Phase Structure Evolution Research Articles

Sintering activation energy and low-temperature sinterable process of Boron-lanthanide glass/Li2Zn3Ti4O12 ceramic composite systems for LTCC technology

This work investigates the characteristics of wettability, activation energy for sintering, evolution of phase structure, and behavior during the low-temperature sintering process of B2O3-La2O3-MgO-TiO2 (BLMT) glass/Li2Zn3Ti4O12 ceramic composites for low temperature co-fried ceramics technology (LTCC). As the BLMT glass content increases from 0 to 10 wt%, the average sintering activation energy (Ea) of the composite decreases from 450 ± 8 to 356 ± 37 kJ/mol. There are two phases the primary Li2Zn3Ti4O12 phase and the secondary LaBO3 phase, the latter precipitates from the BLMT glass after sintering at 700 °C. This indicates that BLMT glass promotes the sintering of Li2Zn3Ti4O12 ceramic below 900 °C. In composites containing 20 wt% or more glass, sintering is governed by both liquid-phase sintering and reactive viscous sintering. As the BLMT glass content increases, the impact of viscous flow on the densification process becomes more pronounced. Simultaneously, when the glass content is greater than 20 wt%, the glass precipitates LaBO3, TiO2, and MgLaB5O10 phases between 700 and 750 °C. After 850 °C, the glass melts and reacts with Li2Zn3Ti4O12 phase to produce a new TiO2 phase. Accordingly, the activation energy (Ea) of sintering the composite material increases from 393 ± 17 to 667 ± 1 kJ/mol.

Phase structure evolution and electric properties of PSN-PIN-PT ferroelectric ceramics near MPB

Phase structure evolution and electric properties of PSN-PIN-PT ferroelectric ceramics near MPB

Evolution of the Active Phase of Pt/Sn-Al2O3 Catalysts During Acidic Impregnation and Their Use in Propane Dehydrogenation.

Alumina-supported PtSn is an industrialized catalyst for propane dehydrogenation. During the catalyst impregnation, the acidic impregnation solution with chloroplatinic acid as a precursor inevitably leads to the partial dissolution of the surface of amphoteric alumina support and finally varies catalytic performance. Herein, the structure evolution of the active phase, induced by an impregnated acidic solution, was studied with special care. According to the diffused double layer theory, we proposed a model of microgels during impregnation. The microgels formed in the solution with suitable acidity on the surface of the catalysts evolved into a structure of Al2O3-coated oxidized Pt by reprecipitation during drying and calcination. The covered Pt species could be exposed by Ar+ sputtering or migrate to the surface during reduction to serve as active sites for propane dehydrogenation. Noticeably, the surface Sn0 species was generated when the pH of the impregnated solution was around 0.56, which is solid proof for the unique active phase with the PtSn alloy present on SnOx species existing on the surface of the Sn-Al2O3 support. The synthesized catalyst exhibited high propylene selectivity (99.4%) and superior stability (kd = 0.002 h-1). This study provides new insight for the precise preparation of Pt/Sn-Al2O3 catalysts.

Phase structure evolution and coercivity mechanism of high-Co containing permanent magnets

Abstract The phase structure and magnetic properties of high-Co containing permanent magnets with high thermal stability have been systematically studied in this work. It is abnormal that the coercivity of annealed samples is slightly lower than that of sintered samples, while the coercivity was usually enhanced after annealing in conventional Nd-Fe-B samples. Further analysis showed that in addition to RE2(Fe,Co)14B main phase and RE-rich grain boundary phase, there are also new Co-rich magnetic phase located in the grain boundary. During annealing, the phase structure of high-Co containing magnets were readjusted, especially the increasing Co-rich magnetic phase and emerging RE-rich particles precipitated from the main phase. Eventually, the isolated RE-rich particles would act as the pinning center of the domain wall movement in demagnetization process. It was confirmed that the coercivity of annealed high-Co containing magnets was controlled by both nucleation and pinning. Pinning mechanism can partially compensate for the weakening of magnetic isolation due to increased Co-rich magnetic phase, which explained the moderate decrease in coercivity of annealed high-Co containing magnets. The discovery of new coercivity mechanism contributed to in-depth understanding of high-Co containing magnets.

Phase structure evolution and its effect on magnetic and mechanical properties of B-doped Sm2Co17-type magnets with high Fe content

Abstract The unique cellular microstructure of Fe-rich Sm2Co17-type permanent magnets is closely associated with the structure of the solid solution precursor. We investigate the phase structure, magnetic properties, and mechanical behavior of B-doped Sm2Co17-type magnets with high Fe content. The doped B atoms can diffuse into the interstitial vacancy, resulting in lattice expansion and promote the homogenization of the phase organizational structure during the solid solution treatment in theory. However, the resulting second phase plays a dominant role to result in more microtwin structures and highly ordered 2 : 17R phases in the solid solution stage, which inhibits the ordering transformation of 1 : 7H phase during aging and affects the generation of the cellular structure, and to result in a decrease in magnetic properties, yet the interface formed between it and the matrix phase hinders the movement of dislocations and enhances the mechanical properties. Hence, the precipitation of high flexural strain grain boundary phase induced by B element doping is also a new and effective way to improve the flexural strain of Sm2Co17-type magnets. Our study provides a new understanding of the phase structure evolution and its effect on the magnetic and mechanical properties of Sm2Co17-type magnets with high Fe content.

Large ferroelectric polarization and high dielectric constant in HfO2-based thin films via Hf0.5Zr0.5O2/ZrO2 nanobilayer engineering

HfO2-based ferroelectric films have been extensively explored and utilized in the field of non-volatile memory and electrical programmability. However, the trade-off between ferroelectric polarization and dielectric constant in HfO2 has limited the overall performance improvement of devices in practical applications. Herein, a novel approach is proposed for the Hf0.5Zr0.5O2/ZrO2 (HZO/ZrO2) nanobilayer engineering, which can effectively regulate the phase structure evolution of HfO2 films to construct a suitable morphotropic phase boundary (MPB). The findings highlight that the top ZrO2 layer can regularly promote the formation of either the ferroelectric o-phase or the antiferroelectric t-phase. An ideal MPB is successfully established in HZO/ZrO2 (6/9 nm) nanobilayer film by carefully optimizing the HZO/ZrO2 thickness ratio, which presents a high dielectric constant of 52.7 and a large 2Pr value of up to 72.3 μC/cm2 without any wake-up operation. Moreover, the HZO/ZrO2 nanobilayer thin films demonstrate faster polarization switching speed (1.09 μs) and better fatigue performance (109 cycles) compared to the conventional HZO solid solution films. The relationship between ferroelectric and dielectric properties can be harmoniously balanced through the designation. The results indicate that the HZO/ZrO2 nanobilayer engineering strategy is quite potential to pave the way for the development of next-generation memory technologies with superior performance and reliability.

Study on the micromorphologies and structural evolution in cold-mixed epoxy asphalt

Cold-mixed epoxy asphalt (CMEA) is a high performance paving material that can be constructed and cured at room temperature. It forms thermal and mechanical performances during curing process. In this study, the phase state and structural evolution characteristics of CMEA during curing were evaluated by curing rheological behavior, mechanical properties, and micromorphology. Viscosity tests and dynamic mechanical analyses (DMA) were applied to study the curing rheological behavior, and tensile tests were used to determine the mechanical properties. Moreover, fluorescence microscopy (FM), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were implemented to investigate the micromorphological and molecular structure evolution. The results showed that the curing reaction behavior of CMEA was closely related to temperature. The viscosity–time curves of CMEA satisfied the Arrhenius equation above 45 ℃ and followed a linear trend at low temperature. During the curing of CMEA, the toughness increased in three stages: the toughness growth stage, toughness stability stage and toughness decay stage. Furthermore, the presence of asphalt and its solvent weakened the curing reaction of epoxy asphalt. However, increasing the reaction temperature could increase the epoxy group conversion rate. When the curing reaction was complete, a considerable amount of asphalt solvent mixed with the asphalt and was uniformly distributed within the three-dimensional network structure of the epoxy resin. This mixture adversely affected the toughness of the cured CMEA.

An Emergent Quadruple Phase Ensemble in Doped Bismuth Ferrite Thin Films Through Site and Strain Engineering

AbstractIn ferroic materials, giant susceptibilities can be realized at artificially constructed phase boundaries through deterministic manipulation of the order parameter. Here, emergent ferroelectric structural phase evolution behavior is demonstrated through a synergistic combination of A‐site doping and strain engineering. Using chemical solution deposition derived (001)‐oriented Sm‐substituted bismuth ferrite (Bi1‐xSmxFeO3) films as a prototypical system, a morphotropic phase boundary comprising a coexistence of four distinct crystallographic phases is uncovered. These ferroelectric, polar, and nonpolar phases form a nanoscale mixture without the presence of crystallographically hard boundaries. The system thus possesses the ability to show both polarization rotation and extension, effectively releasing the polarization from its crystallographic constraint. Consequently, both robust ferroelectric properties and giant electromechanical responses are obtained. For instance, the optimized composition with x = 0.14 has a remnant polarization of 2Pr = 103 µC cm−2 and electromechanical response 175% that of undoped BFO. These findings showcase the tremendous potential of synthetic phase boundaries, particularly in the context of lead‐free functional multiferroics.

Multi-scale study on strength development, hydration behavior and phase evolution of recycled powder multi component cementitious materials

Recycled powder (RP) is considered to be a successful low-carbon alternative to ordinary Portland cement (OPC). However, the microstructure and synergistic mechanism of RP multi-component cementitious materials (RP-MCCM) after physical activation are still unclear. The purpose of this study is to study the strength development, hydration and phase structure evolution of MCCM by constructing RP-MCCM. When the content of RP after grinding activation is 30% (C70RG30), its 28 days compressive strength is increased by 7.6% on the basis of non-activation. Compared with the ternary system of RP and FA mixed with 15% (C70RG15F15), its 28 days compressive strength increased by 8.08%. After RP incorporation, the Al-OH is enhanced, the C-O and CO32- bonds peaks become narrower, and the S is evenly distributed, which is beneficial to the increase of the AFt and the CaCO3 content, but weakens the C-S-H and C-A-H phases. In the C70RG15F15 ternary system, CaCO3, Ca(OH)2, and SiO2 nanostructures are tightly bonded together without obvious faults, which improves the structural compactness and strength. RP grinding activation is mainly manifested in surface improvement, internal C-S-H activation and increase of active sites.

LiNbO3-induced phase structure evolution and improved piezoelectric properties in BiFeO3–BaTiO3 ceramics

Eco-friendly (0.73-x)Bi1.05FeO3-xLiNbO3-0.27BaTiO3 ternary ceramics were designed and prepared via a solid-state sintering route. Based on the X-ray diffraction results and Rietveld refinement, it was found that the structure of the ceramics transformed from rhombohedral to tetragonal symmetry with the addition of LiNbO3, and at x = 0.003, there existed a morphotropic phase boundary separating the two phases. Near the phase boundary, the largest values were achieved for the piezoelectric constant d33 and planar electromechanical coupling coefficient kp, being 180 pC/N and 0.27, respectively. Due to the addition of LiNbO3, the grain size tended to become smaller. Additionally, the ceramics were transitioned from normal to relaxor ferroelectrics with increasing x. Despite the fact that the LiNbO3 addition would result in a gradual decrease of Curie temperature, a relatively high Curie temperature (535 °C) was still maintained at x = 0.003, the phase boundary composition, which also showed good temperature stability of piezoelectric properties. These experimental results can provide a reference for the practical applications of high-temperature lead-free ceramics.

Structural Evolution of GaOx-Shell and Intermetallic Phases in Ga-Pt Supported Catalytically Active Liquid Metal Solutions.

We present a comprehensive scale-bridging characterization approach for supported catalytically active liquid metal solutions (SCALMS) which combines lab-based X-ray microscopy, nano X-ray computed tomography (nano-CT), and correlative analytical transmission electron microscopy. SCALMS catalysts consist of low-melting alloy particles and have demonstrated high catalytic activity, selectivity, and long-term stability in propane dehydrogenation (PDH). We established an identical-location nano-CT workflow which allows us to reveal site-specific changes of Ga-Pt SCALMS before and after PDH. These observations are complemented by analytical transmission electron microscopy investigations providing information on the structure, chemical composition, and phase distribution of individual SCALMS particles. Key findings of this combined microscopic approach include (i) structural evolution of the SCALMS particles' GaOx shell, (ii) Pt segregation toward the oxide shell leading to the formation of Ga-Pt intermetallic phases, and (iii) cracking of the oxide shell accompanied by the release of liquid Ga-Pt toward the porous support.

Effects of hydrogen doping on the phase structure and optoelectronic properties of p-type transparent SnO

Hydrogen (H) is a ubiquitous impurity, which can significantly affect the phase structure and the optoelectronic properties of oxide semiconductors. To date, a well-established understanding of the effects of H doping on the properties of p-type transparent SnO is still lacking. Here, we present a comparative study to reveal the role of H in SnO films by magnetron sputtering. We find that in as-grown undoped SnO films, in addition to the tetragonal SnO phase, secondary phases of SnO2 or Sn3O4 are present under certain growth temperatures. In contrast, a small fraction of metallic Sn phase is included in the as-grown H-doped SnO (SnO:H) films, attributed to the partial reduction of SnO by the H2 in the sputtering gas. Effects of post thermal annealing (PTA) on the properties of SnO films are also explored. Results strongly indicate that H doping or PTA facilitates the formation of Sn phase and Sn vacancies related defects, giving rise to the p-type conductivity observed in the undoped or H-doped SnO films. The present study provides a comprehensive understanding of the evolution of phase structures as well as defect properties of SnO films, which is crucial for their future studies and optoelectronic applications.

Tuning the Electro‐Optic Properties of BaTiO3 Epitaxial Thin Films via Buffer Layer‐Controlled Polarization Rotation Paths

AbstractBaTiO3 thin films emerge as a highly promising material platform for integrated photonics due to their outstanding electro‐optic properties and diverse functionalities. Despite extensive studies, there remains a notable gap in the understanding of the intricate relationship between the phase structure, domain switching kinetics and electro‐optic performance of these materials. By controlling the structural phase evolution, it is possible to gain deep insights into the physical mechanisms underlying the electro‐optic performance. Here, the phase constitution of BaTiO3 epitaxial thin films is successfully tuned by the insertion of a GdScO3 buffer layer. Continuous polarization rotation paths are observed from an out‐of‐plane tetragonal‐like phase, to an intermediate rhombohedral‐like phase, and finally an in‐plane tetragonal‐like phase, achieving an enhanced effective electro‐optic coefficient of 175 pm V−1 compared to unbuffered films. Furthermore, by in situ second harmonic generation microscopy and electro‐optic measurements, the domain switching behaviors in both statistical and spatially resolved manners are examined, resulting in a clear delineation of the key domain nucleation processes. The in‐depth explorations of these structural mechanisms and kinetics inform the rational design of strong electro‐optic thin films and help in the realization of high‐performance integrated photonic devices such as electro‐optic modulators and multilevel phase shifters.

Na1/2Bi1/2TiO3‐based ceramics with increased depolarization temperature and piezoelectric coefficient

AbstractSodium bismuth titanate‐based materials are expected to be an alternative candidate to lead‐based ceramic materials due to their excellent electrical properties. However, the low depolarization temperature (Td) limits their practical application. In this work, the phase structure evolution and microstructure of 0.9(0.4Na1/2Bi1/2TiO3–0.6BiFeO3)–0.1BaTiO3: xZnO (x = 0.01, 0.03, 0.05, and 0.07) (abbreviated as 100xZnO) composite ceramics are investigated, and their piezoelectric properties are improved by combination of constructing 0–3 type composites and quenching treatment technology. The addition of ZnO can increase both Td and d33 because ZnO can enhance the lattice distortion of rhombohedral phase and lead to the increase in ferroelectric order. Specifically, the optimum composition x = 0.03 obtains the d33 value of 106 pC/N (25°C), which retains 84% of the value at room temperature up to 240°C. And the quenching technology further enhances the ferroelectric order and increases Td, which is up to 280°C for x = 0.03.

Effect of electric field on the structure of SiCN pyrolyzed at 1600 °C

Application of electric field is known to influence the phase transformation and sintering conditions of ceramics. In this work, the effect of electric field on the phase structure evolution of SiCN pyrolyzed at 1600 °C was studied in comparison with conventional pressureless pyrolyzed SiCN. The structural information was characterized via X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and Raman spectroscopy. It was found that SiCN ceramic prepared via conventional pressureless pyrolysis was composed of SiC, Si3N4 and free carbon phases, while that produced via electric field-assisted pyrolysis consisted of Si3N4 and free carbon phases. No crystalline SiC was detected in SiCN ceramic pyrolyzed via the field-assisted method, indicating that the electric field affected the carbothermal reaction between Si3N4 and C phases and changed the formation mechanism of SiC. Moreover, the electric field promoted structural ordering rearrangement of the free carbon phase and increased the defect content therein.

Effect of Fe: Cu ratio on microstructure and mechanical properties of Fe-Co-Cu-based diamond tools

Co-based diamond tools are widely appreciated for their exceptional mechanical properties and good holding ability for diamonds. However, the reliance on cobalt (Co) poses challenges due to its high cost and scarcity as a strategic resource. A potential alternative is the Fe–Co–Cu alloy, emerging as a promising substitute for Co matrix alloys. In this work, hot-press sintering was utilized to create pure matrix and diamond tools utilizing Fe–Co–Cu pre-alloyed powders of varying compositions as raw materials without the use of any sintering additives. The investigation explores the influence of different Fe: Cu ratios on the mechanical properties of diamond tools produced from Fe–Co–Cu alloys, focusing on the diamond holding force, microstructure, and phase structure evolution. Results indicate that at a Co content of 15 wt% and Fe: Cu ratios ranging from 7.5:1 to 1:7.5, the Fe–Co–Cu alloy's phase structure primarily comprises α-Fe and a Cu-rich phase. Co predominantly exists in α-Fe as a solid solution. As the Fe: Cu ratio decreases, the alloy's phase structure gradually transitions from α-Fe to a Cu-rich phase, accompanied by a progressive decline in both bending strength and hardness, while the densities gradually increase. The matrix's holding force on the diamond exhibits an increasing and then diminishing trend, peaking at the Fe: Cu ratio of 6:1. The Fe–Co–Cu alloy sintered by hot-pressing has a nearly equiaxed grain structure with no obvious texture.

X‐ray imaging for structural evolution and phase transformation dynamics of battery electrodes

AbstractThe impending energy crisis entails sustainable battery technologies with improved energy density, reliability, safety and lifetime. Hence, it is essential to gain detailed insights into the surface reactions, ionic diffusion, structural and morphological evolution, and degradation mechanisms of battery electrodes. Recently, X‐ray techniques emerged as revolutionary tools to reveal an in‐depth understanding of the battery during operations. This review provides an overview of the use of in situ/operando X‐ray techniques to understand the different functionalities of electrode materials inside the battery. It will focus on the phase transformation, structural evolution and dynamic properties of the battery electrodes, and discuss the relationship between battery failure and electro‐chemo‐mechanical failure in the electrode. Finally, the limitations of these methods are also discussed with the prospects for effective use of these techniques in the development of advanced battery technologies.

The composition / field-induced octahedral tilt, domain switch and improved piezoelectric properties in BF-BT ceramics across phase transition

To clarify the structural mechanism of high piezoelectric activity of (1-x)BiFeO3-xBaTiO3 ((1-x)BF-xBT) solid solution, the evolution of phase structure and domain configuration and their effects on piezoelectric properties were studied...

Evolution of phase structure and fracture toughness induced by carbon nanotubes in thermoplastic-toughened epoxy nanocomposites

The nanomaterials-filled thermoset/thermoplastic ternary nanocomposites exhibit important potential to achieve both toughening and stiffening effect for thermosetting resin. However, the targeted growth in fracture toughness and the synergistic toughening mechanism of thermoplastic resin and nanomaterials has not been attained due to the complex immiscible ternary system. In this work, thermoplastic resin polyetherketone-cardo (PEK-C) and carbon nanotubes (CNTs) were synergistically incorporated in thermosetting epoxy (EP) resin. The structure-property correlation was explored via the investigation of mechanical performance and microstructure. The results showed that the change of fracture toughness was not linearly related to the PEK-C content, while closely related to the dualphase structure formed by EP and PEK-C. After introducing CNTs, the CNTs were selectively located in the continuous phase of EP, which increased the viscosity of the located region and hindered the coarsening and interconnecting of the dispersed phase of PEK-C, weakening the toughening effect of dualphase structure.

Retrospecting the relationship between interlamellar amorphous structure and intrinsic modulus of semicrystalline polymers via in-situ positron annihilation lifetime spectroscopy and in-situ X-ray scattering

The structure-property relationship of the interlamellar amorphous phase in semicrystalline polymers has been a fundamental yet controversial topic in polymer physics for several decades. The intricate hierarchical structure and limited availability of experimental techniques pose significant challenges in quantitatively characterizing the evolution of the amorphous structure and establishing its connection to the mechanical behavior. In this work, the unannealed and annealed isotactic polypropylene hard-elastic films composed of idealized series-arranged lamellar stacks are studied to simplify the mechanical coupling between the two phases. By utilizing the synchrotron-based in-situ small and wide-angle X-ray scattering (SAXS/WAXS) techniques, the apparent modulus and overall volumetric strain of the amorphous phase are estimated. Moreover, with our significant progress in the counting rate of positron annihilation lifetime spectroscopy (PALS), the minute-scale structure evolution of amorphous phase (free-volume pores) during the tensile process is now feasible to be captured. Combing in-situ X-ray scattering and in-situ PALS results, in the elastic regime, it is found that triaxial stress in the amorphous phase leads to the expansion of free-volume pores (about 23% volume increase for the annealed sample, 35% volumetric strain for the unannealed one) and density decrement within occupied volume by overcoming Van Der Waals force. Our quantitative analysis also reveals that the annealing process not only enhances the crystallinity and aspect ratio of lamellae but also weakens the intrinsic modulus and chain packing density of amorphous phase.