Flexible organic–inorganic hybrid layer encapsulation for organic opto-electronic devices

In this work we produce and study the flexible organic–inorganic hybrid moisture barrier layers for the protection of air sensitive organic opto-electronic devices. The inorganic amorphous silicon nitride layer (SiNx:H) and the organic PMMA [poly (methyl methacrylate)] layer are deposited alternatingly by using hot wire chemical vapor deposition (HW-CVD) and spin-coating techniques, respectively. The effect of organic–inorganic hybrid interfaces is analyzed for increasing number of interfaces. We produce highly transparent (∼80% in the visible region) hybrid structures. The morphological properties are analysed providing a good basis for understanding the variation of the water vapor transmission rate (WVTR) values. A minimum WVTR of 4.5 × 10−5g/m2day is reported at the ambient atmospheric conditions for 7 organic/inorganic interfaces. The hybrid barriers show superb mechanical flexibility which confirms their high potential for flexible applications.

In-line rheo-optical microstructural characterization of complex polymer systems

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos.

Poly(2-hydroxyethyl methacrylate): A new star polymer

Multiarm star polymers are attractive materials due to their unusual bulk and solution properties. They are considered analogues of dendrimers with a wide range of applications, such as drug delivery, membranes, coatings and lithography.1 The advent of controlled polymerization made possible the existence of this unique class of organic nanoparticles (ONPs).2 Two major synthetic strategies are usually employed in the preparation of star polymers, the core-first and arm-first approaches. The core-first approach involves a controlled living polymerization using a multiarm initiator core while the arm-first methodology is based in the quenching of living polymers with multifunctional coupling agent or bifunctional vinyl compounds. Herein, we present the synthesis and characterization of a new star polymer, the multiarm star poly(2-hydroxyethyl methacrylate). The tetra-armed star polymer was prepared by reversible addition fragmentation chain-transfer (RAFT) polymerization using the core-first approach. The RAFT chain-transfer agent (RAFT CTA) pentaerythritol tetrakis[2-(dodecylthiocarbonothioylthio)-2-methylpropionate] was used as multiarm initiator core were 2-hydroxyethyl methacrylate (HEMA) was polymerized using AIBN as radical initiator. Structural characterization was performed by 1H NMR and FTIR. The new polymer is able to uptake large quantities of organic solvents, forming gels. The rheological behavior of these gels was also investigated.

Ultrasound enhances lipase-catalyzed synthesis of poly (ethylene glutarate)

The present work explores the best conditions for the enzymatic synthesis of poly (ethylene glutarate) for the first time. The start-up materials are the liquids; diethyl glutarate and ethylene glycol diacetate, without the need of addition of extra solvent. The reactions are catalyzed by lipase B from Candida antarctica immobilized on glycidyl methacrylate-ter-divinylbenzene-ter-ethylene glycol dimethacrylate at 40 °C during 18 h in water bath with mechanical stirring or 1 h in ultrasonic bath followed by 6 h in vacuum in both the cases for evaporation of ethyl acetate. The application of ultrasound significantly intensified the polyesterification reaction with reduction of the processing time from 24 to 7 h. The same degree of polymerization was obtained for the same enzyme loading in less time of reaction when using the ultrasound treatment. The degree of polymerization for long-term polyesterification was improved approximately 8-fold due to the presence of sonication during the reaction. The highest degree of polymerization achieved was 31, with a monomer conversion of 96.77%. The ultrasound treatment demonstrated to be an effective green approach to intensify the polyesterification reaction with enhanced initial kinetics and high degree of polymerization.

Development of a new U 200 pultrusion die to produce GRP composite profiles using different thermosetting resins

In this work, a steel heated pultrusion die was designed, developed and manufactured to produce U200 glass fibre reinforced thermosetting matrix (GRP) profiles. The finite element analysis (FEA) was used to predict and optimise the developed die heating by using cylindrical electrical powered cartridges. To assess the new die performance it was mounted in the 120 kN pultrusion line of the Portuguese company Vidropol SA and used to produce continuously U200 profiles able to meet all requirements specified for the E23 grade accordingly to the European Standard EN 13706: 2002. After setting up the type, orientation and sequence of layers in laminate, orthophthalic, isophthalic and bisphenolic unsaturated polyester as well as vinylester resins were used to produce glass fibre reinforced U 200 composite profiles. An appropriated catalyst system was selected and the processing variables optimised for each case, namely, pultrusion pull-speed and die temperature. Finally, the produced U200 profiles were submitted to visual inspection, calcination and mechanical tests, namely, flexural, tensional and interlaminar shear strength (ILSS) tests, to assess their accomplishment with the EN 13706 requirements.

Using a new developed die and different types of thermosetting resins to produce U200 profiles by pultrusion

In this work, a new steel heated pultrusion die was designed, developed and manufactured to produce U200 glass fibre reinforced thermosetting matrix (GRP) profiles. The finite element analysis (FEA) was used to predict and optimise the developed die heating by using cylindrical electrical powered cartridges. To assess the new die performance it was mounted in the 120 kN pultrusion line of the Portuguese company Vidropol SA and used to produce continuously U200 profiles able to meet all requirements specified for the E23 grade accordingly to the European Standard EN 13706: 2002. After setting up the type, orientation and sequence of layers in the U 200 laminate, different types of thermosetting resins were used in its production. Orthophthalic, isophthalic and bisphenolic unsaturated polyester as well as vinylester resins were used to produce glass fibre reinforced U 200 composite profiles. All applied resins were submitted to SPI gel tests in order to select the more appropriated catalyst system and optimise the processing variables to be used in each case, namely, pultrusion pull-speed and die temperature. The best pultrusion operational conditions were selected by varying and monitoring the pull-speed and die temperature and, at the same time, measuring the temperature on the manufactured U 200 profile during processing. Finally, the produced U200 profiles were submitted to visual inspection, calcination and mechanical tests, namely, flexural, tensional and interlaminar shear strength (ILSS) tests, to assess their accomplishment with the EN 13706 requirements.

Poly-N-acetyl glucosamine expression in Staphylococcus epidermidis biofilm cells affects the immune response and promotes tissue pathology in infected hosts

Staphylococcus epidermidis is a biofilm - forming bacterium and a leading etiological agent of nosocomial infections. The ability to establish biofilms on indwelling medical devices is a key virulence factor for this bacterium. Still, the influence of poly - N - acetyl glucosamine (PNAG), the major component of the extracellular biofilm matrix, in the host immune response has been scarcely studied. Here, t h is influence was assessed in mice challenged i.p. with PNAG - p roducing (WT) and isogenic - mutant lacking PNAG (M10) bacteria grown in biofilm - inducing conditions. Faster bacterial clearance was observed in the mice infected with WT bacteria than in M10 - infected counterparts , which w as accompanied by earlier neutrophil recruitment and higher IL - 6 production. Interestingly, in the WT - infected mice, but not in those infected with M10 , elevated serum IL - 10 was detected . To further study the effe ct of PNAG in the immune response, mice were primed with WT or M10 biofilm bacteria and subsequently infected with WT biofilm - released cells. WT - primed mice presented a higher frequency of splenic IFN - γ + and IL - 17 + CD4 + T cells, and more severe liver patho logy than M10 - primed counterparts. Nevertheless, T reg cells obtained from the WT - primed mice presented a higher suppressive function than those obtained from M10 - primed mice. This effect was abrogated when IL - 10 - deficient mice were similarly primed and infected indicating that PNAG promotes the differentiati on of highly suppressive T reg cells by a mechanism dependent on IL - 10. Altogether, these results provide evidence help ing explain ing the coexistence of inflammation and bacterial persistence often observed in biofilm - originated S. epidermidis infections

Thermal characterization of polyhydroxyalkanoates and poly(lactic acid) blends obtained by injection molding

In this work we present the thermal characterization of the full scope of polyhydroxyalcanoate and poly(lactic acid) blends obtain by injection molding. Blends of polyhydroxyalcanoate and poly(lactic acid) (PHA/PLA) were prepared in different compositions ranging from 0–100% in steps of 10%. The blends were injection molded and then characterized by differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and wide angle X-ray diffraction (WAXD). The increment of PHA fraction increased the degree of crystallinity of the blend and the miscibility of the base polymers as verified by the Fox model. The WAXD analysis indicates that the presence of PHA hindered the PLA crystallization. The crystallization evolution trough PHA weight fraction (wf) shows a phase inversion around 50-60%. SEM analyses confirmed that the miscibility of PHA/PLA blends increased with the incorporation of PHA and became total for values of PHA higher that 50%.

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.

High performance electromechanical actuators based on ionic liquid/poly(vinylidene fluoride)

Due to the increasing need of low voltage actuators, independent from electrochemical processes, electroactive actuators based on poly(vinylidene fluoride) composites with 10, 25 and 40 % of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C2mim] [NTf2], ionic liquid are prepared by solvent casting and melting. We show that the charge structure of [C2mim] [NTf2] induces the complete piezoelectric -phase crystallization of the PVDF within the composite and decreases its crystallinity fraction significantly. [C2mim] [NTf2] also works as a plasticizer of PVDF, reducing the elastic modulus down to 12 % of the initial value. Moreover, the composites show significant displacement and bending under applied voltages of 2, 5 and 10 Vpp. The displacement and bending of the composite membranes are also evaluated as a function of [C2mim] [NTf2] content and sample thickness. Increasing amounts of ionic liquid result in larger deformations independently of the applied voltage.

Gd2O3: Eu Nanoparticle-Based Poly(vinylidene fluoride) Composites for Indirect X-ray Detection

Polymer based scintillator composites have been fabricated by combining poly(vinylidene fluoride) (PVDF) and Gd2O3:Eu nanoparticles (50nm). PVDF has been used since it is a flexible and stable binder matrix and highly resistance to thermal and light deterioration. Gd2O3:Eu has been selected as scintillator material due to its wide band gap, high density and suitable visible light yield. The structural, mechanical, thermal and electrical characteristics of the composites were studied as a function of filler content, together with their performance as scintillator material. The introduction of Gd2O3:Eu nanoparticles into the PVDF matrix does not influence the morphology of the polymer or the degree of crystallinity. On the other hand, an increase of the Young´s modulus with respect to PVDF matrix is observed for filler contents of 0.1-0.75 wt.%. The introduction of Gd2O3:Eu into the PVDF matrix increases dielectric constant and DC electrical conductivity as well as the visible light yield in the nanocomposite, being this increase dependent upon Gd2O3:Eu content and X-ray input power. In this way, Gd2O3:Eu/PVDF composites shows suitable characteristics to be used as X-ray radiation transducers, in particular for large area applications.

Poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) lithium-ion battery separator membranes prepared by phase inversion

Separator membranes based on poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) were prepared by solvent casting technique based on its phase diagram in N,Ndimethylformamide (DMF) solvent. The microstructure of the PVDF-CTFE separator membranes depends on the initial position (temperature and concentration) of the solution in the phase diagram of the PVDF-CTFE/DMF system. A porous microstructure is achieved for PVDF-CTFE membranes with solvent evaporation temperature up to 50 ºC for a polymer/solvent relative concentration of 20 wt%. The ionic conductivity of the separator depends on the degree of porosity and electrolyte uptake, the highest room temperature value being 1.5 mS.cm-1 for the sample with 20 wt% of polymer concentration and solvent evaporation temperature at 25 ºC saturated with 1 mol L-1 lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) in propylene carbonate (PC). This PVDF-CTFE separator membrane in Li/C-LiFePO4 half-cell shows good cyclability and rate capability, showing a discharge value after 50 cycles of 92 mAh.g-1 at 2 C, which is still 55% of the theoretical value. PVDF-CTFE separators are thus excellent candidates for high-power and safety lithium-ion batteries applications.

Ag-TiNx electrodes deposited on piezoelectric poly(vinylidene fluoride) for biomedical sensor applications

Electroactive polymers are one of the most interesting class of polymers used as smart materials in various applications, such as the development of sensors and actuators for biomedical applications in areas such as smart prosthesis, implantable biosensors and biomechanical signal monitoring, among others. For acquiring or applying the electrical signal from/to the piezoelectric material, suitable electrodes can be produced from Ti based coatings with tailored multifunctional properties, conductivity and antibacterial characteristics, through Ag inclusions. This work reports on Ag-TiNx electrodes, deposited by d. c. and pulsed magnetron sputtering at room temperature on poly(vinylidene fluoride), PVDF, the all-round best piezoelectric polymer.. Composition of the electrodes was assessed by microanalysis X-ray system (EDS - energy dispersive spectrometer). The XRD results revealed that the deposition conditions preserve the polymer structure and suggested the presence of crystalline fcc-TiN phase and fcc-Ag phase in samples with N2 flow above 3 sccm. According to the results obtained from SEM analysis, the coatings are homogeneous and Ag clusters were found for samples with nitrogen flow above 3 sccm. With increasing nitrogen flow, the sheet resistivity tend to be lower than the samples without nitrogen, leading also to a decrease of the piezoelectric response. It is concluded that the deposition conditions do significantly affect the piezoelectric polymer, which maintain its characteristics for sensor/actuator applications.

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 ionic liquid anion and cation on the physico-chemical properties of poly(vinylidene fluoride)/ionic liquid blends

Poly(vinylidene fluoride), PVDF, has been blended with different ionic liquids (IL) in order to evaluate the effect of the different IL anions and cations on the electroative -phase, thermal, mechanical and electrical properties of the polymer blend. [C2MIM][Cl], [C6MIM][Cl], [C10MIM][Cl], [C2MIM][NTf2], [C6MIM][NTf2], [C10MIM][NTf2] have been selected and were introduced in the polymer at a weight percentage of 40 wt%. It was found that the incorporation of ILs into the PVDF matrix leads to an increase of the -phase content due to the strong electrostatic interactions between the dipolar moments of PVDF and the ILs. Further, the incorporation of ILs into PVDF strongly decreases the elastic modulus and increases the electrical conductivity of the blend with respect to the pure polymer matrix, all these effects being accompanied by a modification of the crystallization kinetics, as indicated by the modified spherulitic microstructure. Thus, novel PVDF/IL blends films with high transparency, excellent antistatic properties, and highly polar crystal form fraction were successfully achieved.