifications, such as the introduction of oxygen and release of fluorine atoms that significantly changes polymer membrane wettability by a reduction of the contact angle of the polymer fibers and an overall decrease of the surface tension of the membranes.

Biomaterials for cartilage tissue engineering under mechanical stimulus

Tese de Doutoramento em Ciências (Especialidade de Física)

Síntese e testes in vitro de novas pirimido[5,4-d] pirimidinas em células resistentes do cancro coloretal

Dissertação de mestrado em Química Medicinal