Energy principle of ferroelectric ceramics and single domain mechanical model

Many physical experiments have shown that the domain switching in a ferroelectric material is a complicated evolution process of the domain wall with the variation of stress and electric field. According to this mechanism, the volume fraction of the domain switching is introduced in the constitutive law of ferroelectric ceramic and used to study the nonlinear constitutive behavior of ferroelectric body in this paper. The principle of stationary total energy is put forward in which the basic unknown quantities are the displacement u _i , electric displacement D _i and volume fraction ρ _I of the domain switching for the variant I. Mechanical field equation and a new domain switching criterion are obtained from the principle of stationary total energy. The domain switching criterion proposed in this paper is an expansion and development of the energy criterion. On the basis of the domain switching criterion, a set of linear algebraic equations for the volume fraction ρ _I of domain switching is obtained, in which the coefficients of the linear algebraic equations only contain the unknown strain and electric fields. Then a single domain mechanical model is proposed in this paper. The poled ferroelectric specimen is considered as a transversely isotropic single domain. By using the partial experimental results, the hardening relation between the driving force of domain switching and the volume fraction of domain switching can be calibrated. Then the electromechanical response can be calculated on the basis of the calibrated hardening relation. The results involve the electric butterfly shaped curves of axial strain versus axial electric field, the hysteresis loops of electric displacement versus electric filed and the evolution process of the domain switching in the ferroelectric specimens under uniaxial coupled stress and electric field loading. The present theoretic prediction agrees reasonably with the experimental results given by Lynch. The project supported by the National Natural Science Foundation of China (10572138).     

A SIMPLE CONSTITUTIVE MODEL FOR FERROELECTRIC CERAMICS UNDER ELECTRICAL/MECHANICAL LOADING

A simple phenomenological model is developed for describing the macroscopic constitutive response of ferroelectric materials based on consideration of the fact that domain switching is a progressive evolution process with loading. The volume fraction of domain switching is taken as an internal variable, which is derived from the domain nucleation theory. The proposed theory can simulate the dielectric hysteresis, reversed butterfly hysteresis, nonlinear strain-stress hysteresis, as well as electric displacement-stress relation of ferroelectric materials. Its comparison with experimental results and two other theoretical models reveals that the model presented can well predict the nonlinear hysteresis of ferroelectrics under electrical or mechanical loading.     

Numerical simulation of domain switching in multilayer ferroelectric actuators

Micromechanical finite element methods are developed based on a nonlinear constitutive model of ferroelectric polycrystals. Electromechanical behaviors ahead of an internal electrode tip are numerically simulated in multilayer ferroelectric actuators. Around the electrode edge, the nonuniform electric field generates a concentration of stress due to the incompatible strain as well as spontaneous strain. The preferred domain switching enhances the concentration of residual stress and may cause the actuators to crack. An electrically permeable crack emanating from an internal electrode is analyzed. A large scale domain switching zone is found in the vicinity of crack tips. The larger the actuating strain and electric field are, the larger the switching zone will be. The size of switching zone even reaches the scale of crack length with increasing electromechanical loading.     

A continuum analysis of charge induced ferroelectric domain wall motions

A continuum model is presented for the motion of a domain wall in a plane 90°-domain configuration subjected to an isolated extrinsic charge near the surface of a ferroelectric single crystal. Local pinning is postulated for the kinetic law. Before the appearance of the extrinsic charge, all polarization surface charges are taken to be neutralized by environmental charges. The domain wall motion after the appearance of the extrinsic charge is assumed to proceed sufficiently fast without any significant conductive currents on the surface or in the interior of the crystal such that new surface and interface polarization charges remain unscreened and contribute to the ferroelectric anisotropy energy. A non-admissible divergence of the electric field and consequently of the local thermodynamic driving force and of the domain wall velocity appears in the model if the domain wall charged by interface polarization charges intersects the crystal surface charged by surface polarization charges under an arbitrary angle. The physically possible domain wall angle is identified using the condition of a non-divergent driving force. The ferroelectric anisotropy energy and an intrinsic surface energy of the domain wall, however, do not provide stability of the domain wall trajectory against an unlimited increase of its curvature at the surface. The problem has been solved conceptually by proper account of the domain wall bending energy. Numerical and dimensional analysis explain also why domain walls driven by extrinsic charges remain almost straight in soft ferroelectrics.     

GIANT ANHYSTERETIC RESPONSE OF FERROELECTRIC SOLID SOLUTIONS WITH MORPHOTROPIC BOUNDARIES: THE ROLE OF POLAR ANISOTROPY

Computer modeling and simulation for the Pb(Zr 1 x Ti x )O 3 (PZT) system reveal the role of polar anisotropy on the giant anhysteretic response and structural properties of morphotropic phase boundary (MPB) ferroelectrics. It is shown that a drastic reduction of the composition- dependent polar anisotropy near the MPB flattens energy surfaces and thus facilitates reversible polarization rotation. It is further shown that the polar anisotropy favors formation of polar domains, promotes phase decomposition and results in a two-phase multidomain state, which response to applied electric field is anhysteretic when the polar domain reorientation is only caused by polarization rotation other than polar domain wall movement. This is the case for the decomposing ferroelectrics under a poling electric field with the formation of a two-phase multidomain microstructure, wherein most domain walls are pinned at the two-phase boundaries. Indication of the microstructure dependence of the anhysteretic strain response opens new avenues to improve the piezoelectric properties of these materials through the microstructure engineering.     

Unconventional domain band structure at the crack tip in ferroelectric ceramics

Domain polarization switch near the tip of a crack or an electrode plays a critical role in the fracture or toughening of ferroelectric ceramics. The intensive electric field near a crack tip stimulates local domain switching. Experiment indicates that the domain band structure in front of an indentation crack under lateral electric loading is unconventional, attributed to the highly localizing crack tip electric field. The partially switched ferroelectric grain resembles a banded Eshelby inclusion embedded in a polycrystalline ferroelectric matrix. The domain wall energy for unconventional domain structures is estimated via arrays of misfit dislocations. Mesomechanics analysis quantifies the unconventional domain band structures. The predicted parameters include the volume fraction, the thickness, and the orientation of switched domain bands.     

Three-dimensional finite element simulations of ferroelectric polycrystals under electrical and mechanical loading

Complex, non-linear, irreversible, hysteretic behavior of polycrystalline ferroelectric materials under a combined electro-mechanical loading is a result of domain wall motion, causing simultaneous expansion and contraction of unlike domains, grain sub-divisions that have distinct spontaneous polarization and strain. In this paper, a 3-dimensional finite element method is used to simulate such a polycrystalline ferroelectric under electrical and mechanical loading. A constitutive law due to Huber et al. [1999. A constitutive model for ferroelectric polycrystals. J. Mech. Phys. Solids 47, 1663-1697] for switching by domain wall motion in multidomain ferroelectric single crystals is employed in our model to represent each grain, and the finite element method is used to solve the governing conditions of mechanical equilibrium and Gauss's law. The results provide the average behavior for the polycrystalline ceramic. We compare the outcomes predicted by this model with the available experimental data for various electromechanical loading conditions. The qualitative features of ferroelectric switching are predicted well, including hysteresis and butterfly loops, the effect on them of mechanical compression, and the response of the polycrystal to non-proportional electrical loading.     

Toughening under non-uniform ferro-elastic domain switching

The existing models of switch-toughening seldom consider the effect of non-uniform ferro-elastic domain switching in the vicinity of a crack. To explore this issue, an evolution law for the volume fraction of the switched portion under applied electromechanical loading is established from the minimum energy principle. Based on this law, a switching model capable of dealing with the non-uniform distribution of switching strain is developed. The domain switching zone is divided into a saturated inner core and an active surrounding annulus. Mono-domain solution of ferro-elastic toughening is obtained under the model of small scale domain switching. Toughening for ferroelectrics with different poling states is estimated via Reuss type approximation. Two sets of solutions are obtained according to spherical and cylindrical inclusions. The interval of toughening defined by these two models covers the range of experimental data. The same conclusion is reached for the size of the switching zone.     

An electromechanical atomic-scale finite element method for simulating evolutions of ferroelectric nanodomains

In this paper, a novel atomic-level computational method of perovskite ferroelectrics is established by combining the shell model and atomic-scale finite element method (AFEM). Its applicability is carefully testified for both bulk and nanoscale ferroelectrics, by comparing the calculated structural parameters and polarizations with the molecular dynamics (MD) simulations, first-principles calculations and experiment results. A comparison of the CPU time demonstrates that the developed method has a computational speed about 10 times over that of shell model MD method and its advantage becomes more evident as the computational scale becomes larger. Moreover, two effective calculation skills of long-range Coulomb force are introduced which can further enhance the computational efficiency by about 10 times. Using the developed atomic-level method, we investigate the various patterns of nanoscale domain structures in BaTiO₃ and their evolutions under electrical loadings. A domain structure with coexistence of vortex and streamline polarization patterns is revealed. Furthermore, the simulations of domain evolutions not only reproduce well the two-step 90° domain switching process observed in experiments on single domain under an anti-parallel electric field, but also provide a full evolution diagram among different domain patterns under various electric fields. A quantitative analysis indicates that the direction-dependent coercive field of multi-domain structure can be well described by that of single domain based on a simple analytical model. This study on domain patterns and evolutions may help us understand the behaviors of ferroelectrics from the atomic level.     

Fully coupled, multi-axial, symmetric constitutive laws for polycrystalline ferroelectric ceramics

In this paper, a general form for multi-axial constitutive laws for ferroelectric ceramics is constructed. The foundation of the theory is an assumed form for the Helmholtz free energy of the material. Switching surfaces and associated flow rules are postulated in a modified stress and electric field space such that a positive dissipation rate during switching is guaranteed. The resulting tangent moduli relating increments of stress and electric field to increments of strain and electric displacement are symmetric since changes in the linear elastic, dielectric and piezoelectric properties of the material are included in the switching surface. Finally, parameters of the model are determined for two uncoupled cases, namely non-remanent straining ferroelectrics and purely ferroelastic switching, and then for the fully coupled ferroelectric case.     

A phenomenological constitutive model for ferroelastic and ferroelectric hysteresis effects in ferroelectric ceramics

This paper is concerned with a macroscopic constitutive law for domain switching effects, which occur in ferroelectric ceramics. The three-dimensional model is thermodynamically consistent and is determined by two scalar valued functions: the Helmholtz free energy and a switching surface. In a kinematic hardening process the movement of the center of the switching surface is controlled by internal variables. In common usage, the remanent polarization and the irreversible strain are employed as internal variables. The novel aspect of the present work is to introduce an irreversible electric field, which serves instead of the remanent polarization as internal variable. The irreversible electric field has only theoretical meaning, but it makes the formulation very suitable for a finite element implementation, where displacements and the electric potential are the nodal degrees of freedom. The paper presents an appropriate implementation into a hexahedral finite brick element. The uni-axial constitutive model successfully reproduces the ferroelastic and the ferroelectric hysteresis as well as the butterfly hysteresis for ferroelectric ceramics. Furthermore it accounts for the mechanical depolarization effect, which occurs if the polarized ferroelectric ceramic is subjected to a compression stress.     

An energy-consistent fracture model for ferroelectrics

The fracture behavior of ferroelectrics has been intensively studied in recent decades, though currently a widely accepted fracture mechanism is still lacking. In this work, enlightened by previous experimental observations that crack propagation in ferroelectrics is always accompa-nied by domain switching, we propose a micromechanical model in which both crack propagation and domain switch-ing are controlled by energy-based criteria. Both electric energy and mechanical energy can induce domain switching, while only mechanical energy can drive crack propagation. Furthermore, constrained domain switching is considered in this model, leading to the gradient domain switching zone near the crack tip. Analysis results show that stress-induced ferroelastic switching always has a toughening effect as the mechanical energy release rate serves as the driving force for both fracture and domain switching. In compari-son, the electric-field-induced switching may have either a toughening or detoughening effect. The proposed model can qualitatively agree with the existing experimental results.     

An I-integral method for crack-tip intensity factor variation due to domain switching in ferroelectric single-crystals

In the present study, an I-integral method is established for solving the crack-tip intensity factors of ferroelectric single-crystals. The I-integral combined with the phase field model is successfully used to investigate crack-tip intensity factor variations due to domain switching in ferroelectricity subjected to electromechanical loadings, which exhibits several advantages over previous methods based on small-scale switching. First, the shape of the switching zone around a crack tip is predicted by the time-dependent Ginzburg–Landau equation, which does not require preset energy-based switching criterion. Second, the I-integral can directly solve the crack-tip intensity factors and decouple the crack-tip intensity factors of different modes based on superimposing an auxiliary state onto an actual state. Third, the I-integral is area-independent, namely, the I-integral is not affected by the integral area size, the polarization distributions, or domain walls. This makes the I-integral applicable to large-scale domain switching. To this end, the electro-elastic field intensity factors of an impermeable crack in PbTiO₃ ferroelectric single crystals are evaluated under electrical, mechanical, and combined loading. The intensity factors obtained by the I-integral agree well with those obtained by the extrapolation technique. From numerical results, the following conclusions can be drawn with respect to fracture behavior of ferroelectrics under large-scale switching. Under displacement controlled mechanical loading, the stress intensity factors (SIFs) decrease monotonically due to the domain switching process, which means a crack tip shielding or effective switching-induced toughening occurs. If an external electric field is applied, the electric displacement intensity factor (EDIF) increases in all cases, i.e., the formed domain patterns enhance the electric crack tip loading. The energy release rate, expressed by the crack-tip J-integral, is reduced by the domain switching in all examples, which underlines the switching-induced-toughening effect. In contrast, under stress controlled load, the SIF evolves due to large-scale switching to a stable value, which is higher than the non-switching initial value, i.e., fracture is promoted in this case.     

Large electrostrictive actuation of barium titanate single crystals

An experimental investigation of the electromechanical behavior of single crystals of the ferroelectric perovskite barium titanate is presented. An experimental setup has been designed to investigate large strain actuation in single crystal ferroelectrics subjected to combined electrical and mechanical loading. Experiments have been performed on initially single domain crystals of barium titanate with (100) and (001) orientation at compressive stresses between 0 and . Global strain and polarization histories have been recorded. The electrostrictive response is shown to be highly dependent on the level of applied stress with a maximum strain of 0.9% measured at a compressive stress of about and electric field of about . This level of strain is about 5 times higher than in typical commercial piezoelectric PZT. Polarized light microscopy has been used to observe the evolution of the domain pattern simultaneously with the strain and polarization measurement. The observations reveal that the observed large strain behavior is the result of 90° domain switching.     

Effect of electric fields on fracture behavior of ferroelectric ceramics

The asymptotic problem of a semi-infinite crack perpendicular to the poling direction in a ferroelectric ceramic subjected to combined electric and mechanical loading is analyzed to investigate effect of electric fields on fracture behavior. Electromechanical coupling induced by the piezoelectric effect is neglected in this paper. The shape and size of the switching zone is shown to depend strongly on the relative magnitude between the applied electric field and stress field as well as on the ratio of the coercive electric field to the yield electric field. A universal relation between the crack tip stress intensity factor and the applied intensity factors of stress and electric field under small-scale conditions is obtained from the solution of the switching zone. It is found that the ratio of the coercive electric field to the yield electric field plays a significant role in determining the enhancement or reduction of the crack tip stress intensity factor. The fracture toughness variation of ferroelectrics under combined electric and mechanical loading is also discussed.     

Non-linear electromechanical response of 1–3 type piezocomposites

Domain switching in piezoelectric materials is caused by external loads such as electric field and stress that leads to non-linear behaviour. A study is carried out to compare the non-linear behaviour of 1–3 piezocomposites with different volume fractions and bulk piezoceramics. Experiments are conducted to measure the electrical displacement and strain on piezocomposites and bulk ceramics under high cyclic electrical loading and constant compressive prestress. A thermodynamically consistent uni-axial framework is developed to predict the nonlinear behaviour by combining the phenomenological and micromechanical techniques. Volume fractions of three distinct uni-axial variants (instead of six variants) are used as internal variables to describe the microscopic state of the material. In this model, the grain boundary effects are taken into account by introducing the back fields (electric field and stress) as non-linear kinematic hardening functions. An analytical model based on equivalent layered approach is used to calculate effective properties such as elastic, piezoelectric, and dielectric constants for different volume fractions of piezocomposites. The predicted effective properties are incorporated in the proposed uni-axial model and the dielectric hysteresis (electrical displacement versus electric field) as well as butterfly curves (strain versus electric field) are simulated. Comparison between the experiments and simulations show that this model can reproduce the characteristics of non-linear response. It is observed that the variation in fiber volume fraction and compressive stress has a significant influence on the response of the 1–3 piezocomposites.     

A ferroelectric and ferroelastic 3D hexahedral curvilinear finite element

An isoparametric 3D electromechanical hexahedral finite element integrating a 3D phenomenological ferroelectric and ferroelastic constitutive law for domain switching effects is proposed. The model presents two internal variables which are the ferroelectric polarization (related to the electric field) and the ferroelastic strain (related to the mechanical stress). An implicit integration technique of the constitutive equations based on the return-mapping algorithm is developed. The mechanical strain tensor and the electric field vector are expressed in a curvilinear coordinate system in order to handle the transverse isotropy behavior of ferroelectric ceramics. The hexahedral finite element is implemented into the commercial finite element code Abaqus® via the subroutine user element. Some linear (piezoelectric) and non linear (ferroelectric and ferroelastic) benchmarks are considered as validation tests.     

Thermodynamic driving force in ferroelectric crystals with a rank-2 laminated domain pattern, and a study of enhanced electrostriction

The thermodynamic driving force for domain growth in a rank-2 laminated ferroelectric crystal is derived in this article, and we used it, together with a homogenization theory, to study the issue of enhanced electrostrictive actuation recently reported by Burcsu et al. [2004. Large electrostrictive actuation of barium titanate single crystals. J. Mech. Phys. Solids 52, 823-846]. We derived this force from the reduction of Gibbs free energy with respect to the increase of domain concentration. It is shown that both the free energy and the thermodynamic force consist of three parts: the first arises from the difference in M₀ and M₁, the linear electromechanical compliances of the parent and product domains, respectively, at a given level of applied stress and electric field, the second stems from the electromechanical work associated with the change of spontaneous strain and spontaneous polarization during domain switch, and the third from the internal energy due to the distribution of polarizations strain and electric polarization inside the crystal. We prove that the first term is substantially lower than the second one, and the third one is identically zero with compatible domain pattern. The second one is, however, not exactly equal to the commonly written sum of the products of stress with strain, and electric field with polarization during switch, unless both domains have identical moduli in the common global axes. We also show that, with compatible domain patterns and when M₁=M₀, this driving force is identical to Eshelby's driving force acting on a flat interface due to the jump of energy-momentum tensor. Applications of the theory to a BaTiO₃ crystal subjected to a fixed axial compression and decreasing electric field from the [0 0 1] state reveal that the crystal undergoes a three-stage switching process: (i) the 0→90° switch to form a rank-1 laminate, (ii) the 0→180° switch inside the 0° domain to form a laminate I with a concurrent 90°→−90° switch inside the 90° domain to form laminate II, creating a rank-2-laminated domain pattern, and (iii) finally the 90→180° switch. It is the exchange of stability between the 0, 90°, and 180° domains under compression and electric field that is the origin of the enhanced actuation. We illustrate these intrinsic features by showing the evolution of these domains, and demonstrate how the reported large actuation strain can be attained with a rank-2 laminate.     

A principle of virtual work for combined electrostatic and mechanical loading of materials

The equations governing mechanics and electrostatics are formulated for a system in which the material deformations and electrostatic polarizations are arbitrary. A mechanical/electrostatic energy balance is formulated for this situation in terms of the electric enthalpy, in which the electric potential and the electric field are the independent variables, and charge and electric displacement, respectively, are the conjugate thermodynamic forces. This energy statement is presented in the form of a principle of virtual work (PVW), in which external virtual work is equated to internal virtual work. The resulting expression involves an internal material virtual work in which (1) material polarization is work-conjugate to increments of electric field, and (2) a combination of Cauchy stress, Maxwell stress and a product of polarization and electric field is work-conjugate to increments of strain. This PVW is valid for all material types, including those that are conservative and those that are dissipative. Such a virtual work expression is the basis for a rigorous formulation of a finite element method for problems involving the deformation and electrostatic charging of materials, including electroactive polymers and switchable ferroelectrics. The internal virtual work expression is used to develop the structure of conservative constitutive laws governing, for example, electroactive elastomers and piezoelectric materials, thereby determining the form of the Maxwell or electrostatic stress. It is shown that the Maxwell or electrostatic stress has a form fully constrained by the constitutive law and cannot be chosen independently of it. The structure of constitutive laws for dissipative materials, such as viscoelastic electroactive polymers and switchable ferroelectrics, is similarly determined, and it is shown that the Maxwell or electrostatic stress for these materials is identical to that for a material having the same conservative response when the dissipative processes in the material are shut off. The form of the internal virtual work is used further to develop the structure of dissipative constitutive laws controlled by rearrangement of material internal variables.     

Effect of transverse stress on switch-toughening of ferroelectrics

Testing data indicated that T stress significantly altersR-curves of ferroelectrics. The model of stress-induced polarization switching is adopted to evaluate the fracture toughness of ferroelectrics under K field and T stress. Analytical solution is obtained to estimate the steady state fracture resistance of mono-domain ferroelectrics. The result is generalized to multi-domain ferroelectric ceramics via Reuss approximation, which enables us to explain quantitatively R-curves under two testing configurations.