The molecular mobility of a MOF-5 metal-organic framework was investigated by broadband dielectric spectroscopy. Three relaxation processes were revealed. The temperature dependence of their relaxation rates follows an Arrhenius law. The process observed at lower temperatures is attributed to bending fluctuations of the edges of the cages involving the Zn-O clusters. The processes ("region II") at higher temperatures were assigned to fluctuations of phenyl rings in agreement with the NMR data found by Gould et al. (J. Am. Chem. Soc. 2008, 130, 3246). The carboxylate groups might also be involved. The rotational fluctuations of the phenyl rings leading to the low frequency part of relaxation region II might be hindered either by some solvent molecules entrapped in the cages or by an interpenetrated structure and have a broad distribution of activation energies. The high frequency part of region II corresponds nearly to a Debye-like process: This is explained by a well-defined structure of empty pores.
This paper proposes a novel, flexible, low cost administration patch which could be used as a non-invasive, controlled transdermal drug delivery system. The fabricated device consists in a flexible microfiber architecture heater covered with a thermoresponsive hydrogel, namely poly(N-isopropylacrylamide), as a matrix for the incorporation of active molecules. The manufacturing process consists of two main steps. First, the electrospun poly(methyl methacrylate) fiber networks are sputter coated with a thin gold layer and attached to flexible poly(ethylene terephthalate) substrates to obtain the heating platforms. Second, the heaters are encapsulated in poly(ethylene terephthalate) foils and covered with poly(N-isopropylacrylamide) hydrogel sheets. In order to illustrate the functionality of the fabricated patch, the hydrogel layer is loaded with methylene blue aqueous solution and is afterwards heated via Joule effect, by applying a voltage on the metalized fibers. The methylene blue releasing profiles of the heated patch are compared with those of the unheated one and the influence of parameters such as hydrogel composition and morphology, as well as the applied voltage values for microheating are investigated. The results indicate that the fabricated patch can be used as a drug administration instrument, while its performance can be tuned depending on the targeted application.
In this work, new films containing composite materials based on blends of thermoplastic polymers of the polyurethane (TPU) and polyolefin (TPO) type, in the absence and presence of BaTiO3 nanoparticles (NPs) with the size smaller 100 nm, were prepared. The vibrational properties of the free films depending on the weight ratio of the two thermoplastic polymers were studied. Our results demonstrate that these films are optically active, with strong, broad, and adjustable photoluminescence by varying the amount of TPU. The crystalline structure of BaTiO3 and the influence of thermoplastic polymers on the crystallization process of these inorganic NPs were determined by x-ray diffraction (XRD) studies. The vibrational changes induced in the thermoplastic polymer’s matrix of the BaTiO3 NPs were showcased by Raman scattering and FTIR spectroscopy. The incorporation of BaTiO3 NPs in the matrix of thermoplastic elastomers revealed the shift dependence of the photoluminescence (PL) band depending on the BaTiO3 NP concentration, which was capable of covering a wide visible spectral range. The dependencies of the dielectric relaxation phenomena with the weight of BaTiO3 NPs in thermoplastic polymers blends were also demonstrated.
This paper prepared composites under the free membranes form that are based on thermoplastic polymers of the type of polyurethane (TPU) and polyolefin (TPO), which are blended in the weight ratio of 2:1, and ceramic nanoparticles (CNs) such as BaSrTiO3 and SrTiO3. The structural, optical, and conductive properties of these new composite materials are reported. The X-ray diffraction studies highlight a cubic crystalline structure of these CNs. The main variations in the vibrational properties of the TPU:TPO blend induced by CNs consist of the following: (i) the increase in the intensity of the Raman line of 1616 cm−1; (ii) the down-shift of the IR band from 800 to 791 cm−1; (iii) the change of the ratio between the absorbance of IR bands localized in the spectral range 950–1200 cm−1; and (iv) the decrease in the absorbance of the IR band from 1221 cm−1. All these variations were correlated with a preferential adsorption of thermoplastic polymers on the CNs surface. A photoluminescence (PL) quenching process of thermoplastic polymers is demonstrated to occur in the presence of CNs. The anisotropic PL measurements have highlighted a change in the angle of the binding of the TPU:TPO blend, which varies from 23.7° to ≈49.3° and ≈53.4°, when the concentration of BaSrTiO3 and SrTiO3 CNs, respectively, is changed from 0 to 25 wt. %. Using dielectric spectroscopy, two mechanisms are invoked to take place in the case of the composites based on TPU:TPO blends and CNs, i.e., one regarding the type of the electrical conduction and another specifying the dielectric–dipolar relaxation processes.
Herein we report on novel multiferroic core–shell nanostructures of cobalt ferrite (CoFe2O4)–bismuth, sodium titanate doped with barium titanate (BNT–BT0.08), prepared by a two–step wet chemical procedure, using the sol–gel technique. The fraction of CoFe2O4 was varied from 1:0.5 to 1:1.5 = BNT–BT0.08/CoFe2O4 (molar ratio). X–ray diffraction confirmed the presence of both the spinel CoFe2O4 and the perovskite Bi0.5Na0.5TiO3 phases. Scanning electron microscopy analysis indicated that the diameter of the core–shell nanoparticles was between 15 and 40 nm. Transmission electron microscopy data showed two–phase composite nanostructures consisting of a BNT–BT0.08 core surrounded by a CoFe2O4 shell with an average thickness of 4–7 nm. Cole-Cole plots reveal the presence of grains and grain boundary effects in the BNT–BT0.08/CoFe2O4 composite. Moreover, the values of the dc conductivity were found to increase with the amount of CoFe2O4 semiconductive phase. Both X-ray photoelectron spectroscopy (XPS) and Mössbauer measurements have shown no change in the valence of the Fe3+, Co2+, Bi3+ and Ti4+ cations. This study provides a detailed insight into the magnetoelectric coupling of the multiferroic BNT–BT0.08/CoFe2O4 core–shell composite potentially suitable for magnetoelectric applications.
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