Field-induced Phase Transformation Research Articles

An integrated exploration from microstructure to mechanics in austenite to pearlite transformation of high carbon steel under high magnetic fields

The effects of a high magnetic field (12 T) on the microstructural evolution and mechanical properties of high carbon steel during isothermal pearlitic transformation at 720 °C were investigated. The application of a high magnetic field effectively promotes pearlitic transformation and leads to a reduction in the lamellar spacing and the geometrically necessary dislocation density (GND) as well as to a slight increase in the grain size of the pearlite, which leads to a decrease in hardness. This is because the magnetic field reduces the magnetic Gibbs energy of ferrite and cementite, resulting in an increase in the driving force of phase transformation, which shortens the pearlite maturation time and reduces the nucleation barriers of pearlite, thereby accelerating the growth rate of pearlite. In addition, the interfacial energy of ferrite/cementite was found to be increased by the magnetic field from the thermodynamic point of view, and the mechanism of action of the magnetic field -induced precipitation of cementite in the form of particles and short rods was elucidated. The present work will enhance the understanding of the mechanism of magnetic field-induced phase transformation in iron-based materials.

Effects of quenching on domain switching and electric field-induced phase transformations in Na0.5Bi0.5TiO3-NaNbO3 ceramics

Quenching from high temperatures has been identified as a useful means to enhance the piezoelectric properties and thermal stability of bismuth-based perovskite ferroelectrics. In the present work, it is demonstrated that quenching leads to improvement of depolarization temperature, ferroelectric and piezoelectric properties in Na0.5Bi0.5TiO3-NaNbO3 (NBT-0.1NN) ceramics. In-situ synchrotron x-ray diffraction measurements indicated an irreversible transformation from cubic to coexisting cubic and rhombohedral phases during the application of a high electric field, for both as-sintered and quenched ceramics. These results confirm the non-ergodic relaxor ferroelectric nature of the materials. DC poling induced a transformation to single-phase rhombohedral structure in both cases, with highly textured domain configurations. These well-oriented ferroelectric domain states were relatively stable under subsequent bipolar electric field cycling. For the pre-poled NBT-0.1NN ceramics, the quenched samples were found to exhibit the highest intrinsic (lattice strain) and extrinsic (domain switching) contributions to electrostrain, due to the increased rhombohedral distortion.

Light-driven dynamical tuning of the thermal conductivity in ferroelectrics.

Dynamical tuning of the thermal conductivity in crystals, κ, is critical for thermal management applications, as well as for energy harvesting and the development of novel phononic devices able to perform logic operations with phonons. Such a desired κ control can be achieved in functional materials that experience large structural and phonon variations as a result of field-induced phase transformations. However, this approach is only practical within reduced temperature intervals containing zero-bias phase transition points, since otherwise the necessary driving fields become excessively large and the materials' performances are detrimentally affected. Here, based on first-principles calculations, we propose an alternative strategy for dynamically tuning κ that is operative over broad temperature conditions and realizable in a wide class of materials. By shining light on the archetypal perovskite oxide KNbO3, we predict that ultrafast and reversible ferroelectric-to-paraelectric phase transitions are induced, yielding large and anisotropic κ variations (up to ≈30% at T = 300 K). These light-induced thermal transport shifts can take place at temperatures spanning several hundreds of kelvin and are essentially the result of anharmonic effects affecting the phonon lifetimes.

In-Situ Study of Temperature- and Magnetic-Field-Induced Incomplete Martensitic Transformation in Fe-Mn-Ga

Significant interest in the stoichiometric and off-stoichiometric Fe2MnGa alloys is based on their complex phase transition behavior and potential application. In this study, temperature- and magnetic-field-induced phase transformations in the Fe41.5Mn28Ga30.5 magnetic shape memory alloy were investigated by in situ synchrotron high-energy X-ray diffraction and in situ neutron diffraction techniques. It was found that incomplete phase transformation and phase coexistence behavior are always observed while applying and removing fields in Fe41.5Mn28Ga30.5. Typically, even at 4 K and under 0 T, or increasing the magnetic field to 11 T at 250 K, it can be directly detected that the martensite and austenite are in competition, making the phase transition incomplete. TEM observations at 300 K and 150 K indicate that the anti-phase boundaries and B2 precipitates may lead to field-induced incomplete phase transformation behavior collectively. The present study may enrich the understanding of field-induced martensitic transformation in the Fe-Mn-Ga magnetic shape memory alloys.

Variation of Electrical Resistivity During Magnetic Field-Induced Martensitic Transformation in Vanadium added NiMnSnB alloys

In this study, the structural and electrical properties of Ni49-xVxMn37Sn12B2 (x = 0, 1, 2, and 3) ferromagnetic shape memory alloys were investigated. According to XRD analyzes at room temperature, the x=0 sample was in the martensite phase, the x=1 and 2 samples were in the mixture phase, and the x=3 sample was in the austenite phase. The resistivity analyses depend on temperature showed that all samples exhibited martensitic transformation and the phase transformation temperature decreased with V doping. Magnetoresistance (MR) values were calculated using ρ-T curves performed under 0 T and 1 T magnetic fields. The observed negative MR is consistent with Kataoka's s-d model. As-Af interval was determined and M-H measurements were made at constant temperatures determined in this interval. The results were attributed to the magnetic field-induced phase transformation (MFIPT). In order to examine the effects of MFIPT on the electrical resistivity, the resistivity depend on magnetic field was measured using the same thermal process. The overlapping of the curves in the high magnetic field revealed that the resistivity decreased due to the MFIPT as well as the MR.

Structural distortion in ferroelectric HfO2 – The factor that determines electric field-induced phase transformation

The origin of the wake-up effect and the factor that determines the amount of the wake-up effect in ferroelectric (FE) HfO2 were systematically investigated. By observing both the waking-up and the phase transformation induced by electric field cycling on the same scale, we clarified that the wake-up effect in our FE-HfO2 system is dominated by the phase transformation induced by electric field cycling. Nevertheless, other mechanisms might be prominent in other FE-HfO2 systems. In our study, we found an anomalous structural distortion induced in both FE and none-FE HfO2 films. We hypothesized that structural distortion is the factor that governs the phase transformation to be induced by electric field cycling. We verified our hypothesis by conducting a series of experiments to clarify the factor that determines the amount of anomalous structural distortion, and that the amount of structural distortion would be the universal factor that determines the amount of the phase transformation. We found that the structural distortion is originating from the shrinkage in the volume of HfO2 films during crystallization due to the difference in the densities among the crystallized phases. Finally, we verified that the amount of structural distortion can be regarded as the universal factor that determines the amount of phase transformation to be induced by electric field cycling.

Stroboscopic in situ neutron diffraction approach to elucidate the kinetics of strain mechanisms in ferroelectric materials

The electromechanical properties of ferroelectrics are often strongly frequency-dependent, but the underlying structural kinetics are not well known or understood. Here, we use in situ stroboscopic neutron diffraction combined with a comprehensive structural refinement method to examine the frequency-dependent structural change in the commercial actuator material PIC 151 at realistic operating frequencies. A broad range of frequencies was measured and analyzed in detail. This work further underlines the crucial role of the field-induced phase transformation for explaining the kinetics in ferroelectric materials. Both the tetragonal majority phase and the rhombohedral minority phase contribute with different effects to the frequency dependence of the strain mechanisms. Even creep effects well beyond the probed frequencies can be explained with the observations.

Electric field-induced two-step phase transformation and its contribution to the electromechanical strain in lead-free relaxor-based ceramics

Sodium bismuth titanate-based solid solutions are important lead-free piezoelectrics with potential applications. Large electromechanical strain is of particular interest, which can be realized via the structural change in the relaxor states under an electric field. In this work, a polycrystalline ceramic 0.85Na1/2Bi1/2TiO3–0.15BaZr0.2Ti0.8O3, in which a long-range ordered ferroelectric phase and a relaxor state coexist, has been investigated to unveil the origin of its electromechanical strain using various experimental techniques. An ergodic-relaxor to nonergodic-relaxor transition is first observed under a relatively weak electric field, and a more stable long-range ferroelectric phase is induced under a larger electric field. This two-step phase transformation is accompanied with the process of local polarization freezing as well as ferroelectric domain growth. The domain formation during the reversible phase transition is found to be the main contribution to the macroscopic strain. Our investigation provides an in-depth understanding of the origin of reversible electromechanical strain in the NBT-based relaxor-ferroelectric system.

Electric field-induced irreversible phase transformations in Pb(Zr, Ti)O3-based piezoceramics

La-modified Pb(Zr,Ti)O3 (PLZT) (d33 ∼ 650 pC/N) and unmodified Pb(Zr1-x, Tix)O3 in the composition range (0.35 = x ≤ 0.51) were electrically poled through a novel powder poling technique. The mechanisms of large piezoelectric response in morphotropic phase boundary (MPB) and non-MPB-based compositions were discussed. Structural analysis suggests MPB-based compositions undergo irreversible structural phase transformation and lattice distortion after poling, and non-MPB undergo irreversible structural phase transformation. In the framework of theories, it has been argued that the MPB compositions satisfy the polarization rotation cum structural distortion phenomenon and non-MPB-based compositions follow the polarization rotation model.

Strain manipulation of magnetocaloric effect in a Ni39.5Co8.5Mn42Sn10 melt-spun ribbon

Heusler-type Ni-Mn-based alloys can demonstrate large magnetocaloric effect through magnetic field-induced phase transformation, but it usually occurs in a relatively narrow temperature region. In this work, we fabricate a bilayer composite with a Ni39.5Co8.5Mn42Sn10 ribbon adhered to a Ni50Ti50 substrate in order to manipulate the magnetocaloric properties by using the recovery strain of the predeformed substrate. The transformation temperatures of the ribbons can be effectively shifted to higher temperature region through the external strain transferred from the substrate, which contributes to the extended cooling temperature region. Moreover, the effective refrigeration capacity can also be improved by such strain manipulation.

Spatially-resolved relaxor to ferroelectric phase switching in 0.93Na1/2Bi1/2TiO3-0.07BaTiO3 ceramics

In situ, spatially-resolved synchrotron X-ray diffraction was utilized to investigate the electric field-induced heterogenous phase transformation of nonergodic relaxor 0.93Na1/2Bi1/2TiO3-0.07BaTiO3 ceramics. A Cu electrode was coated on one surface of a rectangular sample by aerosol deposition (AD), while a Pt layer was deposited on the opposite surface by sputter deposition. It is anticipated that a different stress state and/or domain morphology should occur on the AD deposited Cu electrode side due to the particle impact-consolidation deposition process. Under an electric field, different sample regions, i.e., AD, Middle, and Sputter sides, showed systematic changes in the relaxor to ferroelectric phase transition behavior. In particular, most <001> grains transformed at a sub-coercive field of 0.8 kV/mm, while the majority of the <111> grains only appeared to undergo transitions at a higher field (2.4 kV/mm). Also, the tetragonal phase became the dominant structure at higher field levels. Importantly, both <111> and <001> grains undergo phase switching at lower fields in the region close to the AD-processed layer. The study indicates that the AD process-induced stress can facilitate the electric field-induced relaxor to ferroelectric phase transition, i.e., the AD Cu side showed more significant lattice strain and domain texture than the sputter Pt side.

Structural and microstructural description of relaxor-ferroelectric transition in quenched Na1/2Bi1/2TiO3[sbnd]BaTiO3

Quenching lead-free Na1/2Bi1/2TiO3-based ceramics from sintering temperature is established to increase the depolarization temperature, Td and the lattice distortion. In situ synchrotron X-ray diffraction measurements were carried out on furnace cooled and quenched Na1/2Bi1/2TiO3 - BaTiO3 (NBT-BT) with 6 and 9 mol. % BT to discern the field-induced ferroelectric order. Phase fractions were determined from full pattern Rietveld refinements and utilized together with the change in unit cell volume to calculate volumetric strain resulting from phase transformations. NBT-6BT demonstrates a cubic symmetry in the furnace cooled state but quenching stabilizes the rhombohedral R3c phase and delays the formation of a field-induced, long range-ordered tetragonal phase, thereby shifting the onset of macroscopic strain to higher fields. A field-induced phase transition from a weakly distorted rhombohedral to tetragonal phase can be observed in furnace cooled NBT-9BT. However, this phase transition cannot be detected in quenched NBT-9BT, since the ferroelectric tetragonal P4mm phase is stabilized in the initial state. In contrast to the furnace cooled materials, both the quenched compositions exhibit overall negligible volumetric strain as a function of electric field. Furthermore, scanning electron micrographs of chemically etched, poled and unpoled samples reveal an increased lamellar domain contrast in the quenched materials. All these findings strengthen the hypothesis of a stabilized ferroelectric order resulting in the absence of a field-induced phase transformation in quenched NBT-BT.

Uncovering the symmetry of the induced ferroelectric phase transformation in polycrystalline barium titanate

Microstructural design is a widespread approach to tailor the properties of functional materials with the size effect being an effective constraint that modifies physical phenomena. In this work, we investigate the grain size effect on the properties and the electric field induced phase transformation behavior in barium titanate. A broad range of unimodal average grain size distribution between 0.4 and 15 μm was successfully sintered avoiding abnormal grain growth. Samples with a grain size close to the range of 1–2 μm, balancing microstructural strain, presence, and mobility of domain walls to allow the field induced crystal phase transformation, showed optimal electromechanical and dielectric properties. By means of in situ high energy x-ray diffraction and a high-resolution multianalyzer detector, we distinguish and quantify a tetragonal–orthorhombic phase transformation induced by an electric field, providing unambiguous proof of this induced phase transformation. These results contribute to the understanding of fundamental questions about the piezoelectric effect in barium titanate and consequently other similar systems.

Revealing intrinsic and extrinsic piezoelectric contributions in phase coexistence system of PbTiO3-BiScO3

PbTiO3-BiScO3 ceramics possess high piezoelectricity and high Curie temperature simultaneously, presenting a very promising candidate for high-temperature actuators and transducers. Figuring out the underlying piezoelectric mechanisms is of great importance for its application. Herein, we reveal the quantified intrinsic and extrinsic contributions to the high electrostrain of the morphotropic composition with phase coexistence by employing the advanced in situ electrical biasing high-energy synchrotron X-ray diffraction combined with the STRAP (strain, texture, and Rietveld analysis for piezoceramics from diffraction) methodology. An electric field-induced phase transformation is observed between the coexisting tetragonal and rhombohedral phases. It is found that the tetragonal phase contributes most of the domain switching strain, while the predominant lattice strain is from the rhombohedral phase. With phase fraction changes, the quantitative results demonstrate that the field-induced electrostrain is mainly contributed by the intrinsic lattice strain. In contrast, the high irreversible domain switching strain dominates the large remanent strain. It implies that transforming the large remanent strain into reversible strain would be a strategic direction to improve the piezoelectric response. The present results provide a further understanding of the high piezoelectricity and could help to advance the application of PbTiO3-BiScO3.

The role of intermediate S-polymorph towards high piezoelectricity in La-doped BiFeO3 epitaxial thin films

Mixed phases with stripe patterns are considered as a prerequisite for remarkable piezoelectric properties in epitaxial BiFeO3 (BFO) thin films. Among the mixed phases in BFO epitaxial thin films, the vital role in achieving high piezoelectric response is attributed to the intermediate S-polymorph that bridges the transition between rhombohedral and tetragonal phases. However, the correlation between the S-phase and the piezoelectric strain in mixed-phase BFO has not been understood well due to the lack of a probe technique that can investigate the structural and electromechanical variations simultaneously. Here, using the time-resolved X-ray microdiffraction technique, we investigate the electric field induced phase transformation dynamics of a mixed-phase epitaxial La-doped BFO (BLFO) thin film. The BLFO thin film exhibits phase transformations between monoclinic MC and tilted MC, S/tilted S (Stilt) phases under an applied electric field. Among the competing phases, we found that the S- or tilted S-phases exhibit the highest piezoelectric strain variation up to 0.7% at an electric field pulse of strength 1.3 MV/cm and width 5 μs. The present study correlates the high piezoelectric response in mixed-phase BLFO thin films with the presence of S/Stilt -phases, which offers a useful pathway into designing strain-engineered ultra-high piezoelectric BFO thin films.

Versatile Device for the Study of Coupling Properties in Multifunctional Materials. Example: Ni-(Co)-Mn-In Heusler Materials

We report on a versatile experimental setup for the study of the electro-magneto-elasto-thermal coupling for bulk materials having coupling properties. The setup enables measurement of stress and electrical resistivity in a 80-450 K temperature range under controlled uniaxial pressure in a magnetic field up to 8 T. The strong influence of uniaxial pressure and magnetic field on strain and transport properties is shown for Ni-Co-Mn-In Heusler single crystal material. Phase transformation, magnetostress and magnetic field-induced phase transformation, and elastocaloric effect can be estimated using this versatile setup. This device is very complementary to the studies focused on the modeling of thermo-electro-magneto-mechanical behavior for functional materials.

Optimizing the Piezoelectric Strain in ZrO2- and HfO2-Based Incipient Ferroelectrics for Thin-Film Applications: An Ab Initio Dopant Screening Study.

HfO2 and ZrO2 have increasingly drawn the interest of researchers as lead-free and silicon technology-compatible materials for ferroelectric, pyroelectric, and piezoelectric applications in thin films such as ferroelectric field-effect transistors, ferroelectric random access memories, nanoscale sensors, and energy harvesters. Owing to the environmental regulations against lead-containing electronic components, HfO2 and ZrO2 offer, along with AlN, (K,Na)NbO3- and (Bi0.5Na0.5)TiO3-based materials, an alternative to Pb(ZrxTi1-x)O3-based materials, which are the overwhelmingly used ceramics in industry. HfO2 and ZrO2 thin films may show field-induced phase transformation from the paraelectric tetragonal to the ferroelectric orthorhombic phase, leading to a change in crystal volume and thus strain. These field-induced strains have already been measured experimentally in pure and doped systems; however, no systematic optimization of the piezoelectric activity was performed, either experimentally or theoretically. In this screening study, we calculate the ultimate size of this effect for 58 dopants depending on the oxygen supply and the defect incorporation type: substitutional or interstitial. The largest piezoelectric strain values are achieved with Yb, Li, and Na in ZrO2 and exceed 40 pm V-1 or 0.8% maximal strain, which exceeds the best experimental findings by a factor of 2. Furthermore, we discovered that Mo, W, and Hg make the polar-orthorhombic phase in the ZrO2 bulk stable under certain circumstances, which would count in favor of these systems for the ceramic crystallization process. Our work guides the development of the performance of a promising material system by rational design of the essential mechanisms so as to apply it to unforeseen applications.

Analyses of Electric Field-Induced Phase Transformation by Luminescence Study in Eu3+-doped (Na, K)0.5Bi0.5TiO3 Ceramics.

Most analyses of phase transformations detected by rare earth ions are based on the luminescence spectrum, while in this study we focus on the luminescence decay processes. We prepared Eu3+-doped (Na, K)0.5Bi0.5TiO3 ceramics and studied their phase structure before and after poling by luminescence spectra, decay curves, and X-ray diffraction (XRD). Luminescence spectra indicated that electric fields induced a transformation in (Na0.8, K0.2)0.5Bi0.497Eu0.003TiO3 (NKBET20) ceramic from tetragonal to rhombohedral phase (R phase). Based on the decay kinetics and the Judd–Ofelt theory, decay curves were shown to identify the fraction of the transformation quantitatively. The data from decay curves suggest that with electric fields increasing from 0 to 50 kV/cm, the R phase fraction increases from about 23 to 89% and the tetragonal phase (T phase) fraction decreases from about 77 to 11%. XRD Rietveld analyses further confirmed the results. In this work, the analyses of the phase fractions are simplified by the monoexponential decay of the pure phases and the biexponential decay of the mixed phase, showing an easy and inexpensive way of studying the phase structures of the materials.

Research progress of the investigation of intrinsic and extrinsic origin of piezoelectric materials by X-ray diffraction

Ferroelectric/piezoelectric perovskites are an important class of functional material and have broad application prospects in commercial, industrial, military and other areas because of their high dielectric constants, high piezoelectric coefficients, and high electromechanical coupling coefficients. Their structures, applications, and physical mechanisms have been intensively studied in condensed matter physics and material science. The piezoelectric properties of ferroelectric materials mainly originate from the intrinsic field-induced lattice distortion and extrinsic domain inversion and domain wall motion. Therefore, the understanding of and the distinguishing between these mechanisms are important for ascertaining the origin of the high-piezoelectric properties and developing new functional materials. In this article, we review the research progress of technical means and methodology of analyzing the changes of crystal lattices and magnetic domains of materials under the action of an externally applied electric field through the high-energy synchrotron X-ray diffraction experiments. The techniques and analysis methods involved in the review cover the time-resolved X-ray diffraction, single/double-peak analysis, full-pattern refinement, center-of-mass calculation, and field-induced phase transformation analysis, which are used to study the intrinsic and extrinsic contributions to sample’s macroscopic properties. It is expected to provide the research methods, which fulfill the individual experimental requirements, and the technical support for the mechanism analysis of various piezoelectric materials through the introduction and review of various methods.

Effect of La doping on structure and dielectric properties of PLZST antiferroelectric ceramics

For the ABO3 perovskite structure in PZT-based antiferroelectrics, the cations with different radii at A or B position will affect the phase structure of the material. In this paper, the effect of La on the phase structure, dielectric property and field-induced phase transformation of PZT-based ceramics was studied by replacing Pb2+ with smaller ions La3+ with the formula of (Pb1−3x/200Lax/100)(Zr0.75Sn0.16Ti0.09)O3 ceramics (x = 0, 2, 4 and 6) and all samples were prepared through conventional solid-phase reaction sintering. It was found that the samples were ferroelectric rhombohedral phase with x = 0 and turned into an antiferroelectric tetragonal phase with increasing La content. Higher forward/backward switching fields and smaller hysteresis were achieved with increasing La content. The results also indicated proper content of La could effectively enhance the stability of antiferroelectric in this PZT-based antiferroelectric. Furthermore, the released energy density and energy storage efficiency were improved as the La content increased, reaching a maximum of 3.45 J/cm3 and efficiency of 91.3% when x = 0.06. It can be reasonably concluded that La doping can tailor the electric properties in PZT-based energy storage materials. For L4, as the field strength approaches the switching field, the Imax/E and the released charge also increase significantly.