Primary Crystals Research Articles

Impact of secondary ice in a frozen NaCl freeze-concentrated solution on the extent of methylene blue aggregation

Freezing and lyophilization have been utilized for decades to stabilize pharmaceutical and food products. Freezing a solution that contains dissolved salt and/or organic matter produces pure primary ice crystal grains separated by freeze-concentrated solutions (FCS). The microscopic size of the primary ice crystals depends on the cooling conditions and the concentration of the solutes. It is generally accepted that primary ice crystals size influences the rate of sublimation and also can impact physico-chemical behaviour of the species in the FCS. This article, however, presents a case where the secondary ice formed inside the FCS plays a critical role. We microscoped the structures of ice-cast FCS with an environmental scanning electron microscope and applied the aggregation-sensitive spectroscopic probe methylene blue to determine how the microstructure affects the molecular arrangement. We show that slow cooling at −50 °C produces large salt crystals with a small specific surface, resulting in a high degree of molecular aggregation within the FCS. In contrast, fast liquid nitrogen cooling yields an ultrafine structure of salt crystals having a large specific surface area and, therefore, inducing smaller aggregation. The study highlights a critical role of secondary ice in solute aggregation and introduces methylene blue as a molecular probe to investigate freezing behaviour of aqueous systems with crystalline solute.

Differences in hardness and microstructure of laser cladding M2 coatings

The M2 coatings on medium carbon steel were prepared using a laser cladding process, and the microstructure and microhardness of the coatings were studied. The results show that the microhardness of the coating shows an increasing trend from the coating top to the bonding interface. The microhardness is 694 HV1 at the surface of the coating, which reaches 836 HV1 in the bottom regions of the coating. The wear rate of the coating is 0.32 mm3/N·m, which shows lower wear rate and better wear resistance. The coating microstructure is also different, and the coating consists of overlapping and non overlapping regions. The microstructure of overlapping region is a dendritic solidified crystalline structure encapsulated on α - Fe phase primary crystals with a dispersed carbide. The microstructure of non overlapping zone is composed of columnar crystal zone, basket crystal zone, and dendritic zone from the bottom of the coating to the surface, respectively, with the carbides distributed along the grain boundaries in the form of a network. Near the coating interface, needle-like high-carbon martensite forms in the coating. The carbides in the coating are relatively coarse.

Self-assembled hybrid phosphate nanoflowers as oil-based lubricant additive: Interfacial adsorption and lubrication mechanism

In this work, a self-assembled hybrid phosphate nanoflower (HPN) containing Ba3(PO4)2 and NaBaPO4 was synthesized via BaCO3 primary crystals inducement. A ball-on-disc reciprocating tribometer was used to explore the tribological behavior of HPN as an additive for polyalphaolefin 8 (PAO8) on titanium alloy. Compared with the neat PAO8, after being lubricated with PAO8 containing HPN, the friction coefficient and wear rate decreased by 74.98% and 99.89%, respectively. The tribofilm at the friction interface was characterized and conformed by SEM, EDS, XPS, and cross-sectional TEM. Asan additive toPAO8, HPN can participate in the formation of tribofilm and exhibit superior friction-reducing and anti-wear properties for titanium alloy. It was demonstrated that due to the P-O-Ti bonds, HPN can easily adsorb and deposit at the friction interface to form a tribofilm against wear. Besides, the simulation experiments showedthat the repulsive force at the solid-liquid interface between HPN and oil molecules is the key to friction reduction and lubrication, and the comparative tribological experiments of different types of base oils were performed to verify the results of molecular dynamics.

Analysis of Fractures and Microstructures on Different Injection Speeds in High-Pressure Die-Casting Magnesium Alloy

In this study, to clarify the unknown physical properties of the Mg-Al-Th-RE alloy, the relationship between the injection conditions and the internal porosities, and the mechanical properties exerted by the solidification microstructure was investigated. The obtained cast samples were investigated using X-ray CT internal measurements, tensile tests, Vickers hardness tests, and solidification microstructure observations. The tensile strength and the elongation at the injection speed of 5.0 m/s were higher than at 2.0 m/s. The number of porosities affected the tensile strength and the elongation even at the same fracture position. In addition, it was confirmed that segregation affected the destruction smaller the porosity size and the greater the variability of porosity. As the injection speed increased, the amount of heat transferred between the molten metal and the wall surface also increased, resulting in quick freezing and solidification. The tensile strength increased at the injection speed of 5.0 m/s because the interface between the scattered primary crystals and eutectic systems was narrow. On the other hand, at the injection speed of 2.0 m/s, the tensile strength decreased because the molten metal was delayed in solidification and dendrite growth became remarkable.

Characteristics of Pore Morphology in Aluminum Alloy Foams Fabricated by Semi-Solid Route among Multiple Experimental Runs

A semi-solid route is expected to be a fabrication method that can fabricate aluminum alloy foams with a variety of mechanical properties, but the allowance fluctuation of the fabrication conditions of aluminum alloy foams with high reproducibility is not clear. The objective of this study was to reveal the allowance fluctuation between the setting temperature and the actual temperature of the melt to fabricate stable foams, having pores with small pores and high circularity, and the influence of the increasing volume fraction of the solid on the pore morphology. Al-Si alloy foams were fabricated five times by adding a blowing agent into a semi-solid slurry under the same setting fabrication conditions, such as the temperature and concentration of oxygen in the atmosphere. The results of small relative standard deviations of pore diameter and circularity indicated that the conducted fabrication process had high reproducibility, even if the volume fraction of the solid changed in a range of 5%. When the volume fraction of the solid exceeds the minimal fraction of primary crystals for prevention of drainage, the clogging effect works more efficiently because the ratio of clogged cell walls increases. Additionally, the preferred range of the volume fraction of the solid for the fabrication of stable foam was revealed to be around 15% to 35%.

Lithium in felsic magmas: a volcanological perspective

Volcanic eruptions are unpredictable phenomena that pose a challenge to crisis management, owing to the fact that contrasted eruptive styles (explosive versus effusive) exhibited at the surface depend on unobservable deep processes occurring in the reservoir and the volcanic conduit. Constricting the behaviour of magma during ascent, and the degassing in particular, allows for a clearer understanding of the relationships between petrological and volcano monitoring signals, and hence a better description of the volcanic hazard. To this aim, lithium (Li) has been used to track magmatic and post-eruptive processes, as a geospeedometer for processes operating on short time scales due to its high mobility in silicate melts and crystals. Yet, the accurate use of Li to assess syn- and post-eruptive processes still lack complete dataset. We propose a review of our current knowledge on Li behavior, with an emphasis on felsic (andesitic to rhyolitic) magmas whose explosive behavior during volcanic eruptions is still poorly understood. We present current knowledge regarding the Li concentration and isotopic compositions, intracrystalline diffusion, and crystal-melt-fluid partition coefficients discovered in felsic magmas and primary crystals. We describe difficulties in interpreting Li data to investigate the differentiation, degassing, ascent rate, volatile fluxing, and cooling of magmas. Finally, we suggest future directions for expanding our understanding of Li behavior.

Turbulence induced shear controllable synthesis of nano FePO4 irregularly-shaped particles in a counter impinging jet flow T-junction reactor assisted by ultrasound irradiation

FePO4 (FP) particles with a mesoporous structure amalgamated by nanoscale primary crystals were controllably prepared using an ultrasound-intensified turbulence T-junction microreactor (UTISR). The use of this type of reaction system can effectively enhance the micro-mixing and remarkably improve the mass transfer and chemical reaction rates. Consequently, the synergistic effects of the impinging streams and ultrasonic irradiation on the formation of mesoporous structure of FP nanoparticles have been systematically investigated through experimental validation and CFD simulation. The results revealed that the FP particles with a mesoporous structure can be well synthesised by precisely controlling the operation parameters by applying ultrasound irradiation with the input power in the range of 0–900 W and the impinging stream volumetric flow rate in the range of 17.15–257.22 mL·min−1. The findings obtained from the experimental observation and CFD modelling has clearly indicated that there exists a strong correlation between the particle size, morphology, and the local turbulence shear. The application of ultrasonic irradiation can effectively intensify the local turbulence shear in the reactor even at low Reynolds number based on the impinging stream diameter (Re < 2000), leading to an effective reduction in the particle size (from 273.48 to 56.1 nm) and an increase in the specific surface area (from 21.97 to 114.97 m2·g−1) of FP samples. The FPirregularly-shaped particles prepared by UTISR exhibited a mesoporous structure with a particle size of 56.10 nm, a specific surface area of 114.97 m2·g−1and a total pore adsorption volume of 0.570 cm3·g−1 when the volumetric flow rate and ultrasound power are 85.74 mL·min−1and 600 W, respectively.

Nanocrystallization of Cu46Zr33.5Hf13.5Al7 Metallic Glass

The recently discovered Cu46Zr33.5Hf13.5Al7 (at.%) bulk metallic glass (BMG) presents the highest glass-forming ability (GFA) among all known copper-based alloys, with a record-breaking critical casting thickness (or diameter) of 28.5 mm. At present, much remains to be explored about this new BMG that holds exceptional promise for engineering applications. Here, we report our study on the crystallization behavior of this new BMG, using isochronal and isothermal differential scanning calorimetry (DSC), X-ray diffraction (XRD), and transmission electron microscopy (TEM). With the calorimetric data, we determine the apparent activation energy of crystallization, the Avrami exponent, and the lower branch of the isothermal time–temperature–transformation (TTT) diagram. With XRD and TEM, we identify primary and secondary crystal phases utilizing samples crystallized to different degrees within the calorimeter. We also estimate the number density, nucleation rate, and growth rate of the primary crystals through TEM image analysis. Our results reveal that the crystallization in this BMG has a high activation energy of ≈360 kJ/mole and that the primary crystallization of this BMG produces a high number density (≈1021 m−3 at 475 °C) of slowly growing (growth rate &lt; 0.5 nm/s at 475 °C) Cu10(Zr,Hf)7 nanocrystals dispersed in the glassy matrix, while the second crystallization event further produces a new phase, Cu(Zr,Hf)2. The results help us to understand the GFA and thermal stability of this new BMG and provide important guidance for its future engineering applications, including its usage as a precursor to glass–crystal composite or bulk nanocrystalline structures.

Revealing the Grain-Boundary-Cracking Induced Capacity Decay of a High-Voltage LiCoO2 at 4.6 V.

During a practical battery manufacture process, the LiCoO2 (LCO) electrodes are usually rolled with high pressure to achieve better performance, including reducing electrode polarization, increasing compact density, enhancing mechanical toughness, etc. In this work, a high-voltage LCO (HV-LCO) is achieved via modulating a commercialized LCO with an Al/F enriched and spinel reinforced surface structure. We reveal that the rolling can more or less introduce risk of grain-boundary-cracking (GBC) inside the HV-LCO and accelerate the capacity decay when cycled at 3-4.6 V vs Li/Li+. In particular, the concept of interface structure is proposed to explain the reason for the deteriorated cycle stability. As the GBC is generated, the interface structure of HV-LCO alters from a surface spinel phase to a hybrid of surface spinel plus boundary layer phases, leading to the exposure of some the nonprotective layer phase against the electrolyte. This alternation causes serious bulk structure damage upon cycles, including expanding GBC among the primary crystals, forming intragranular cracks and inactive spinel phases inside the bulk regions, etc., eventually leading to the deteriorated cycle stability. Above all, we realize that it is far from enough to achieve a eligible high-voltage LCO via only applying surface modification. This work provides a new insight for developing more advanced LCO cathodes.

Effect of TiO&lt;sub&gt;2&lt;/sub&gt; Addition and Cooling Rate on Crystallization Behavior of Separated Slag Containing Low-grade RE

With the continued exploitation and utilization of high-grade rare earth ores, it is increasingly important to extract rare earths from separated slag containing low-grade rare earth. The X-ray powder diffraction, scanning electron microscopy, electron probe micro-analyzer and confocal laser scanning microscopy were used to explore the influence of TiO2 and cooling rate on the crystallization of CaO-SiO2-TiO2-10 wt% P2O5-8 wt% Nb2O5-5 wt% CeO2-5 wt% CaF2 slag system. In this study, the britholite was precipitated selectively as the Ce-enriched phase. When TiO2 was added at less than 12 wt%, the britholite was promoted to crystallize meanwhile the Ca2Nb2O7 was suppressed. However, CaTiSiO5 inhibited the growth of britholite when the TiO2 content exceeded 15 wt%. The non-isothermal crystallization kinetics had also been investigated for the TiO2 content and cooling rate varied from 0-18 wt% and 10-40°C/min, respectively. The continuous cooling transformation diagram and the relative crystallinity of the primary crystals were also constructed. Based on the observation and measurement of crystallization process, the modified Avrami model was applied to determine the crystallization mode of britholite with 9 wt% TiO2 addition. It was constant nucleation rate and one-dimensional growth with diffusion controlled. Considering the nucleation and growth of crystals, 20–30°C/min was preferred to be the reasonable parameter during cooling stage.

High-temperature interactions of liquid magnesium with a pure copper substrate

For the first time, experimental results of the high-temperature interaction of liquid magnesium with pure copper are presented. The investigation was performed using the sessile drop method and capillary purification procedure allowing both non-contact heating of the Mg/Cu couple and in situ cleaning of the Mg drop from a native oxide film. The test was done under isothermal conditions at 710 °C in a protective atmosphere, which was a mixture of Ar + 5 wt% H2.The images of the Mg/Cu couple collected during the high-temperature measurements were used to determine the time-dependent values of the contact angle (θ) formed between the liquid magnesium drop and the copper substrate.The solidified couple was subjected to detailed microstructural observations by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), both coupled with energy-dispersive X-ray spectroscopy (EDS).Under the applied measurement conditions, immediately after contact with the Cu substrate, the liquid Mg drop showed a very good wetting (θ0 ∼ 22°), followed by rapid spreading over the substrate, forming a final contact angle θf ∼ 11°. However, SEM/EDS analysis revealed that θf is an apparent angle due to the deep crater (∼200 μm) formed in the substrate under the Mg drop by the dissolution of Cu in liquid Mg.The comparative SEM/TEM/EDS analysis suggests that good wetting and rapid spreading in the Mg/Cu couple are dominated by the reactive wetting mechanism due to the dissolution of the Cu substrate in the liquid Mg drop and its saturation with a high amount of dissolved Cu. Consequently, the microstructure of the solidified drop was composed of large Cu-rich primary MgCu2 crystals surrounded with a two-phase eutectic mixture (MgCu2 + Mg2Cu) formed at the final stage of cooling. In addition, the MgCu2 phase was also nucleated and grown at the Mg/Cu interface to form a continuous layer.

Composition design of high Bs Fe-based amorphous powders with good sphericity

Fe83SixByC(17-x-y) has good glass forming ability (GFA), and high saturation magnetic induction (Bs), and spherical amorphous powder can be prepared using a gas–water coupling atomization (GWC) device. Herein, the effects of metalloid elements (B, C, Si and P) on the thermal parameters and magnetic properties of the Fe83SixByC(17-x-y) powder are discussed. The research conclusion shows that the Fe83Si2.5B11.5C3 amorphous powder exhibits the best comprehensive performance. Through the Lorentz microscope pattern of Fe83Si2.5B11.5C3 amorphous powder, magnetic domains walls are observed to gather and interlace in the outer region of the particle. The Fe83Si2.5B11.5C3 amorphous powder exhibits a high initial crystallization temperature (Tx1), followed by a ΔTx of 27 ℃, and then crystallization completion at 561.1 ℃. Some clusters or primary crystals are produced in the amorphous matrix after annealing at 520 ℃ (below Tx1 534 ℃) for 1 h. A further increase in the annealing temperature to 570 ℃ (beyond Te1 561.1 ℃) causes the precipitation of a large amount of crystalline phase α- Fe (Si) and hard magnetic phase Fe2B, thereby resulting in the rapid deterioration of the magnetic properties of the amorphous powder.

Структура, фазовий склад і властивості сплаву АК12М2МгН з підвищенням вмістом заліза, обробленого в рідкому стані електричним струмом

The possibility of replacing the piston eutectic alloy of the Al-Si-Cu system AK12M2MgN, which was produced at OJSC "Zaporizhsky Aluminum Combine" from primary aluminum, with AK12M2MgNZH with an increased iron content, which will allow expanding the raw material base of production due to the use of scrap and waste. It is proposed to solve this problem by introducing into the technological process of processing the melt with a unipolar pulsed electric current during pouring according to specially developed modes. To investigate this possibility, experiments were conducted on the effect of electric current on the microstructure, phase composition of AK12M2MgN and AK12M2MgNZH alloys and their mechanical properties at temperatures of 20 oC and 300 oC. The melt was treated with an electric current in the following modes: electric current density (j) 100 - 400 A/cm2, pulse frequency (ν) 50 - 2000 Hz. The phase composition of alloys is considered. It is shown that the main iron-containing phase of the AK12M2MgN alloy is (Fe,Mn)3Si2AI15 (α) in the form of branched eutectic crystals. The acicular β-FeSiAI5 phase is practically absent. Unlike AK12M2MgN, the composition of AK12M2MgNZH alloy includes β-FeSiAl5 intermetallic and primary coarse crystals of (Fe,Mn)3Si2AI15 phase. After treatment of alloys in the liquid state with pulsed electric current in different modes, their microstructure and phase composition change significantly. The degree of differentiation of eutectic components increases. In particular, the linear size of eutectic silicon crystals, depending on the density and frequency of the electric current, decreases by 2-3 times. Primary crystals of the intermetallic (Fe,Mn)3Si2Al15 are formed in the AK12M2MgN alloy, which in cross-section have the appearance of compact, close to globular crystals. X-ray spectral studies have shown that despite the same crystallographic structure, eutectic and primary crystals of the (Fe,Mn)3Si2Al15 phase differ in the higher concentration of iron, manganese, copper and nickel in the latter. In the composition of the AK12M2MgNZH alloy, there is practically no acicular intermetallic β-FeSiAl5, the formation of which is one of the main reasons for the decrease in mechanical properties. Similar to the AK12M2MgN alloy, compact crystals of the primary phase (Fe,Mn)3Si2Al15 and a significant amount of the π-FeMg3Si6Al8 phase appear. Such structural changes ensured an increase in the mechanical properties at 20 and 300 oC of both the AK12M2MgN alloy and AK12M2MgNZH. The highest properties of both alloys are achieved at j = 100 A/cm2; ν = 1000 ‒ 2000 Hz. The characteristics of mechanical properties increase from 25 % to 40 %. The structural and phase changes caused by the processing of the AK12M2MgNZH melt with an electric current according to experimentally established modes provide it with mechanical properties at the level of the AK12M2MgN alloy with several higher heat resistance indicators. In addition, treatment of the melt with electric current allows to reduce the consumption of sodium-potassium fluxes by 15-50%; time of heat treatment for T1 from 10-12 hours. up to 2-3 hours.

Quasi-critical condition to balance the scaling and membrane lifespan tradeoff in hypersaline water concentration

Mineral scaling is an inconvenient obstacle for membrane distillation in hypersaline wastewater concentration applications, compromising membrane lifespan to maintain high water recovery. Although various measures are devoted to alleviating mineral scaling, the uncertainty and complexity of scale characteristics make it difficult to accurately identify and effectively prevent. Herein, we systematically elucidate a practically applicable principle to balance the trade-off between mineral scaling and membrane lifespan. Through experimental demonstration and mechanism analysis, we find a consistent concentration phenomenon of hypersaline concentration in different situations. Based on the characteristics of the binding force between the primary scale crystal and the membrane, the quasi-critical concentration condition is sought to prevent the accumulation and intrusion of mineral scale. The quasi-critical condition achieves the maximum water flux on the premise of guaranteeing the membrane tolerance, and the membrane performance can be restored by undamaged physical cleaning. This report opens up an informative horizon for circumventing the inexplicable scaling explorations and develops a universal evaluation strategy to provide technical support for membrane desalination.

INVESTIGATION OF THE STRUCTURE OF ALSI25CU4CR AND ALSI25CU5CR ALLOYS

The hypereutectic aluminium-silicon alloys AlSi25Cu4Cr and AlSi25Cu5Cr are heat treated T5, T6 and T7. The quenching of the alloys was carried out under the same conditions. Artificial aging at T5 was carried out at a temperature of 180º C for 2, 4 and 6h, and at T6 at 180º C for 8, 10, 12 and 14h. The artificial aging of the studied compositions at T7 was carried out at a temperature of 370º C for 20, 40 and 60 min. The influence of heat treatment on the size, shape and distribution of primary and eutectic silicon crystals in the alloy structure was investigated. It was established that the proposed heat treatment regimes do not lead to a significant change in the shape and size of the primary silicon crystals, but contribute to their uniform distribution in the structure of the studied alloys. Rounding of the silicon crystals in the composition of the eutectic of the investigated alloys was observed.

Effects of Multiple Reflow on the Formation of Primary Crystals in Sn-3.5Ag and Solder Joint Strength: Experimental and Finite Element Analysis.

The growth and formation of primary intermetallics formed in Sn-3.5Ag soldered on copper organic solderability preservative (Cu-OSP) and electroless nickel immersion gold (ENIG) surface finish after multiple reflows were systematically investigated. Real-time synchrotron imaging was used to investigate the microstructure, focusing on the in situ growth behavior of primary intermetallics during the solid-liquid-solid interactions. The high-speed shear test was conducted to observe the correlation of microstructure formation to the solder joint strength. Subsequently, the experimental results were correlated with the numerical Finite Element (FE) modeling using ANSYS software to investigate the effects of primary intermetallics on the reliability of solder joints. In the Sn-3.5Ag/Cu-OSP solder joint, the well-known Cu6Sn5 interfacial intermetallic compounds (IMCs) layer was observed in each reflow, where the thickness of the IMC layer increases with an increasing number of reflows due to the Cu diffusion from the substrate. Meanwhile, for the Sn-3.5Ag/ENIG solder joints, the Ni3Sn4 interfacial IMC layer was formed first, followed by the (Cu, Ni)6Sn5 IMC layer, where the formation was detected after five cycles of reflow. The results obtained from real-time imaging prove that the Ni layer from the ENIG surface finish possessed an effective barrier to suppress and control the Cu dissolution from the substrates, as there is no sizeable primary phase observed up to four cycles of reflow. Thus, this resulted in a thinner IMC layer and smaller primary intermetallics, producing a stronger solder joint for Sn-3.5Ag/ENIG even after the repeated reflow process relative to the Sn-3.5Ag/Cu-OSP joints.

Features of the formation of crystalline hydrosulfoaluminates during hydration of stoichiometric mixtures of calcium aluminates with calcium sulfate

Calcium aluminates as mineral binders allow to produce cements and concretes with high early strength, low porosity, increased heat resistance, frost resistance and corrosion resistance compared to materials based on Portland cement. An important structure-forming process in aluminate cements is formation of hydrosulfoaluminate phases (ettringite, monosulfoaluminate). Finding out the parameters that allow to control this process is of exceptional importance for construction practice. Hydration of various calcium aluminates C3A, C12A7, CA, and CA2 in the presence of stoichiometric amounts of various forms of calcium sulfate (CaSO4⋅2H2O, α-CaSO4⋅0.5H2O, anhydrite) was studied in order to determine the comparative ratio and the peculiarities of nucleation and growth of the hydrosulfoaluminate phase crystals. It was found that the highest yield of ettringite (∼100 wt% by 28 days) is achieved during hydration hardening of the composition C3A + 3CS¯H2, the yield is reduced in the series C12A7–CA–CA2. Monosulfoaluminate is not formed as the predominant product, its yield reaches 25 wt% during hydration of low-base aluminates. Ettringite crystals can form as a highly dispersed mass (from C3A) or prismatic (fibrous) crystals (from other aluminates). It was clearly shown for the first time that the origin and growth of ettringite crystals occurs in the matrix of aluminum hydroxide gel formed during hydration of calcium aluminates. Varying the pH of aluminate-sulfate mixtures changes the morphology, size and number of primary ettringite crystals. Lamellar hexagonal crystals of monosulfoaluminate are formed from hydroaluminates of type C4AH13-19 at low availability of calcium sulfate. The explanation of the experimental data was carried out using thermodynamic calculations. The results obtained can be used in practice to control the content, ratio and morphology of hydrosulfoaluminate phases in cement stone.

Refractive index measurement of hydrogen isotopologue mixture and applicability for homogeneity of hydrogen solid at cryogenic temperature in fusion fuel system

Deuterium (D)-Tritium (T) nuclear fusion reaction has potential as an energy source in the future. In both magnetic confinement and inertial confinement fusion reactors, solid D–T will generally be supplied as fusion fuel. The efficiency of the nuclear fusion reaction depends on the quality of solid D–T fuel, which is related to the composition, homogeneity, helium-3 (3He) content, and so on. However, there is no technique for in-situ examination of solid D–T fuel. In this study, we consider a simple and precise method for the characterization of solid hydrogen isotopologues at cryogenic temperature using refractive index measurement, and evaluate the distribution of hydrogen isotopologue composition and homogeneity. To evaluate without the effect of tritium decay, the homogeneity of the hydrogen (H2)-deuterium (D2) mixture is measured at first. By the in-situ refractive index measurement at cryogenic temperature, the homogeneity of solid H2–D2 mixture is roughly quantified. The phase diagram of the H2–D2 mixture shows a solid solution type. D2-rich crystal first appears from the liquid phase as a primary crystal. The composition of D2 in liquid phase ias homogeneous, whereas it reduces by obeying the liquidus line in the phase diagram with the crystallization. On the other hand, the composition of the H2–D2 mixture in solid phase is inhomogeneous because the mobility of H2 and D2 in solid phase was too slow to be homogeneous and solid. The compositions of H2–D2 mixture in liquid and solid phases could be evaluated by the in-situ refractive index measurement in time. Consequently, the refractive index measurement shows great potential as an inspection method of solid D–T fuel in fusion reactors.

Effect of chemical defects on electrostriction-enhanced piezoelectric property of poly(vinylidene fluoride) via high-power ultrasonication

Among all ferroelectric polymers, poly(vinylidene fluoride) (PVDF)-based polymers exhibit the best piezoelectric properties and thus are promising for sensors, actuators, and energy harvesters in flexible/wearable electronics and soft robotics. Despite decades of research effort, the structure-property relationship is still unclear for ferroelectric polymers, and their piezoelectric performance is often limited to ∼30 pC/N. In this study, we report the effects of chemical defects [i.e., the head-to-head and tail-to-tail (HHTT) sequence] and high-power ultrasonication on the piezoelectric performance of PVDF. Two PVDF homopolymers with different HHTT contents were studied. The PVDF with a lower HHTT content (4.3 %) exhibited a higher melting temperature (Tm, denoted as HMT), whereas that with a higher HHTT content (5.9 %) exhibited a lower Tm (denoted as LMT). In addition to the primary crystals (PCs) and the isotropic amorphous fraction, wide-angle X-ray diffraction also suggested the presence of the oriented amorphous fraction (OAF) and secondary crystals (SCs), which are important in enhancing the piezoelectricity for PVDF. Intriguingly, the LMT PVDF exhibited higher piezoelectric performance than the HMT PVDF, because it had a higher OAF/SC content. In addition, high-power ultrasonication was shown to effectively break relaxor-like SCs off from the PCs, further enhancing the piezoelectric performance. That is, the inverse piezoelectric coefficient d31 reached as high as 76.2 pm/V at 65 °C for the ultrasonicated LMT PVDF. The insight from this study will enable us to design better piezoelectric PVDF polymers for practical electromechanical applications.

Modeling Anisotropic Transport in Polycrystalline Battery Materials

Hierarchical structures of many agglomerated primary crystals are often employed as cathode materials, especially for layered-oxide compounds. The anisotropic nature of these materials results in a strong correlation between particle morphology and ion transport. In this work, we present a multiphase-field framework that is able to account for strongly anisotropic diffusion in polycrystalline materials. Various secondary particle structures with random grain orientation as well as strongly textured samples are investigated. The observed ion distributions match well with the experimental observations. Furthermore, we show how these simulations can be used to mimic potentiostatic intermittent titration technique (PITT) measurements and compute effective diffusion coefficients for secondary particles. The results unravel the intrinsic relation between particle microstructure and the apparent diffusivity. Consequently, the modeling framework can be employed to guide the microstructure design of secondary battery particles. Furthermore, the phase-field method closes the gap between computation of diffusivities on the atomistic scale and the effective properties of secondary particles, which are a necessary input for Newman-type cell models.