Toughening due to domain switching in single crystal ferroelectric materials

In this paper Mode I steady state crack growth in single crystal ferroelectric materials is investigated. Specifically, the fracture toughness enhancement due to domain switching near a steadily growing crack tip is analyzed. For this purpose, an incremental phenomenological constitutive law for single crystal ferroelectric materials is implemented within a finite element model to calculate the stress and remanent strain fields around the crack tip. Also, the ratio of the far field applied energy release rate to the crack tip energy release rate, i.e. the toughening, is calculated. The numerical computations are carried out for single crystal ferroelectric materials of tetragonal or rhombohedral structure with different switching hardening and irreversible remanent strain levels. Toughening levels for crack growth along different crystallographic directions and planes are obtained and compared. Results from numerical computations for the toughening anisotropy for both tetragonal and rhombohedral crystals are presented and discussed.     

The influence of fabrication processing on domain structure and polarization switching in PZN-based ferroelectric ceramics

Lead zinc niobate (Pb(Zn_1/3Nb_2/3)O₃, PZN) based ceramics are prepared by using conventional mixing oxide and complex phase reaction-sintering ceramic techniques. From the results of X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), it is clear that these two fabrication processing routes produce different microstructures and ferroelectric domains in the same Pb(Zn_1/3Nb_2/3)O₃–BaTiO₃–Pb(Zr_0.4Ti_0.6)O₃ composition. Furthermore, different phase transitions are observed for the temperature dependence of the dielectric permittivity that can be confirmed by differential scanning calorimetry (DSC). Different polarization switching characteristics are also examined by using high field-induced strain and ferroelectric hysteresis loop. It is suggested that the distribution of the inner stress and domain configuration should be related with the fabrication processing of ferroelectric ceramics.     

铁电陶瓷中电畴翻转研究进展

电畴为铁电陶瓷固有的独特微观组织特征之一,铁电陶瓷的许多性能均与其密切有关.综述了铁电陶瓷中的电畴结构,系统介绍了电场、机械作用引起的电畴翻转,概述了电畴翻转对铁电陶瓷断裂韧性的影响及其研究进展.     

A thermodynamically consistent model with evolving domain structures in ferroelectrics

A thermodynamically consistent uniaxial model combining the benefits of both phenomenological and micromechanical models is proposed. The driving forces derived from irreversible thermodynamics induce domain switching on reaching certain critical values. The back stress and electric fields, assumed as linear functions of remanent strain and polarization, developed by the domain switching process are introduced to assist or resist further changes in microscopic state of the crystal depending on the loading history. In this model, volume fractions of three distinct uniaxial variants act as internal variables describing the microscopic state of the crystal. Domain switching process for general cases involving two variants and for simultaneous evolution cases where three distinct variants participate the switching process are dealt with. The model is found to reproduce the characteristics of the responses of ferroelectric polycrystals under uniaxial complex electro-mechanical loading cases that are consistent with the experimental observations.     

In situ observation of electric-field-induced domain switching and crack propagation in poled PMNT62/38 single crystals

It is important to in situ observe the crack propagation and the corresponding domain switching in ferroelectrics subjected to electric loading since domain switching has been widely assumed to play a critical role in the electric-field-induced crack growth. In this investigation, we in situ observed the crack propagation and the domain switching in PMNT62/38 single crystals poled along the [001] orientation. An experimental setup was designed and constructed to investigate the crack propagation and the domain switching in thin plate specimens with pre-crack subjected to electric field by using polarized light microscope (PLM). The pre-crack began to propagate forward accompanied by the appearance of domain switching zones near the crack tip and the disappearance of switched zones behind the crack tip at the unipolar electric field of E = 0.8E_C. The results indicate that the structure mismatch of the adjacent switched zones with different polarizations stimulated by the intensive electric field near the crack tip results in the electric-field-induced crack growth.     

铁电陶瓷的电畴及畴变观测研究进展

铁电陶瓷材料，特别是锆钛酸铅(PZT)在众多领域具有广泛的应用前景，影响其推广应用的主要因素是使用过程中外电、力场引起的材料性能的退化。观测铁电电畴及畴变的方法对研究其在外场下性能破坏机理、提高其使用的可靠性和预防其失效具有重要的理论和实际意义。本文比较了不同实验方法和测试技术的优缺点，对铁电陶瓷的电畴观测进行了综述，并简要总结了铁电陶瓷的畴变观测技术研究现状，指出了目前该领域研究中存在的问题。     

Multiaxial behavior of ferroelectric single and polycrystals with pressure dependent boundary effects

The external electric and mechanical fields applied at angles to the initial poled direction of the ferroelectric ceramics produce a significantly different nonlinear behavior to that of external fields applied parallel to the poling direction. This angle dependent response of ferroelectric single and polycrystals are predicted by the model proposed based on irreversible thermodynamics and physics of domain switching. The dissipation associated with boundary constraints in thin ferroelectric single crystals are incorporated in the model. As well, the pressure dependent constraints imposed by the surrounding grains on the grain of interest at its boundary during domain switching is correlated with the resistance experienced by a ferroelectric single crystal on its boundary during domain switching. Taking all the domain switching possibilities, the volume fractions of each of the variants in a grain are tracked and homogenized for macroscopic behavior. Numerical simulations were carried out for the multiaxial behavior of ferroelectric single and polycrystals under electrical, mechanical and electromechanical loading conditions.     

Nanoscale domain switching in Bi3.15Eu0.85Ti3O12 thin films annealed at different temperature by scanning probe microscopy

The nanoscale domain switching behavior of Bi_3.15Eu_0.85Ti₃O₁₂ (BET) thin films annealed at temperatures of 600, 650 and 700 °C is investigated by scanning probe microscopy (SPM) via the direct observation on their domain structure. It is shown that most ferroelectric domains are clearly detectable and confined in the grains. Some domains opposite to the polarizing electric field were observed by SPM, and their formations are attributed to the grain boundaries playing an active roles in pinning a preferential polarization state. The remnant polarization (2P_r) values of BET thin films increase with the annealing temperature due to the increase of nanoscale domains switched into the direction of polarizing electric field.     

Domain switching in ferroelectric single crystal/ceramics under electromechanical loading

Domain switching in PMN-PT single crystal and PZT-5 ceramics under electromechanical loading were studied in two different ways. For the single crystal, domain switching was in situ investigated with polarized light microscopy. A 90° domain-switching zone was observed near the crack tip and the size of the switching zone changed with the acuity of the crack tip. For PZT-5 ceramics, domain switching under orthogonal electromechanical loading (E₃ and compressive stress σ₁₁) was studied by measuring the hysteresis loops, butterfly curves and reversed butterfly curves (₁₁ versus E₃). Experimental results show that 90° domain switching is suppressed in the planes parallel to the compression direction. A domain-switching model dividing each 180° switching to two successive 90° switching was proposed to explain the experimental results.     

A finite element prediction of ferroelectric switching behavior using a regular dodecahedron RVE

Some piezoelectric ceramic materials do behave in a nonlinear way when they are subjected to large electric or mechanical stress fields. This macroscopic nonlinearity comes from microscopic domain switchings during which one type of variant switches to other types of variants under large electromechanical fields. This switchable piezoelectric ceramic materials are called ferroelectric ceramics. In the present paper, a typical ferroelectric material particle is represented by a regular dodecahedron representative volume element (RVE) which includes twenty distinct types of variants, and a finite element analysis is carried out on a cubic specimen subjected to both a constant compressive stress and an electric field cycling. The calculation results are compared with experimental observations and isotropy of the responses is discussed.The authors gratefully acknowledge the support of the Agency for Defense Development through Grant ADD 01-05-01.     

Conduction at domain walls in insulating Pb(Zr0.2 Ti0.8)O3 thin films

Domain wall conduction in insulating Pb(Zr(0.2) Ti(0.8))O(3) thin films is demonstrated. The observed electrical conduction currents can be clearly differentiated from displacement currents associated with ferroelectric polarization switching. The domain wall conduction, nonlinear and highly asymmetric due to the specific local probe measurement geometry, shows thermal activation at high temperatures, and high stability over time.     

Enhancement of ferroelectric and piezoelectric characteristics in europium substituted SrBi2Ta2O9 ferroelectric ceramics

Europium substituted samples of compositions Sr_1 − xEu_xBi₂Ta₂O₉ were synthesized by solid-state reaction method. The prepared samples were characterized for their structural and electrical properties. X-ray analysis confirms the formation of the single-phase layered perovskite structure. The microstructural studies reveal that the average grain size increases with increase in Eu content. An increase in remanent polarization and d₃₃ values with increasing concentration of europium has been observed. The maximum 2P_r ~ 14 μC/cm² is observed in the sample with x = 0.20. The observed results have been discussed in terms of contribution from the cation vacancies introduced into the lattice structure due to donor doping.     

A comparative study on the domain switching characteristics of near stoichiometric lithium niobate and lithium tantalate single crystals

For pure SLN and SLT crystals the coercive field measured from ferroelectric hysteresis loop was found to be independent of ramp rate. Decreased lithium concentration in pure SLN samples, the coercive field and internal field are strongly enhanced. Nb_Li antisites are the major contribution to the internal field. Coercive field depends strongly on the ramp rate in case of MgSLN and MgSLT samples, because of domain pinning. The coercive field is considerably reduced in Mg doped SLN and SLT compared to pure samples, indicating that the switching fields are strongly dependent on the nonstoichiometry of the crystals. The coercive field values were found to be constant under multiple cycling in case of Mg (1 mol%) doped SLN crystal. A strong correlation is found to exist between coercive field value and the Curie temperature.     

Reflection of light by domain walls in the uniaxial ferroelectric Sn2P2S6

The occurrence of light scattering during light transmission is described for some orientations of an incident laser beam in polydomain crystals of the uniaxial ferroelectric tin thiohypodiphosphate. This scattering is probably caused by the presence of a reflecting layer near the 180° domain walls. A reflecting layer may be formed as a result of the appearance of charged nonparallel domain walls. Pis’ma Zh. Tekh. Fiz. 23, 45–50 (August 26, 1997)     

Fully coupled non‐linear analysis of piezoelectric solids involving domain switching

Domain switching is the cause of significant non‐linearity in the response of piezoelectric materials to mechanical and electrical effects. In this paper, the response of piezoelectric solids is formulated by coupling thermal, electrical, and mechanical effects. The constitutive equations are non‐linear. Moreover, due to the domain switching phenomenon, the resulting governing equations become highly non‐linear. The corresponding non‐linear finite element equations are derived and solved by using an incremental technique. The developed formulation is first verified against a number of benchmark problems for which a closed‐form solution exists. Next, a cantilever beam made of PZT‐4 is studied to evaluate the effect of domain switching on the overall force–displacement response of the beam. A number of interesting observations are made with respect to the extent of non‐linearity and its progressive spread as the load on the beam increases. Copyright © 2002 John Wiley & Sons, Ltd.     

Unlocking the catalytic activities of 2H-phase Mo-based compounds via topological conversion reaction

Although 2H molybdenum disulfide (MoS₂) layers are highly desirable for hydrogen evolution reaction (HER) owing to their high chemical stabilities and low cost, the inert basal plane and semiconducting nature severely hinder their practical applications. Here, the catalytic activities of 2H phase molybdenum-based compounds are unlocked via topological conversion reaction from Mo₂GeC MAX phase to accordion-like molybdenum phosphosulphide. During the conversion reaction, phosphorus atoms can be implanted into the sandwich-like S-Mo-S planes and gradually substitute sulfur atoms, which are beneficial to optimize the electronic configuration and facilitate to absorb water molecules, unlocking the inert basal planes of 2H phase molybdenum-based compounds. The accordion-like molybdenum phosphosulphide exhibits high hydrogen production rates up to 288 mmol g⁻¹ h⁻¹ cm⁻² at a high loading of 3 mg cm⁻² and ultralong durability up to 35,000 cycles, satisfying the practical application for HER.     

Phase diagram of domain walls in the cubic superstructures of the fcc lattice

The thermodynamical behavior of non-conservative [100] domain walls is investigated in the L1₂ and L1₀ binary alloys, close to their respective first order–disorder transition lines. Calculations are made using an inhomogeneous cluster variation method in the tetrahedron approximation, within the framework of antiferromagnetic Ising Hamiltonian formulation. Critical phenomena are discussed close to the L1₂–disorder and L1₀–disorder transitions, and in the vicinity of the triple point. Different kinds of wetting are exhibited in relation to the relative orientations of the outer variants. The following features are examined: (i) the translational domain wall in the L1₂ phase is found to be wetted by the disordered phase on the coexistence line; (ii) the orientational domain wall between two L1₀ variants undergoes a first-order dewetting transition close to the triple point; and (iii) the translational domain wall in the L1₀ phase undergoes a prewetting transition followed by a wetting process up to the transition line.     

SFM in acoustic mode and its applications to observation of ferroelectric domain

Ferroelectric domain structures as well as other surface topologies such as grain boundaries and scratches in transparent (PbLa)(ZrTi)O₃ (PLZT) ceramics and BaTiO₃ ceramics have been respectively investigated by scanning probe acoustic microscopy (SPAM). A periodic striation-like domain pattern has been imaged. The observed SPAM domain contrast is related to acoustic signals generated through a local piezoelectric coupling mechanism. The submicron domain structure was confirmed by scanning force microscopy (SFM) in the piezoresponse mode.