Evolution Of Crystalline Phases Research Articles

Exploring equilibrium conditions in liquid metal dealloying of powders by in situ synchrotron X-ray diffraction

Liquid metal dealloying is a recently developed method to elaborate micro and nano-porous materials. It consists in the selective dissolution of an alloying element from a precursor alloy by immersing it in a liquid metal bath. In this paper, we monitor the dealloying reaction of Invar (Fe65Ni35) powders in liquid Mg using in situ synchrotron X-ray diffraction. Rietveld refinement of the diffraction spectra enables quantifying the evolution of different crystalline phases throughout the process, thereby gaining new insights into the kinetics, phase equilibria, and the role of intermetallics on the reaction. These results are systematically compared to post mortem observations of dealloyed samples, showing a good agreement between both techniques. In particular, we show that adjusting the thermodynamic conditions of the reaction (temperature, FeNi/Mg ratio) enables to tailor the microstructure of the dealloyed powders, by modifying the dealloyed fraction to achieve core–shell structures, and altering the composition of ligaments.

In Situ Mapping of Phase Evolutions in Rapidly Heated Zr-Based Bulk Metallic Glass with Oxygen Impurities.

Metallic glasses exhibit unique mechanical properties. For metallic glass composites (MGC), composed of dispersed nanocrystalline phases in an amorphous matrix, these properties can be enhanced or deteriorated depending on the volume fraction and size distribution of the crystalline phases. Understanding the evolution of crystalline phases during devitrification of bulk metallic glasses upon heating is key to realizing the production of these composites. Here, results are presented from a combination of in situ small- and wide-angle X-ray scattering (SAXS and WAXS) measurements during heating of Zr-based metallic glass samples at rates ranging from 102 to 104 Ks-1 with a time resolution of 4ms. By combining a detailed analysis of scattering experiments with numerical simulations, for the first time, it is shown how the amount of oxygen impurities in the samples influences the early stages of devitrification and changes the dominant nucleation mechanism from homogeneous to heterogeneous. During melting, the oxygen rich phase becomes the dominant crystalline phase whereas the main phases dissolve. The approach used in this study is well suited for investigation of rapid phase evolution during devitrification, which is important for the development of MGC.

Solution-driven processing of calcium sulfate: The mechanism of the reversible transformation of gypsum to bassanite in brines

Here, we show that calcium sulfate dihydrate (gypsum) can be directly, rapidly and reversibly converted to calcium sulfate hemihydrate (bassanite) in high salinity solutions (brines). The optimum conditions for the efficient production of bassanite in a short time (<5 min) involve the use of brines with c(NaCl) > 4 M and maintaining a temperature, T > 80 °C. When the solution containing bassanite crystals is cooled down to around room temperature, eventually gypsum is formed. When the temperature is raised again to T > 80 °C, bassanite is rapidly re-precipitated. This contrasts with the better-known behaviour of the bassanite phase in low-salt environments. In low-salinity aqueous solutions, bassanite is considered to be metastable with respect to gypsum and anhydrite, and therefore gypsum-to-bassanite conversion does not occur in pure water. Interestingly, the high-salinity transformation of gypsum-to-bassanite has been reported by many authors and used in practice for several decades, although its very occurrence actually contradicts numerical thermodynamic predictions regarding solubility of calcium sulfate phases. By following the evolution of crystalline phases with in situ and time-resolved X-ray diffraction/scattering and Raman spectroscopy, we demonstrated that the phase stability in brines at elevated temperatures was inaccurately represented in the thermodynamic databases. Most notably for c(NaCl) > 4 M, and T > 80 °C gypsum becomes readily more soluble than bassanite, which induces the direct precipitation of the latter from gypsum. The fact that these transformations are controlled by the solution provides extensive opportunities for precise manipulation of crystal formation. Our experiments confirmed that bassanite remained the sole crystalline phase for many hours before reverting into gypsum. This property is extremely advantageous for practical processing and efficient crystal extraction in industrial scenarios.

In-situ synchrotron X-ray diffraction of hydroxyapatite-zirconia composite during conventional and flash sintering

We conducted in-situ X-ray diffraction to study the crystalline phase evolution in hydroxyapatite-zirconia composites during both conventional and flash sintering processes. Additionally, we examined the thermal history and microstructure of the composite under these sintering conditions. Despite both sintering methods reaching similar average temperatures, they yielded distinct results in terms of crystalline phase composition and microstructure. In the flash sintered samples, we observed a complete transformation of hydroxyapatite into α- tricalcium phosphate and a complete tetragonal to cubic phase transition in zirconia. Conversely, the conventionally sintered samples remained practically stable. Notably, the flash sintered samples exhibited needle-like microstructures, which were absent in their conventionally sintered counterparts. This divergence suggests that the application of an electric field plays a role in generating athermal effects during the sintering of hydroxyapatite-zirconia composites.

Mechanical properties of porous Si3N4–SiC composites fabricated at 1200 °C

Porous Si3N4–SiC composites are potentially very attractive for various advanced applications such as aerospace and solar thermal power plants. However, processing of these porous composites is difficult and expensive due to the requirement of very high temperatures. In the present work, porous Si3N4–SiC composites were fabricated at only 1200 °C using phosphoric acid both as a pore former and binder. Porous composites with a constant SiC content were fabricated using various H3PO4 content and the morphology and mechanical properties of the porous composites were systematically investigated. The addition of SiC particles resulted in significant improvement of stiffness, compressive strength, and flexural strength over monolithic porous Si3N4, and porous composites fabricated using 40 vol% H3PO4 yielded the best properties of longitudinal elastic constant >50 GPa, flexural strength >80 MPa, and compressive strength >180 MPa. The achieved mechanical properties have been discussed in light of the analytical micromechanical models for Young's modulus and minimum solid area theory. Finally, the influence of processing temperature on the evolution of porosity and crystalline phases has been systematically studied and the dependence of porous composites' stiffness on these parameters has been investigated in detail.

Designing transition metal-based porous architectures for supercapacitor electrodes: a review.

Over the past decade, transition metal (TM)-based electrodes have shown intriguing physicochemical properties and widespread applications, especially in the field of supercapacitor energy storage owing to their diverse configurations, composition, porosity, and redox reactions. As one of the most intriguing research interests, the design of porous architectures in TM-based electrode materials has been demonstrated to facilitate ion/electron transport, modulate their electronic structure, diminish strain relaxation, and realize synergistic effects of multi-metals. Herein, the recent advances in porous TM-based electrodes are summarized, focusing on their typical synthesis strategies, including template-mediated assembly, thermal decomposition strategy, chemical deposition strategy, and host-guest hybridization strategy. Simultaneously, the corresponding conversion mechanism of each synthesis strategy are reviewed, and the merits and demerits of each strategy in building porous architectures are also discussed. Subsequently, TM-based electrode materials are categorized into TM oxides, TM hydroxides, TM sulfides, TM phosphides, TM carbides, and other TM species with a detailed review of their crystalline phase, electronic structure, and microstructure evolution to tune their electrochemical energy storage capacity. Finally, the challenges and prospects of porous TM-based electrode materials are presented to guide the future development in this field.

High strength Y2O3-stabilized zirconia continuous fibers up to 1500°C: Crystalline phase and microstructure evolution as well as grain growth kinetics

For zirconia continuous fibers, tensile strength is a very important performance parameter, which is affected by the crystal phase, its stability, grain size, processing temperatures, and so on. In this paper, the crystalline phases were adjusted through the Y2O3 contents and heat treatment temperatures in the range of 1000–1500°C. We found that interfacial segregation of Y3+ at high temperatures led to crystal phase instability, which was observed near the grain boundaries of the 13.8YSZ fibers. At high temperatures, the grain growth of different fibers occurred to different degrees. The regularities between the tensile strength, the strength retention and temperature, Y2O3 contents were discussed in detail. According to the highest tensile strength of a single fiber and Weibull modulus m, we found that the 5.4YSZ fibers were the most stable with the highest tensile strength and slow grain growth rate. The average strength was 1.6 GPa after heat-treating at 1500°C and the strength retention rate was about 54% under 1500°C for 60 min. Finally, the twistable 5.4YSZ continuous fibers with high strength were obtained by dry spinning technology. These results can provide reliable theoretical support and data sources for its high-temperature applications.

Multiscale Process Modeling of Semicrystalline PEEK for Tailored Thermomechanical Properties.

Polyether ether ketone (PEEK) is a semicrystalline thermoplastic that is used in high-performance composites for a wide range of applications. Because the crystalline phase has a higher mass density than that of the amorphous phase, the evolution of the crystalline phase during high-temperature annealing processing steps results in the formation of residual stresses and laminate deformations, which can adversely affect the composite laminate performance. Multiscale process modeling, utilizing molecular dynamics, micromechanics, and phenomenological PEEK crystal kinetic laws, is used to predict the evolution of volumetric shrinkage, elastic properties, and thermal properties, as a function of crystalline phase evolution, and thus annealing time, in the 306-328 °C temperature range. The results indicate that lower annealing temperatures in this range result in a faster evolution of thermomechanical properties and shrinkage toward the pure crystalline values. Therefore, from the perspective of composite processing, it may be more advantageous to choose the higher annealing rates in this range to slow the volumetric shrinkage and allow PEEK stress relaxation mechanisms more time to relax internal residual stresses in PEEK composite laminates and structures.

Study on the structural evolution and heat transfer performance of Cu supported on regular morphology CeO2 in CO catalytic combustion and chemical looping combustion

Chemical looping combustion (CLC) and catalytic combustion (CC), which are potential technologies to promote CO→CO2 efficient conversion and energy conservation for the steelmaking off-gas, are investigated in reaction activity, structure evolution catalysts/oxygen carriers (OCs) and energy recovery using Cu/CeO2 materials. Activity results suggest that the rod-shaped samples with well-defined (100) crystal faces exhibit higher activity than the sphere-shaped samples with (111) crystal faces, obtaining the optimized copper content of 3 wt%. IR spectra confirmed the proposed reaction pathway that the CO adsorbed on copper sites (Cu+–CO) at the Cu–Ce interface reacts with adjacent surface lattice oxygen. The gaseous oxygen continuously migrates to the external surface of materials, thus resulting in strongly exothermic CO self-sustained combustion during CC. Such a violent reaction does not cause obvious evolution of chemical composition, crystalline phase and structure. Since the active lattice oxygen is gradually consumed but not replenished by external gaseous O2 in time, CO combustion is not self-sustained during CLC. Therefore, the reduction cycle is no longer confined to the surface of the material but penetrates deep into its body, which accelerates Cu+ enrichment at the surface and leads to irreversible sintering and agglomeration of the material.

Composition-Driven Polarization Distribution in Poly(vinylidene fluoride)-Based Copolymer Blends for High Power Density Capacitors

High power density capacitors have been highly demanded in modern electronics and pulsed power systems. Yet the long-standing challenge that restricts achieving high power in capacitors lies in the inverse relationship between the breakdown strength and permittivity of dielectric materials. Here, we introduce poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) into the host poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) to produce PVDF-based copolymer blends, resulting in composition-driven 0-3 type microstructures, featuring nanospheres of P(VDF-TrFE) lamellar crystals dispersed homogeneously in a P(VDF-HFP) matrix together with crystalline phase evolution from the γ-phase to the α-phase. At the critical composition, the TrFE/HFP mole ratio is equal to 1, and the blend film achieves maximum energy storage performance with discharged energy density (Udis) ∼ 24.3 J/cm3 at 607 MV/m. Finite element analyses reveal the relationship between microstructures, compositions, and the distribution of local electric field and polarization, which provide an in-depth understanding of the microscopic mechanism of the enhancement in energy storage capability of the blend films. More importantly, in a practical charge/discharge circuit, the blend film could deliver an ultrahigh energy density of 20.4 J/cm3, i.e., 88.3% of the total stored energy to 20 kΩ load in 2.8 μs (τ0.9), resulting a high power density of 7.29 MW/cm3, outperforming the reported dielectric polymer-based composites and copolymer films in both energy and power densities. The study thus demonstrates a promising strategy to develop high-performance dielectrics for high power capacitors.

Sintering behavior and microstructure of (1-x)MgAl2O4-xMg2TiO4 spinel solid solutions prepared by isostructural heterogeneous nucleation

Magnesium aluminate (MgAl2O4) spinel has grasped considerable attention in high-temperature application by right of its excellent properties. However, the poor sintering behavior of MgAl2O4 is detrimental to its further development. In the present work, the application of isostructural heterogeneous nucleation method provides a novel idea for optimizing the sintering behavior of refractory materials. A series of (1-x)MgAl2O4-xMg2TiO4 (x = 0, 0.02, 0.04, 0.06, 0.08, and 0.1) spinel solid solutions with a present ration of components were fabricated from light calcined magnesia, reactive alumina and pre-preparation Mg2TiO4. The effect of Mg2TiO4 heterogeneous nucleating agent on the crystalline phase, densification, and microstructure evolution of MgAl2O4–Mg2TiO4 spinel solid solutions was studied. The XRD, XPS, and EDS results showed that Mg2TiO4 entered the lattice of MgAl2O4 to form a spinel solid solution, and the heterovalent substitution process was identified, where Ti4+ and Mg2+ ions of larger radius in the Mg2TiO4 replaced the Al3+ of smaller radius in the MgAl2O4. For the sample at x = 0.08, the spinel solid solutions exhibited the optimized densification with a relative density of 93.3%, an apparent porosity of 1.2%, and a compressive strength of 84.5 MPa. A significant increase in densification was related to the lattice distortion induced by ion size mismatch during the heterovalent substitution, thus accelerating the diffusion rate of Mg2+ and Al3+ ions in the spinelisation state. Moreover, the solid solubility content of Ti4+ in the MgAl2O4–Mg2TiO4 spinel solid solutions had a significant effect on the grain morphologies. The Mg2TiO4 heterogeneous nucleating agent significantly increased the spinelisation rate of MgAl2O4 spinel with negligible effect on densification.

Defect-Induced Self-Poling in a W18O49/PVDF Piezoelectric Energy Harvester.

W18O49 nanostructures, previously used for electrocatalysis, energy storage, electrochromic, and gas sensing applications, are incorporated in poly(vinylidene fluoride) (PVDF) in this work for mechanical energy-harvesting applications. X-ray diffraction spectroscopy (XRD), high-resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, differential scanning calorimetry (DSC), and the polarization-electric (P-E) field loop test prompts the addition of W18O49 nanorods in PVDF nucleates and stabilizes the piezoelectric polar γ-phase in the nanocomposite. Electrochemical experiments were employed for the first time to relate the event of the evolution of crystalline phases in PVDF to the transfer of electrons to the electrolyte from PVDF using the data from cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). High dielectric constant (ε') and low dielectric loss (ε″) values were obtained proportionately for different weight percentage additions of W18O49 nanorods in PVDF. DSC was employed to study the crystallization kinetics of γ-phase evolution. Piezoresponse force microscopy (PFM) was used to compare the piezoelectric responses from the PVDF nanocomposites. The W18O49/PVDF nanocomposite could generate a peak open circuit voltage of ∼6 V and a peak short circuit current of ∼700 nA. The W18O49/PVDF nanocomposite could light two commercial blue-light-emitting diodes (LEDs) with hand impulse imparting.

Insight into evolution of chemical structure and mineralogy to reveal the mechanism of temperature-dependent phosphorus release from hydrochars

Shrimp shell (SS) is sustainable biomass with abundant minerals and developable phosphorus (P) resource. Hydrothermal carbonization of SS can solve the shortage of P resources and the utilization of waste. However, few studies on the application of SS hydrochar as fertilizer have been conducted. Having an insight into the evolution of chemical structure and mineralogy could understand the mechanism of P release. In this study, Olsen method was employed to determine the available P (AP) release, and the temperature-dependent evolution of crystalline phase, carbon skeleton structures and surface functionalities were characterized by XRD, XPS, FTIR and TG. The results of AP release from SS hydrochar showed the following temperature (120−280 °C in 20 °C intervals) dependence: 120 °C derived hydrochars (2.30 mg/g) >feedstock (1.51 mg/g) > 160−280 °C derived hydrochars. In addition, AP dissolution kinetic data were well fitted to pseudo-second-order equation (R2 >0.999). Two-dimensional correlation spectroscopy revealed that phosphate crystallinity degree was negatively corresponding to release behavior. Meanwhile, calcite crystal growth and the transformation of P species influence the P bioavailability of SS hydrochar. Therefore, hydrochar with lower phosphate crystalline could benefit the P fertilizing efficiency.

Mechanical properties and machinability of lithium silicate glass-ceramics with varying MgO content

This study focused on the role of lithium metasilicate crystalline phase and microstructural evolution on altering the mechanical properties and machinability of two glass-ceramic system, (Li2O–K2O–Na2O–CaO–MgO–ZrO2–Al2O3–P2O5–SiO2), previously developed by our research group. Our previous study showed that increasing MgO content introduced phase separation and thus controlling the crystallization and microstructure of the glass-ceramics. For this study we chose the glass ceramic system with 1.5 and 4.5 mol% MgO. The glass-ceramics were prepared by melt cast method followed by heat treatment at 650 °C to induce partial crystallization. The crystalline phase in the glass-ceramics was identified by x-ray diffraction and the quantification of crystalline and amorphous phase content was done using Rietveld refinement. The hardness and elastic moduli were measured by nanoindentation. Vickers hardness and fracture toughness were determined by micro indentation. Nano scratch test was performed and scratch morphology was characterized using AFM and FEG-SEM. In order to compare the machinability of the prepared glass-ceramic samples, milling experiments were carried out using CNC milling machine, and machining characteristics were compared by analysing machining force, surface roughness and microstructure of the machined surface. Presence of higher amount of lithium metasilicate (LS) crystals in higher magnesia containing glass-ceramic (G2) resulted in lower average force (Fyrms) as compared to lower MgO containing glass-ceramic. However, due to a wide range of variation in crystal size (150 nm - 2 μm) in higher MgO containing glass-ceramic, the force fluctuation was more than lower MgO containing glass-ceramics.

Sintering behavior, structure and dielectric properties of CuO-ZnO-MgO-B2O3 glass-ceramics for ULTCC applications

High performance ultra-low temperature co-fired ceramic (ULTCC) materials were prepared from CuO- MgO- ZnO- Al2O3- B2O3- Li2O glass-ceramics. The sintering behaviors, crystalline phase evolution, microstructure and dielectric properties, as well as their compatibility with Ag and Al electrodes, were investigated. With the suitable substitution of MgO for ZnO, the dielectric properties of glass-ceramics were improved. It is mainly associated with the fine microstructure, highly crystallinity, and decrease in tetrahedral distortion in the crystal lattice. All the glasses completed the densification at 575–600 °C, and ZnB4O7 is the only crystalline phase precipitated from the glasses. Moreover, the glass-ceramic with 1 wt% MgO sintered at 575 °C for 5 h, exhibited low relative permittivity ~ 7.1 and low dielectric loss ~ 6.40 × 10−4. And the glass-ceramic with 4 wt% MgO sintered at 600 °C for 5 h, also displayed low relative permittivity ~ 7.1 and low dielectric loss ~ 5.77 × 10−4. Both two glasses have good sintering compatibility with silver and aluminum electrodes, which provided high potential for ULTCC application.

Influence of crystalline phase evolution of shells on microwave absorption performance of core-shell Fe3O4@TiO2 nanochains

Core-shell electromagnetic nanostructures with dielectric-magnetic dual-loss mechanisms are promising candidates for highly efficient microwave absorption attenuation. Herein, chain-like Fe3O4@TiO2 nanomaterials have been first prepared, and the crystalline phase composition of TiO2 shells has been regulated through controlling the sintering temperatures as 450 °C, 550 °C, and 650 °C. According to XRD patterns, the components of Fe3O4, TiO2, and FeTiO3 are ascertained, and the proportion of amorphous, anatase, and rutile phases is approximately determined. XPS results confirm the existence of Ti4+ and absence of oxygen vacancy in three samples. Investigation of microwave absorption properties indicates that S650 can possess the minimum reflection loss value of −21.29 dB (5.58 GHz) and the maximum effective absorption bandwidth of 5.09 GHz (11.83–16.92 GHz), superior than two other samples. Analyses of electromagnetic parameters reveal that dielectric loss plays a major role in the microwave absorption, heterogeneous interfaces are more conducive to strengthening dielectric loss than heterophase interfaces in the TiO2 shells, and increasing crystal phases is beneficial for improving impedance matching. This work first reports the influence of crystalline phase evolution on dielectric loss and impedance matching, which delivers a new approach to optimize the microwave absorption performance.

Virtual Development of Process Parameters for Bulk Metallic Glass Formation in Laser-Based Powder Bed Fusion.

The development of process parameters and scanning strategies for bulk metallic glass formation during additive manufacturing is time-consuming and costly. It typically involves trials with varying settings and destructive testing to evaluate the final phase structure of the experimental samples. In this study, we present an alternative method by modelling to predict the influence of the process parameters on the crystalline phase evolution during laser-based powder bed fusion (PBF-LB). The methodology is demonstrated by performing simulations, varying the following parameters: laser power, hatch spacing and hatch length. The results are compared in terms of crystalline volume fraction, crystal number density and mean crystal radius after scanning five consecutive layers. The result from the simulation shows an identical trend for the predicted crystalline phase fraction compared to the experimental estimates. It is shown that a low laser power, large hatch spacing and long hatch lengths are beneficial for glass formation during PBF-LB. The absolute values show an offset though, over-predicted by the numerical model. The method can indicate favourable parameter settings and be a complementary tool in the development of scanning strategies and processing parameters for additive manufacturing of bulk metallic glass.

Structure/property nonlinear variation induced by gamma ray irradiation of boroaluminosilicate transparent glass ceramic containing gahnite nanocrystallite

Transparent glass ceramics (TGC) used in radioactive condition should exhibit different characteristics from pure glass and pure ceramic. Boroaluminosilicate TGCs containing gahnite nanocrystallite were synthesized and irradiated with various dose of gamma ray and were comparatively characterized in structure and property. Phase and network microstructural analysis reveal nonlinear evolution of crystalline phase in addition to incidental improved network connectivity of the residual glass phase, which agree well with the derived parabolic relation with gamma dose based on thermal spike and crystallization kinetics models. Consequently, irradiation induced optical absorption of the TGC is lower than the precursor glass despite optical contribution of Ti4+ photoreduction. The variation of optical as well as mechanical properties upon irradiation reaches an extremum at certain dose followed by reversal to saturation at higher dose and is consistent with the nonlinear structural modification as a function of gamma ray dose.

Simulation of phase evolution in a Zr-based glass forming alloy during multiple laser remelting

Additive manufacturing by laser-based powder bed fusion is a promising technique for bulk metallic glass production. But, reheating by deposition of subsequent layers may cause local crystallisation of the alloy. To investigate the crystalline phase evolution during laser scanning of a Zr-based metallic glass-forming alloy, a simulation strategy based on the finite element method and the classical nucleation theory has been developed and compared with experimental results from multiple laser remelting of a single-track. Multiple laser remelting of a single-track demonstrates the crystallisation behaviour by the influence of thermal history in the reheated material. Scanning electron microscopy and transmission electron microscopy reveals the crystalline phase evolution in the heat affected zone after each laser scan. A trend can be observed where repeated remelting results in an increased crystalline volume fraction with larger crystals in the heat affected zone, both in simulation and experiment. A gradient of cluster number density and mean radius can also be predicted by the model, with good correlation to the experiments. Prediction of crystallisation, as presented in this work, can be a useful tool to aid the development of process parameters during additive manufacturing for bulk metallic glass formation.

Analyzing the Effects of Milling and Sintering Parameters on Crystalline Phase Evolution and Mechanical Properties of Al86Ni8Y6 and Al86Ni6Y4.5Co2La1.5 Amorphous Ribbons

Analyzing the Effects of Milling and Sintering Parameters on Crystalline Phase Evolution and Mechanical Properties of Al86Ni8Y6 and Al86Ni6Y4.5Co2La1.5 Amorphous Ribbons