Degradation of hybrid material l,d-PLA : 5CB : SWCN under the influence of neutral, acidic, and alkaline environments.

The aim of the study was to investigate the influence of the environment's pH on the degradation of the layers of the ternary composite l,d-PLA : 5CB : SWCN (10 : 1 : 0.5, w/w/w), where l,d-PLA (poly(lactic acid)) is a biodegradable polymer, 5CB is a well-known liquid crystal (4'-pentyl-4-biphenylcarbonitrile), and SWCN are single-walled carbon nanotubes. For this purpose, the samples were stored in air, distilled water, and solutions of 0.1 M NaOH and 0.1 M HCl, for up to 62 days. Using differential scanning calorimetry, atomic force microscopy, and infra-red spectroscopy methods it was observed that for both neat l,d-PLA and composite layers there was a poor degradation process after the storage under standard air conditions, distilled water, and 0.1 M HCl solution, while the erosion of the surface layer kept in 0.1 M NaOH solution was revealed just after 6 days. The longer storage in 0.1 M NaOH solution resulted in complete degradation of the l,d-PLA polymer layer, while the composite layer survived for up to 62 days. The solubilization of the polymeric l,d-PLA matrix in the composite after 62 days was so severe that it resulted in the vanishing of thermal effects on the DSC curve except for one that was probably connected with the glass transition of the residual quantity of the polymer that remained in the layer or the isotropisation of 5CB. As a result, we have shown that admixtures of 5CB and SWCN accelerate the degradation of l,d-PLA in the composite layer due to the hydrophilic/hydrophobic interface in the layer and act as plasticizers. The mechanism of the degradation process is also discussed.

Comparison of the Dielectric Properties of Ecoflex® with L,D-Poly(Lactic Acid) or Polycaprolactone in the Presence of SWCN or 5CB.

The main goal of this paper was to study the dielectric properties of hybrid binary and ternary composites based on biodegradable polymer Ecoflex®, single walled carbon nanotubes (SWCN), and liquid crystalline 4'-pentyl-4-biphenylcarbonitrile (5CB) compound. The obtained results were compared with other created analogically to Ecoflex®, hybrid layers based on biodegradable polymers such as L,D-polylactide (L,D-PLA) and polycaprolactone (PCL). Frequency domain dielectric spectroscopy (FDDS) results were analyzed taking into consideration the amount of SWCN, frequency, and temperature. For pure Ecoflex®, two relaxation processes (α and ß) were identified. It was shown that the SWCN admixture (in the weight ratio 10:0.01) did not change the properties of the Ecoflex® layer, while in the case of PCL and L,D-PLA, the layers became conductive. The dielectric constant increased with an increase in the content of SWCN in the Ecoflex® matrix and the conductive behavior was not visible, even for the greatest concentration (10:0.06 weight ratio). In the case of the Ecoflex® polymer matrix, the conduction relaxation process at a frequency ca. several kilohertz appeared and became stronger with an increase in the SWCN admixture in the matrix. Addition of oleic acid to the polymer matrix had a smaller effect on the increase in the dielectric response than the addition of liquid crystal 5CB. Fourier transform infrared (FTIR) results revealed that the molecular structure and chemical character of the Ecoflex® and PCL matrixes remained unchanged upon the addition of SWCN or 5CB in a weight ratio of 10:0.01 and 10:1, respectively, while molecular interactions appeared between L,D-PLA and 5CB. Moreover, adding oleic acid to pure Ecoflex® as well as the binary and ternary hybrid layers with SWCN and/or 5CB in a weight ratio of Ecoflex®:oleic acid equal to 10:0.3 did not have an influence on the chemical bonding of these materials.

Research of Binary and Ternary Composites Based on Selected Aliphatic or Aliphatic-Aromatic Polymers, 5CB or SWCN Toward Biodegradable Electrodes.

The main goal of this paper was to study the optical, electrical, and thermal properties of hybrid composites based on biodegradable polymers (L,D-poly(lactic acid), polycaprolactone or Ecoflex®), single walled carbon nanotubes (SWCN), and 4'-pentyl-4-biphenylcarbonitrile (5CB). The biodegradable polymers' binary and ternary compositions were analyzed in detail by ultraviolet and visible (UV-Vis) spectroscopy taking into consideration their chemical structure and interactions with 5CB and SWCN. Differential scanning calorimetry (DSC) studies of the created hybrid layers showed thermal stability and changes in glass transition temperature and melting point in comparison to neat polymers, depending on the chemical structure of the polymer used and the type of composition. Morphology of the created layers were investigated by atomic force and polarizing microscopy. The static contact angle measurements of a water drop showed that all of the neat polymer layers were hydrophobic with angle values ranging from 108° to 115°. In addition, in the case of the Ecoflex layers, both with and without additives, a rapid sorption of the deposited water drop was observed. Finally, a simple device with poly(ethylene terephthalate) (PET)/indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/poly [[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl ]] (PTB7) : [6,6]-phenyl-C71-butyric acid methyl ester (PC70BM)/Ag/biodegradable polymer:SWCN architecture was constructed and tested using an infrared (IR) thermographic camera to investigate the surface defects on the created hybrid layers. Increasing the SWCN admixture from 0.01 to 0.5% significantly improved the conductivity only in the case of L,D-poly(lactic acid):SWCN (10:0.5), for which above 5 V, a current with a resistance of 3030.7 Ω could be measured. In order to use the created layers as flexible electrodes, the first experiments were carried out with an admixture of SWCN and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) as conductive compounds.

Modification of AFLC Physical Properties by Doping with BaTiO3 Particles.

In this paper, for the first time, the influence of the BaTiO3 particles on the antiferroelectric liquid crystalline phase was shown. Low concentrations and two different sizes of BaTiO3 particles (nano- and submicroparticles) were used. It was found that admixture of the ferroelectric particles causes a decrease in the concentration of free ions in the liquid crystal matrix. Despite the small amount of admixture, a decrease in spontaneous polarization, switching time and rotational viscosity, was observed, while the tilt angle of molecules and the smectic layer thickness did not change. It turns out that BaTiO3 particles have a very large impact on the dielectric spectra not only in the antiferroelectric phase but also in the ferroelectric and paraelectric phases of the polymorphic mixture studied. The dopants affect also the complex conductivity. In this paper, we explain why some properties are modified by BaTiO3 particles and others are not.

Dielectric, Thermal and Mechanical Properties of l,d-Poly(Lactic Acid) Modified by 4'-Pentyl-4-Biphenylcarbonitrile and Single Walled Carbon Nanotube.

We report here the preparation and thermal, electrical and mechanical characterization of binary and ternary films based on l,d-poly(lactic acid) (l,d-PLA) and 4'-pentyl-4-biphenylcarbonitrile (5CB) and Single Walled Carbon Nanotubes (SWCN) with various weight ratio. The transitions for all investigated hybrid compositions detected by differential scanning calorimetry method were shifted to lower temperatures with increasing the concentration of 5CB in the mixture with polymer. Frequency domain dielectric spectroscopy method and thermal imaging together with polarized optical microscope were used to study electric and structural properties of created hybrid compositions. The best electrical conductivity was observed for hybrid composite l,d-PLA:5CB:SWCN with ratio 10:1:0.5 w/w/w - resistance of 41.0 Ω and thermal response up to 160 °C without causing any damages. Films in crystal form are much more inflexible than in amorphous and can be explain by the cold crystallization occurs at heating while the materials changed their physical state. The value of ε' increases with increasing the 5CB admixture. Moreover, the addition of 5CB to l,d-PLA resulted in increased flexibility of polymeric base films. The best material flexibility and short-term strength were obtained for l,d-PLA sample with 9% 5CB content.

Synthesis and characterization of two new TiO2-containing benzothiazole-based imine composites for organic device applications.

The effect of the presence of titanium dioxide in two new imines, (E,E)-(butane-1,4-diyl)bis(oxybutane-4,1-diyl) bis(4-{[(benzo[d][1,3]thiazol-2-yl)methylidene]amino}benzoate) (SP1) and (E)-N-[(benzo[d][1,3]thiazol-2-yl)methylidene]-4-dodecylaniline (SP2), on the properties and stability of imine:TiO2 composites for organic device applications were examined. The investigated titanium dioxide (in anatase form, obtained via the sol-gel method) exhibited a surface area of 59.5 m2/g according to Brunauer-Emmett-Teller theory, and its structure is a combination of both meso- and microporous. The average pore diameter calculated by the Barrett-Joyner-Halenda method was 6.2 nm and the cumulative volume of pores was 0.117 m3/g. The imine SP1 exhibited columnar organization (Col), while SP2 revealed a hexagonal columnar crystalline phase (Colhk). The imine:TiO2 mixtures in various weight ratio (3:0, 3:1, 3:2, 3:3) showed a lower energy gap and HOMO-LUMO energy levels compared to pure TiO2. This implies that TiO2 provides not only a larger surface area for sensitizer adsorption and good electron collection, but also causes a shift of the imine energy levels resulting from intermolecular interaction. Also the temperature of the phase transition was slightly affected with the increase of TiO2 concentration in imine-based composites. The changes observed in the Fourier transform middle-infrared absorption (FT-MIR) spectra confirmed the significant influence of TiO2 on structural properties of both investigated imines. Similar interactions of oxygen vacancies existing on the TiO2 surface with SP1 and SP2 were observed. The imine:TiO2 mixtures showed good air stability and reusability, which demonstrates its potential for organic device applications.

Hybrid Materials Based on l,d-Poly(lactic acid) and Single-Walled Carbon Nanotubes as Flexible Substrate for Organic Devices.

We report on the application of l,d-poly(lactic acid) (l,d-PLA) with dispersed Single-Walled Carbon Nanotubes (SWCN) as a flexible translucent electrode for organic devices. We used commercially available nanotubes in various weight ratios from 0 to 8% dispersed in chloroform polymeric solution by ultrasonication and were drop cast. The created hybrid materials were investigated by differential scanning calorimetry to determine the influence of SWCN content on the thermal behavior, while polarizing optical microscope was used to find the effect of mechanical deformations on the textures. Drop-cast films were studied by optical transmittance, conductivity, dielectric properties and by thermal imaging under applied potential. Thermal imaging provided evidence of visible voltage-activated conduction. Simple mechanical deformation such as bending with stretching at edge to ca. 90 and elongation test were performed. Moreover, interactions between l,d-poly(lactic acid) and SWCN were investigated by FT-IR and NMR spectroscopy. Finally, we can conclude that the thermographic examination of created films permits fast, simple and inexpensive localization of defects on the surface of l,d-PLA:SWCN film, together with the electrical properties of the films.