Incipient Crystallization Research Articles

Melt viscosity tracks the volcanic and magmatic evolution of the 2021 Tajogaite eruption, La Palma (Canary Islands)

After more than 50 years of repose, on September 19th, 2021, a volcanic eruption began at the Cumbre Vieja ridge on La Palma, Canary Islands. The combined effusive and explosive activity generated a > 12 km2 lava flow field with a new cone nearly 200 m higher than pre-eruptive topography and a vast tephra blanket. The immediate impact was locally devastating, destroying nearly 2000 buildings, blocking two main and numerous secondary roads, and inundating high-value agricultural land.The hybrid nature of the eruption and the observed variations in eruption intensity motivated a thorough investigation of bulk liquid viscosity at high temporal resolution. Collection of 82 lava samples was achieved at a near daily resolution over the course of the 85-day-long event (through the end of the eruption on December 13th, 2021). All the samples were remelted, and liquid viscosity was measured in a concentric cylinder viscometer from 1490 °C down to incipient crystallization temperatures. These data constitute the highest temporal resolution viscosity dataset obtained for an eruptive sequence to date.A tripartite viscosity pattern is identified at isothermal conditions: 1) during the fissure opening and establishing stage (days 1–20) a linear decrease in melt viscosity occurred; 2) during most of the eruption duration (days 21–70) viscosity was constant and 3) from day 70 until the end of the eruption viscosity increased again. We interpret this pattern as magma being extracted from different parts of the plumbing system over the course of the eruption. Accordingly, we show that viscosity time series can help shed light on some of the complexities of volcanic plumbing system. Additionally, the presented results highlight the monitoring potential of the viscosity assessment approach, specifically in regard to forecasting eruption behavior using direct information about magma mobility and detecting changes in magmatic plumbing system dynamics.

Mechanical characterization of FDM components made of polyaryletherketone (PAEK) for aerospace applications: a comparison of direct printing and box-cut sample manufacturing strategies

This study delves into the manufacturing strategies employed for fabricating tensile samples utilized in the mechanical characterization of material extrusion (MEX) components constructed with polyaryletherketone (PAEK) for aerospace applications. Two distinct methods were investigated for obtaining tensile test samples: direct cutting and extraction from a box. These methods were examined under both as-printed and annealing conditions. Quasistatic tensile tests were conducted along the building direction to evaluate the impact of processing conditions on the adhesion of overlying layers. The results unveiled significant disparities in mechanical behavior and crystallinity between directly printed samples and those derived from the box. The Young’s modulus exhibited marginal influence; however, the tensile strength of directly printed samples measured at 30 MPa (prior to annealing), corresponding to 50% of the strength observed in samples cut from the box (60 MPa). Moreover, the elongation at rupture of directly printed samples was found to be less than 2%, while that of cut samples exceeded 8%. Notably, directly printed samples exhibited a significant degree of incipient crystallization (12.18%), contrasting with the lower level of crystallinity observed in samples cut from the box (3.27%). These findings underscore the importance of recognizing the limitations associated with direct sample printing, emphasizing its crucial role in accurately characterizing components destined for the aerospace industry. Furthermore, this understanding is pivotal for optimizing the performance and reliability of MEX-printed PAEK components in aerospace engineering applications.

Mold material and dimension effects on the microstructural gradient in a glass-ceramic

Microstructural gradients can significantly affect the properties of glass-ceramics (GCs). Such spatial variations in glass-ceramic (GC) microstructure may result from a non-uniform cooling rate when the glass-forming liquid is cast into a mold. This study investigates the material and mold size influence on the cooling process, leading to a non-uniform distribution of crystalline nuclei in the parent glass. We used a high-nucleation rate, non-stoichiometric, lithium metasilicate GC as a model. Initially, the glass-forming liquid was cooled in cylindrical molds with diameters of 7 and 14 mm, made from copper and 304 stainless steel – materials with distinct thermal diffusivities. Simulated thermography, validated by thermocouple data, showed contrasting cooling profiles across the samples. Our key findings are: i) cooling rate: faster cooling in the smaller mold resulted in a lower crystal number density and a reduced crystallized volume fraction (αv) as expected; ii) mold material: surprisingly, copper molds led to quicker glass shrinkage, which facilitated the earlier formation of air gaps with reduced heat transfer and slower cooling than steel, favoring incipient crystallization during the cooling path; iii) microstructure: samples cooled in both molds exhibited higher αv in the central and upper (mold contact-free) regions due to slower cooling compared to the mold base and edges. Therefore, this study reveals how mold material and size affect microstructural gradients in GCs, paving the way for tailoring crystallization and microstructure through strategic mold design.

Bi2ZnTiO6 thin films for next-generation photovoltaics: Study of material properties characterization and deposition conditions optimization

The perovskite-like oxide Bi2ZnTiO6 (BZT) combines a narrow band gap with significant ferroelectric polarization, key parameters for the development of next-generation photovoltaic devices. Nevertheless, BZT remains a relatively unexplored material due to its difficult synthesis. The present experimental work unfolds and optimizes the deposition of BZT phase thin films by rf-sputtering method on standard Pt(111)/TiO2/SiO2/Si(001) substrates. The series of thin films explores different deposition conditions: Substrate temperature (350º-600ºC), RF power (50–80 W), exposure time (30–120 min), O2:Ar ratio (25–50%) and thermal treatments (air-O2). Thin films deposited between 350 and 475ºC are mainly amorphous. Above 490–550ºC the films show incipient crystallization. Depositions at temperatures above 600ºC and heat treatments resulted in partial recrystallization of spurious Bi- or Zn-rich oxides and aurivillius or pyrochlore-like phases. At 550 ºC, the films are dominated by a polycrystalline BZT phase in P4mm tetragonal structure, and the increase of the O2:Ar ratio contributes to improve the B-site order. Not least, no significant structural changes were observed after ∼3 years ageing. Diffuse reflectance measurements show relatively narrow optical band gaps between 1.4–1.9 eV within expected values for this system. Piezo-force microscopy revealed domains contrast and hysteresis loops correlated with the quality of the film crystallized BZT phase.

Assigning Viscosity Values in the Glass Softening Temperature Range

A new optical method for assigning glass viscosity values in the softening temperature range is presented. In this method, an irregular particle, a few millimeters in size, laying on an alumina plate, is heated up to temperature T, and then remains at this temperature. T should be within the softening temperature range of the glass. There are no external applied shear stresses, the only acting shear forces are those coming from the particle's own surface energy. At the fixed temperature T, the surface free energy of the sample decreases by viscous flow while its shape evolves from a polyhedron or irregular shape towards a spherical or rounded shape. This shape evolution is recorded using a photographic camera. From each image, the sample's roundness is determined, obtaining a characteristic time τ from the roundness against time. Simultaneously, using the available software, a value for the viscosity η was calculated, at temperature T, allowing for building sets of T, τ, η, namely three data values. Accordingly, if T, τ are considered as independent variables, a master function η = η (T, τ) can be built. Now, if we measure T, τ data on a glass of an unknown viscosity, the master function makes it possible to assign a η value. When incipient crystallization or liquid-liquid phase separations are present, effective viscosity values are obtained. This method requires a high temperature microscope, as well as tridimmensional samples with a few cubic millimeters of volume. Each isothermal τ determination can take from minutes to several hours. We tested the method with two glasses of known viscosity values: borosilicate glass (VG98) and alumimoborosilicate glass (SG7), both of which are used for radioactive waste immobilization and have assigned log(η) values between 6 and 7.3 with η in Pa s. The discrepancy between the log(η) values assigned here and those values fitted with a VFT function on the values measured for the SG7 and VG98 glasses were within ±14%.

Simulation of surface regolith gardening and impact associated melt layer production under ns-pulsed laser ablation

The effect of surface regolith gardening and melt layer production produced by space weathering (SW) (owing to micrometeorite bombardment) of surficial regolith layers of airless planetary surfaces was investigated in an experimental setup by using laser-induced ablation of powdered analog material (synthetic Fo100) under vacuum with a ns-pulsed infrared laser. The investigated analog pellets were prepared from the fine fraction (< 1 μm) up to a grain size of 280 μm, which resembles the uppermost regolith surface of many airless planetary bodies. The Fo-powder was pressed into shape to form a pellet. We focused here on nanometer-sized structural modifications that are induced in the relocated grains, sputtered off ejecta material and melt sprinkles that formed away from the craters caused by laser irradiation of the pressed pellet surface. The ejecta particles were redistributed over the entire pellet surface and beyond. The forming sputter film, melt sprinkles and ballistically ejected grains were caught on carbon film grids positioned nearby the craters. The grids were investigated with a transmission electron microscope (TEM) to discern between the distinct deposition types that were formed by ejecta condensate and partially molten ejected nanometer-size analog grains. Apart from a heavily modified pellet surface, we found that deposited droplets are mostly amorphous with minor nanocrystalline subdomains. Eight out of ten droplets show distinct incipient crystallization stages. This indicates at a relatively high amount of amorphous regolith material at the incipient stage of SW for airless bodies, if the regolith is altered via micrometeorite bombardment.

Soils developed on the Si-poor, alkali-rich pyroclastic rocks of the Colli Albani volcanic district (Central Italy): The effect of leucite, clinopyroxene and phlogopite on the base cations mobility

The Colli Albani volcanic district emplaced huge pyroclastic-flow deposits up to 20 m thick in the southeastern suburbs of the City of Rome. The soil quality onto the gentle slopes of the Colli Albani has certainly contribute to the growth of Ancient Rome, a city with one million inhabitants as early as 2000 years ago. Interestingly, the Colli Albani soils developed on K-foiditic pyroclastic rocks with peculiar low silica, high alkali and high CaO composition. In the past, the productivity of the Colli Albani soils was maximized without the understanding of the unique physical, chemical, and mineralogical properties of these soils; now an in-depth knowledge of the Colli Albani soils is necessary to respond to the current and increasingly demand of sustainable soil use. Textural, mineralogical and chemical data indicate that the evolutionary stages of soil development are bedrock →leucite (Lct)-bearing soils→quartz (Qz)-bearing soils. The bedrock is made up mainly of leucite, clinopyroxene, phlogopite, zeolites and K-foiditic glass that is turned in an amorphous phase characterized by the Al-rich, cations base-poor and hydrated composition (i.e. halloysite-like chemistry). This reaction occurs in the syndepositional conditions (i.e. temperature up to ∼600 °C) and causes the absence of glass and the abundant crystallization of halloysite in the Colli Albani soils. The Lct-bearing soils are organic matter-poor, weakly weathered volcanic matter, comparable to the vitric andosols, showing incipient halloysite crystallization. As the degree of weathering increases, i) grain size decrease, ii) pH remain neutral, iii) highly soluble leucite, analcime and other zeolites, are rapidly dissolved, iv) alkali, Ca and Mg are leached, v) silica, Al and Fe activities increase and vi) halloysite stability field enlarges. The resulting Qz-bearing soils are made up mainly of halloysite, quartz, oxy-phlogopite and calcic clinopyroxene showing a lower cation exchange capacity (CEC) compared to the Lct-bearing soils. However, in Qz-bearing soils the CEC it is rarely <20 cmol (+)kg−1 because KEx, MgEx and CaEx are released from the oxy-phlogopite and the strongly weathered clinopyroxenes characterized by the “gothic” texture.

Global insight into microwave stoneware firing: Crystallochemical transformations

Microwave heating technology is presented as an alternative to conventional stoneware firing, with focus on the crystallochemical transformations. Scanning electron micrographs of microwave fast-fired samples show similar features as those of conventionally fired in a natural gas kiln, taken as reference samples. Electrically fast-fired samples present incipient mullite type-II crystals, while in the microwave and conventionally (gas) fired samples it is fully formed. X-ray diffraction pattern show that the crystallochemical transformations occur at lower temperatures when samples are microwave fired, particularly for temperatures lower than the vitrification temperature. Kaolinite dehydroxylation is fully accomplished at 500 °C when the samples are microwave fired, being still incomplete at 800 °C in electrically fired samples. Stoneware crystallochemical and microstructural transformations point to lower microwave firing temperatures (up to 100 °C lower) than that required by electric firing. These observations are in good agreement with what is reported in the literature, explaining at the microscopic level what happens at the macroscopic level.

Spark plasma sintering, mechanical and in-vitro behavior of a novel Sr- and Mg-containing bioactive glass for biomedical applications

The so-called BGMS10, a bioactive glass containing 10 mol.% SrO and 10 mol.% MgO, displays a low inclination to crystallize, as confirmed by its high activation energy (538.9 kJ/mol). Such peculiar aspect and the beneficial use of SPS allow for the obtainment of 99.7 % dense and fully amorphous products at 750 °C. The incipient crystallization in the glass is observed when temperature is increased to 850 °C, while 95 wt. % crystallized ceramics are produced at 950 °C. Main crystalline phases are α- and β-CaSiO3, with grain size of 89 and 97 nm, respectively. Glass crystallization is accompanied by Young’s modulus increase from 90.92 to 98.38 GPa. On the other hand, partially crystallized samples (850 °C) exhibit higher Vickers hardness (718.8) compared to fully crystallized ones (619.8), which show lower density (98.6 %). In-vitro tests in SBF indicate that the silica-gel film preceding apatite nucleation is mostly formed on the amorphous substrate region.

Nanoscale Textural and Chemical Evolution of Silica Fault Mirrors in the Wasatch Fault Damage Zone, Utah, USA

AbstractHigh‐spatial resolution textural and geochemical data from thin slip surfaces in exhumed fault zones archive thermal and rheological signatures of past fault slip. A network of minor, glossy, iridescent silica fault mirrors (FMs) cut Paleoproterozoic gneiss in the Wasatch fault zone (WFZ), Utah. We report field to nanoscale observations from scanning electron microscopy, electron backscattered diffraction, and transmission electron microscopy with energy‐dispersive X‐ray spectroscopy of a silica FM to infer deformation mechanisms during FM development. The FM volume comprises a ∼40–90 μm‐thick basal layer of sintered, µm‐ to nm‐diameter silica particles with polygonal to anhedral morphologies, pervasive crystalline Ti‐bearing phases containing measurable N, and µm‐ to nm‐scale void spaces. Silica particles lack shape and crystallographic preferred orientation and some are predominantly amorphous with internal crystalline domains. The basal layer is overlain by a ∼10–130 nm‐thick, chemically heterogeneous, amorphous film at the FM interface. Mass balance calculations of Ti in the basal layer and host rock indicate the FM volume can be sourced from the underlying gneiss. Multiple textural and geochemical lines of evidence, including N substitution in Ti‐bearing phases, support temperature rise during deformation, associated amorphization of host gneiss, and creation of the FM volume. During thermal decay, interstitial anatase and titanite fully crystallized, silica textures capture their incipient crystallization, and some residual elements are solidified in the nanofilm. Our results support a mechanism of weakening and re‐strengthening of silica FM during fault slip and, together with data from adjacent hematite FMs, record shallow, ancient microseismicity in the WFZ.

Chirality-Induced Phonon Dispersion in a Noncentrosymmetric Micropolar Crystal.

Features of the phonon spectrum of a chiral crystal are examined within the micropolar elasticity theory. This formalism accounts for not only translational micromotions of a medium but also rotational ones. It is found that there appears the phonon band splitting depending on the left- and right-circular polarization in a purely phonon sector without invoking any outside subsystem. The phonon spectrum reveals parity breaking while preserving time-reversal symmetry, i.e., it possesses true chirality. We find that hybridization of the microrotational and translational modes gives rise to the acoustic phonon branch with a "roton" minimum reminiscent of the elementary excitations in the superfluid helium-4. We argue that a mechanism of this phenomena is in line with Nozières' reinterpretation P. Nozières, [J. Low Temp. Phys. 137, 45 (2004)JLTPAC0022-229110.1023/B:JOLT.0000044234.82957.2f] of the rotons as a manifestation of an incipient crystallization instability. We discuss a close analogy between the translational and rotational micromotions in the micropolar elastic medium and the Bogoliubov quasiparticles and gapful density fluctuations in ^{4}He.

Viscosity behaviour of silicate melts during cooling under variable shear rates

The viscosity of a crystal-bearing shoshonite from Vulcanello (Aeolian Archipelago, Italy) was measured using the concentric cylinder method. Experiments were performed in the temperature interval from superliquidus (1573 K) to 1373 K with the aim to investigate the rheological response of the magma during variable cooling rate (i.e. 1000, 100 and 10 K/h) and shear rate (0.01, 0.1 and 1 s−1). In one experiment, with a cooling rate of 10 K/h and shear rate of 1 s−1, clinopyroxenes (ca. 11 vol.%) with hopper texture crystallized. One further experiment was performed for a longer time with a cooling rate of 100 K/h and shear rate of 1 s−1 to the final temperature of 1323 K. In this case, the final product showed skeletal crystals of pyroxenes (ca. 17 vol.%) and an apparent viscosity of 1.10 × 104 Pa s, which was very close to the experiment performed at 10 K/h and shear rate of 1 s−1 to 1373 K (1.18 × 104 Pa s). The comparison between experiments performed at cooling rate of 100 K/h, and finally quenched at to 1373 and 1323 K, respectively, showed that a temperature decrease of 50 K produces an increase in the apparent viscosity of ca. 1 log unit due to the transition from crystal-free to crystal-bearing melts.This study provides new data on apparent viscosity variation as cooling and shear rates vary in a crystallizing magmatic system. Results show that, on average, the viscosity of a shoshonitic system can increase by about two orders of magnitude due to temperature decrease from 1573 to 1373 K and the incipient crystallization occurring at the lowest temperatures. Finally, the results confirm that crystal nucleation and growth kinetics, as well as magma viscosity, are controlled by the dynamic state of the system.

Highly micro- and mesoporous oxycarbide derived materials from HF etching of silicon oxycarbide materials

Abstract Highly micro-mesoporous silicon oxycarbide-derived carbon materials (SiOC-DC) with elevated specific surface area up to 895 m 2 g -1 and high pore volumes of mesopores (0.3 cm 3 g -1 ) and micropores (0.2 cm 3 g -1 ) have been obtained by direct etching of SiOC with HF. Initial organic-inorganic hybrids were synthesized by the sol-gel method employing triethoxysilane and polydimethylsiloxane (PDMS) of different molecular weights (550, 1750 and 4200 gmol -1 ). These hybrids were pyrolyzed from 1100 to 1400 °C. Short PDMS chains (550 gmol -1 ) within the hybrid structure rendered dense SiOC materials after pyrolysis, however long PDMS chains (1750 and 4200 gmol -1 ) produced highly micro-mesoporous SiOC materials up to 1300 °C. The etching of SiOC employing HF produced the selective removing of silica nano-domains and as a result highly micro-mesoporous SiOC-DC materials were created. In dense SiOC the HF attack is favored at the highest temperatures (1400 °C) when the SiOC is more phase separated. On the other hand, in porous SiOC there is an agreement between the pyrolysis temperature and the porosity and, therefore the SiOC materials are etched easier at 1200 °C. SiOC-DC materials are composed by a porous glassy network enriched with carbon (graphene-like carbon and turbostratic carbon) and SiC which present an incipient crystallization.

Measuring the degree of “nanotilization” of volcanic glasses: Understanding syn-eruptive processes recorded in melt inclusions

Iron and water content substantially affect the physical properties of natural silicate melts and may, therefore, influence magmatic and volcanic processes such as crystallization, degassing, flow behaviour and eruptive style. Here we present Raman spectroscopic data for a set of synthetic and natural multicomponent glasses with varying iron oxidation state and water content. We systematically study the effect of different Raman excitation sources on the spectral response of both crystal free and magnetite nanolite bearing glasses spanning basaltic to calc- and per-alkaline rhyolitic compositions. Based on these data we document changes in Raman spectra resulting from the formation of nano-scale crystals. We show that the peak located at ~970 cm−1 is directly related to the presence of Fe2O3 dissolved in the quenched melt structure and that this feature is present regardless of the chemical composition of the sample and the Raman excitation source. We further show that a peak between 670 and 690 cm−1, which is not related to any other spectral feature of the glass structure, reveals the presence of nanolites. Based on systematic spectral investigations of this feature, we present a new index that allows to identify if iron is present in the nanocrystalline state and/or bound in the glass structure. Since the melt structural and physical effects of the formation of nanolites can heavily affect the flow behaviour of melts and the eruptive style of volcanoes, the results presented in this study significantly broaden the application of Raman spectroscopy for investigations of nano-heterogeneity in synthetic and natural glasses.We apply this method to study both the degree of nanolitization as well as the H2O content and iron oxidation state of groundmass glasses as well as melt inclusions and glass embayments in explosive products from Pantelleria island (Italy). We observe that the process of nanotilization is not purely restricted to magnetite nanolites but that Raman spectroscopy may also identify the incipient crystalization of pyroxene and feldspar at sub-micron scale. The data document that nanolite formation correlates well with the observed intensity of the respective eruptions suggesting that structural changes in the melt, caused by incipient crystallization play an important role in defining the eruptive style of relatively low viscosity magmas.

Complex Morphology Formation in Electrospinning of Binary and Ternary Poly(lactic acid) Solutions

Electrospinning of ternary systems containing a nonsolvent is of interest because it can produce fibers that are highly porous on the surface and in the core. Despite the growing interest and applications, electrospinning of such ternary systems is challenging due to their evolving viscoelastic properties prior to electrospinning. In this study, we produce porous/rough poly(lactic acid) (PLA) fibers via electrospinning of binary and ternary systems of PLA, dichloromethane (solvent) and hexane (nonsolvent). We introduce a rheological approach to determine the appropriate time for electrospinning of ternary systems which is within at most 10% of their induction time of crystallization, when incipient crystals are formed within the polymer-rich phase. These incipient crystals act as nucleators for further crystallization during the process leading to higher crystallinity and more α form crystals. Surprisingly, the pore morphology and crystallinity of the as-electrospun fibers are drastically changed after a ...

Free Energy of Nucleation and Interplay between Size and Composition in CuNi Systems.

Using molecular simulation, we shed light on the crystal nucleation process in systems of Cu, Ni, and their nanoalloy. For each system, we simulate the formation of the crystal nucleus along the entire nucleation pathway and determine the free energy barrier overcome by the system to form a critical nucleus. Comparing the results obtained for the pure metals to those for the nanoalloy, we analyze the impact of alloying on the free energy of nucleation, as well as on the size and structure of the crystal nucleus. Specifically, we relate the greater free energy of nucleation, and bigger critical nuclei, obtained for the nanoalloy, to the difference in size and cohesive energy between the two metals. Furthermore, we characterize the dependence of the local composition of the incipient crystal cluster on its size, which is of key significance for the applications of bimetallic nanoparticles in catalysis.

Submicrometer-scale spatial heterogeneity in silicate glasses using aberration-corrected scanning transmission electron microscopy

Experimental silicate glasses are often used as analog and calibration material for terrestrial and planetary materials. Measurements of Fe oxidation state using electron energy loss spectroscopy (EELS) in an aberration-corrected scanning transmission electron microscope (ac-STEM) show that a suite of experimental silicate (e.g., basaltic, andesitic, rhyolitic) glasses have spatially heterogeneous oxidation states at scales of tens of nanometers. Nano-crystals are observed in several of the glasses, indicating nucleation and incipient crystallization not seen at the scale of electron microprobe analysis (EMPA). Glasses prepared in air are uniformly oxidized while glasses prepared at the iron-wustite (IW) or quartz-fayalite-magnetite (QFM) buffers range from reduced to highly oxidized. EELS spectral shapes indicate that oxidized glasses have tetrahedral Fe3+. The nanoscale compositional and structural heterogeneities present in the experimental glasses mean that the suitability of such glasses as analogs for natural materials and calibration standards depends strongly on the scale of the measurements being done. The electron beam quickly damages silicate glass, but data showing changes in oxidation state among and within samples can be obtained with careful control of the beam current and dwell time. Determination of oxidation state in silicate glasses via STEM-EELS is very challenging, and accurate and reliable measurements of Fe3+/ΣFe require careful sample preparation and control of microscope conditions and benefit from comparison to complementary techniques.

Terahertz time-domain spectroscopy and Raman scattering studies of incipient ferroelectric BaZrO3

ABSTRACTWe have studied an incipient ferroelectric BaZrO3 single crystal with perovskite structure by terahertz time-domain and Raman scattering spectroscopies. The phonon-polariton dispersion relation of the low-frequency infrared active TO1 and TO2 modes was studied from the real and imaginary parts of the complex dielectric constants at 8 K. The experimentally observed complex polariton dispersion relations are discussed by a damped harmonic oscillator model. First-order Raman active modes, forbidden in cubic Pmm symmetry, have been observed in a BaZrO3 single crystal, indicating the lowering of cubic symmetry.

Ultrafast heating of metallic glasses reveals disordering of the amorphous structure

Studies of the transition from the supercooled liquid into the high temperature liquid of a glass forming metal is commonly hindered by incipient crystallization processes. In this contribution we show that a metallic glass exhibits a significant sudden increase in the specific heat while crossing the transition from the supercooled liquid into the high temperature liquid without crystallizing. At this increase, high temporal resolution X-ray studies show that the liquid structure changes and the crystallization behavior also deviates from the common Zr2(Cu,Al)-phase formation. We associate the increase in specific heat capacity with the disordering of the amorphous structure like a scenario of a first order liquid–liquid phase transition.

Morphology Changing at Incipient Crystallization Condition

Brushite (Dicalcium phosphate dihydrate, (DCPD), CaHPO4·2H2O) is one of key components in calcium phosphate system due to wide attractive material not only as bioceramics but also environmental materials. Morphology of DCPD crystals is important factor when one uses its functionality with chemical reaction; because its surface crystal face, shape and size rule the chemical reactivity, responsiveness. Moreover, physical properties are also changed the morphology; such as cohesion, dispersiveness, permeability and so on. If one uses DCPD crystals as environmental renovation materials to catch the fluoride ions, their shape require 020 crystal surfaces; which usually restricts their shape as plate-like structure. After the chemical reaction, the shape of sludge is not good for handling due to their agglutinate property. Therefore searching an effective parameter and developing the method to control the morphology of DCPD crystals is required. In past, we reported that initial concentration and pH value of starting solution, prepared by dissolving calcium nitrate, Ca(NO3)2 and ammonium dihydrogen phosphate, NH4H2PO4, changes the morphology of DCPD crystals and phase diagram of morphology of DCPD crystal depend on those parameter. The DCPD crystallization shows unique behaviour; products obtained higher initial concentration form single crystal-like structure and under lower condition, they form agglomerate crystal-like structure. These results contradict usual crystallization. Here we report that the effect of mixing process of two solutions. The morphology of DCPD crystals is changed from plate structure to petal structure by the arrangement. Our result suggests that morphology of DCPD crystals strongly depends at incipient crystallization condition and growth form is controllable by setting initial crystallization condition.