A progressive reduction of tetragonal distortion, heat of transition, Curie temperature, and relative dielectric constant has been observed on dense ${\mathrm{BaTiO}}_{3}$ ceramics with grain size decreasing from 1200 to $50\phantom{\rule{0.3em}{0ex}}\mathrm{nm}$. The correlations between grain size, extent of tetragonal distortion, and ferroelectric properties strongly support the existence of an intrinsic size effect. From the experimental trends the critical size for disappearance of ferroelectricity has been evaluated to be $10--30\phantom{\rule{0.3em}{0ex}}\mathrm{nm}$. The strong depression of the relative permittivity observed for the nanocrystalline ceramics can be ascribed to the combination of the intrinsic size effect and of the size-dependent ``dilution'' effect of a grain boundary ``dead'' layer.

Grain-size effects on the ferroelectric behavior of dense nanocrystalline BaTiO 3 ceramics

The paper presents an overview of experimental evidence and present understanding of nonlinear dielectric, elastic and piezoelectric relationships in piezoelectric ceramics. This topic has gained an increasing recognition in recent years due to the use of such materials under extreme operating conditions, for example in electromechanical actuators and high power acoustic transducers. Linear behaviour is generally confined to relatively low levels of applied electric field and stress, under which the dielectric, elastic and piezoelectric relationships are described well by the standard piezoelectric constitutive equations. Nonlinear relationships are observed above certain ‘threshold’ values of electric field strength and mechanical stress, giving rise to field and stress-dependent dielectric (e), elastic (s) and piezoelectric (d) coefficients. Eventually, strong hysteresis and saturation become evident above the coercive field/stress due to ferroelectric/ferroelastic domain switching. The thermodynamic method provides one approach to describing nonlinear behaviour in the ‘intermediate’ field region, prior to large scale domain switching, by extending the piezoelectric constitutive equations to include nonlinear terms. However, this method seems to fail in its prediction of the amplitude and phase of high frequency harmonic components in the field-induced polarisation and strain waveforms, which arise directly from the nonlinear dielectric and piezoelectric relationships. A better fit to experimental data is given by the empirical Rayleigh relations, which were first developed to describe nonlinear behaviour in soft magnetic materials. This approach also provides an indication of the origins of nonlinearity in piezoelectric ceramics, in terms of ferroelectric domain wall translation (at intermediate field/stress levels) and domain switching (at high field/stress levels). The analogy with magnetic behaviour is also reflected in the use of Preisach-type models, which have been successfully employed to describe the hysteretic path-dependent strain-field relationships in piezoelectric actuators. The relative merits and limitations of the different modelling methods are compared and possible areas of application are identified.

Nonlinearity in piezoelectric ceramics

Electrospun polymer biomaterials

Chitosan films incorporated with thyme oil for potential applications of wound dressing were successfully prepared by solvent casting method. The water vapor permeability, oxygen transmission rate, and mechanical properties of the films were determined. Surface and cross-section morphologies and the film thicknesses were determined by Scanning Electron Microscopy (SEM). Fourier transform infrared (FT-IR) spectroscopy was conducted to determine functional group interactions between the chitosan and thyme oil. Thermal behaviors of the films were analyzed by Thermal Gravimetry (TGA) and Differential Scanning Calorimetry (DSC). In addition, the antimicrobial and the antioxidant activities of the films were investigated. The antimicrobial test was carried by agar diffusion method and the growth inhibition effects of the films including different amount of thyme oil were tested on the gram negative microorganisms of Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa and a gram positive microorganism of Staphylococcus aureus. The minimum thyme oil concentration in chitosan films showing the antimicrobial activity on all microorganisms used in the study was found as 1.2 % (v/v). In addition, this concentration showed the highest antioxidant activity due to mainly the carvacrol in thyme oil. Water vapor permeability and oxygen transmission rate of the films slightly increased, however, mechanical properties decreased with thyme oil incorporation. The results revealed that the thyme oil has a good potential to be incorporated into chitosan to make antibacterial and permeable films for wound healing applications.

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Physical, antibacterial and antioxidant properties of chitosan films incorporated with thyme oil for potential wound healing applications.

Fracture behaviors of piezoelectric materials

A detailed analysis of polarization reversal in ferroelectrics has been performed, in the framework of the Landau model for phase transitions. Some important characteristics of homogeneous switching have been emphasized and later used in studying the more general case of inhomogeneous switching. The two extremes of switching current correspond to the inflexion points of the dielectric hysteresis loop. Hysteresis loops of poled ferroelectric samples are expected to include negative-susceptibility regions, for high-frequency applied electric fields. The switching current minimum is eliminated by the experimental method used for recording the switching responses. Equivalent Landau coefficients and electric fields have been defined, in order to integrate the size effects and inhomogeneity contribution to switching of the global order parameter. We correlated the size effects on the critical parameters of the switching (the coercive field) and the ferroelectric-to-paraelectric phase transition (the Curie temperature). Polarization reversal in small-size ferroelectrics can be regarded as a diffuse phase transition, whereas its character is closer to normal for large-size samples. The size dependencies of the reversal speed and maximum current result from the size dependencies of the equivalent Landau coefficients and electric field inducing reversal.

https://iopscience.iop.org/article/10.1088/0953-8984/10/2/026/pdf

Analysis of ferroelectric switching in finite media as a Landau-type phase transition

Chitosan films obtained by dry phase inversion were prepared from an aqueous solution of chitosan in acetic acid. The films, of thickness less than 20 μm, were transparent, very flexible and had smooth surfaces. Increasing the film thickness induced an increase of the internal tensions and the consequent formation of a rough surface. Structural investigations by X-ray diffraction and Fourier transform IR analysis, showed that the chitosan films, as prepared, are amorphous. Further annealing to evaporate acetic acid and water traces, changed the amorphous phase into a more ordered phase, characterized by diffraction peaks at 2θ values of 9, 17, 20 and 23 degrees. Thermal investigations by TG, DTG, and DTA revealed that the decomposition of the chitosan films as prepared proceeds in two stages, starting from 180°C and 540°C.

https://www.degruyter.com/downloadpdf/j/chem.2004.2.issue-4/BF02482727/bf02482727.xml

Vasile Tura

Papers

Analysis of ferroelectric switching in finite media as a Landau-type phase transition

Physico-chemical properties of Chitosan films

Progress in the synthesis and characterization of magnetite nanoparticles with amino groups on the surface

Optimization of polyurethane membranes: Morphology and structure studies

Electrospun PVC/Fe3O4 composite nanofibers for microwave absorption applications