The effect of solidification direction with respect to gravity on ice-templated TiO2 microstructures

Unidirectional ice-templating produces materials with aligned, elongated pores via: (i) directional solidification of particle suspensions wherein suspended particles are rejected and incorporated between aligned dendrites, (ii) sublimation of the solidified fluid, and (iii) sintering of the particles into elongated walls which are templated by the ice dendrites. Most ice-templating studies utilize upward solidification techniques, where solid ice is located at the bottom of the solidification mold (closest to the cold source), the liquid suspension is above the ice, and the solidification front advances upward, against gravity. Liquid water reaches its maximum density at 4 °C; thus, liquid nearest the solid/liquid interface, at 0ºC, is less dense than warmer liquid above (up to 4 °C, above which, a density inversion occurs, and liquid density decreases with increasing temperature). The lower density liquid nearest the solidification front is thus expected to rise due to buoyancy, promoting convective fluid motion in the liquid during solidification. Here, we investigate the effect of solidification direction with respect to the direction of gravity on ice-templated microstructures to study the role of buoyancy-driven fluid motion during solidification. We hypothesize that, for upward solidification, the convective fluid motion that results from the liquid density gradient occurs near the solidification front. For downward solidification, we expect that this fluid motion occurs farther away from the solidification front. Aqueous suspensions of TiO₂ nanoparticles (10–30 nm in size, 10, 15, and 21 vol.%) are solidified upward (against gravity, with ice on bottom and water on top), downward (water on bottom, ice on top), and horizontally (perpendicular to gravity). Microstructural investigation of sintered samples shows evidence of buoyancy-driven, convective fluid flow during solidification for samples solidified upwards (against gravity), including (i) tilting of the wall (and pore) orientation with respect to the induced temperature gradient, (ii) ice lens defects (cracks oriented perpendicular to the freezing direction), and (iii) radial macrosegregation. These features are not observed for downward nor horizontal solidification configurations, consistent with the hypothesis that convective fluid motion does not interact directly with the solidification front for downward solidification.     

In Situ X-Ray Radiography and Tomography Observations of the Solidification of Aqueous Alumina Particles Suspensions. Part II: Steady State

This paper investigates the behavior of colloidal suspensions of alumina particles during directional solidification, by in situ high-resolution observations using X-ray radiography and tomography. This second part is focussed on the evolution of ice crystals during steady-state growth (in terms of interface velocity) and on the particle redistribution taking place in this regime. In particular, it is shown that particle diffusion cannot determine the particle concentration profile in this regime of interface velocities (20–40 μm/s). Particles are redistributed by a direct interaction with the moving solidification interface. Several parameters controlling the particle redistribution were identified, namely the interface velocity, the particle size, the shape of the ice crystals, and the orientation relationships between the crystals and the temperature gradient.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Evolution of Surface Morphology in Laser-Dressed Alumina Grinding Wheel Material

An approach to laser dressing of alumina grinding wheels is proposed based on solidification microstructures associated with rapid cooling rates obtained in laser surface processing. Laser dressing of alumina grinding wheels forms surface microstructures characterized by multifaceted grains that are expected to facilitate the micro-scale material removal during precision machining. A detailed investigation of variation of grain size and melt depth with laser fluence is conducted. The results are correlated with calculated cooling rates derived from a thermal model. In addition, based on microscopic observations, the formation of surface grains by stacking of individual multifaceted grains formed during laser dressing is suggested.     

纯水和氯化钠溶液凝固过程的实验研究

近几年国内外学者对冰浆的各种特性进行了大量研究,但大多都集中在冰浆生成器的装置设计、冰浆在管道中的流动及传热特性,很少有从冰晶颗粒在壁面生成及结晶过程的机理进行研究讨论。本文对纯水和不同浓度氯化钠溶液在不同材料表面的凝固特性进行了实验研究,搭建了多组分溶液表面凝固性能研究装置,并对装置布置测点同时可更换测试表面。实验采取不同浓度的氯化钠溶液,分别记录在粗糙度不同的铜板、铝板以及塑料板表面凝固时的温度、时间,分析不同表面粗糙度、不同材质以及氯化钠浓度对溶液成核能的影响。通过对实验数据的分析和处理分别得出开始凝固温度与粗糙度的变化关系以及凝固时间与过冷度的变化关系。实验结果表明：溶液在平板表面凝固的初始温度会随着粗糙度的增大而逐渐升高。溶液在平板表面凝固的凝固时间会随着过冷度的增大而逐渐降低。     

快速凝固镁合金的研究进展

综述了快速凝固镁合金的制备方法、组织结构及性能特征，分析了快速凝固镁合金的强化机制，并指出了当前快速凝固镁合金的发展动向。     

A parametric study of axial segregation in granular systems

When a cylindrical container, partially filled with a binary granular mixture of particles that differ in size or density, is rotated around its axis, a spontaneous segregation of the two granular components may occur. In order to better understand this phenomenon, we have carried out an experimental study probing the effect of average particle size and relative size difference between particles on the onset of segregation. The experimental study is followed by a novel scaling analysis which relates the deterministic, convective driving force for particle segregation to the randomizing diffusional driving force present in these systems through the definition of an axial granular Péclet number. Values of this granular Péclet number are shown to successfully correlate with segregation behavior in the present study, as well as in comparable results in the literature.     

Intrinsic microstructures of silica-bonded porous nano-SiC ceramics

Silica-bonded porous SiC ceramics were fabricated using nano-β-SiC powder-carbon black template compacts by sintering in air at 600°C-1200°C. The intrinsic microstructures of the porous ceramics were characterized by high-resolution transmission electron microscopy, which led to the following observations: (a) a core (SiC)-shell (SiO₂) structure was formed, owing to the partial oxidation of nano-SiC particles during sintering; (b) a low-temperature (800°C) β-to-α polytypic phase transformation was observed, owing to the oxidation-induced residual thermal stresses; and (c) non-graphitic carbons were precipitated inside the SiC core, owing to the segregation of C atoms emitted at the strained SiC-SiO₂ interface.     

SLM printing of cermet powders: Inhomogeneity from atomic scale to microstructure

It is very challenging for 3D printing based on the selective laser melting (SLM) technology to obtain cermet bulk materials with high density and homogeneous microstructures. In this work, the SLM process of the cermet powders was studied by both simulations and experiments using the WC-Co cemented carbides as an example. The results indicated that the evolution of the ceramic and metallic phases in the cermet particle during the heating, melting and solidification processes were all significantly inhomogeneous from atomic scale to mesoscale microstructures. As a consequence, the microstructural defects were caused intrinsically in the printed bulk material. The formation and growth of the bonding necks between the particles were mainly completed at the later stage of laser heating and the early stage of solidification. Both simulations and experiments demonstrated that thin amorphous layers formed at the ceramics/metal interfaces. This work disclosed the mechanisms for the evolution from the atomic scale to microstructure during the SLM printing of cermet powders, and discovered the origin of the defects in the printed cermet bulk materials.     

Microstructural development in a rapidly cooled eutectic Sn-3.5% Ag solder reinforced with copper powder

Experiments using eutectic Sn-3.5% Ag solder paste were conducted with the objective of examining the conjoint influence of copper particles addition and rapid cooling on microstructural development. The composite solder mixture was made by thoroughly mixing a pre-weighed amount of copper particles with a commercial Sn-3.5% Ag solder paste. The experiments were quite similar to the heating and cooling cycle of an industrial reflow soldering process. Heating of the samples was conducted in a furnace whose temperature was carefully controlled. The cooling process was conducted on a chilled aluminum block through which coolant was circulated at 0.5 °C. When the solder temperature reached 250 °C, the circulating system would turn on automatically and the sample, which is still molten, is forced to cool rapidly. Temperature records of the solder samples revealed that addition of copper particles to the eutectic Sn-3.5% Ag did not appreciably affect the heating and melting properties when compared to the unreinforced Sn-3.5% Ag counterpart. However, copper particles did change the solidification temperature of the composite solder. Detailed observations for varying amounts of copper particle addition revealed that copper particles less than 1.0 wt.% lowered the solidification temperature of the composite solder. For copper particles greater than 1.0 wt.%, the solidification temperature increased a few degrees Celsius, indicating that some of the copper particles did not completely dissolve in the Sn-dominant solder during the melting process. Results reveal that as-solidified microstructures of the eutectic Sn-3.5% Ag solder contain columnar type dendrites of the Sn-rich phase and a eutectic mixture of the Sn₃Ag and Sn-rich phase located between the dendrite columns. The addition of copper particles to the eutectic Sn-3.5% Ag solder does refine the morphology of the primary phase, which is attributed to the presence and distribution of the Cu₆Sn₅ intermetallic in the solder matrix.     

Microstructural Control of Colloidal‐Based Ceramics by Directional Solidification Under Weak Magnetic Fields

The use of weak magnetic fields to control the microstructural evolution of colloidal‐based systems in conjunction with directional solidification is demonstrated as a convenient processing route to fabricate anisotropic ceramic scaffolds with complex microarchitectures. A variety of graded and aligned microstructures were formed by applying external static magnetic fields oriented radially, axially, and transversely with respect to the solidification direction of freezing slurries containing micro/nanoparticles of ZrO₂ and Fe₃O₄. The graded structures, formed by the radial and axial fields, resemble core–shell architectures composed of dense outer perimeters surrounding porous inner cores. The aligned structures, formed by transverse fields, exhibit two modes of microstructural alignment: lamellar walls aligned by the growing ice crystals and mineral bridges aligned by the magnetic fields. The alignment of mineral bridges that connect adjacent lamellae, provide these scaffolds enhanced strength and stiffness when compressed parallel to their orientation (parallel to the direction of the magnetic field).     

Characterization of transverse mixing in a screw mixer by image analysis

Transverse mixing of particles in a screw mixer is investigated by a digitized image analysis method coupled with a solidification technique. The effects of screw rotation speed, filling level, and particle size on the transverse mixing index and mixing rate constant are investigated experimentally. The results show that a decrease in screw rotation speed and filling level results in an increase in the mixing rate. Faster mixing is observed with large particles, and the mixing rate constant of coarse particles is 1.5–2 times higher than that of fine particles. The particle size difference of materials puts the particles at a risk of segregation.     

喷雾冷冻法单个液滴冻结过程模拟

喷雾冷冻液滴的冻结过程决定着干燥产品的微结构。本文以单个雾化液滴为研究对象,利用数值模拟的方法研究了液滴大小、气体流速和环境温度3个参数对其冻结过程的影响。结果发现,液滴越大冻结时所需的形核时间和完全固化时间越长,而且冻结过程随着气体流速的增大和环境温度的降低而缩短。通过方差分析发现,液滴大小较气体流速和环境温度对液滴完全固化时间的影响有较显著差异。液滴冷冻过程中,其质量损失率随着液滴大小的增大而略有减小,随着气体流速的增加及环境温度的降低而减小,其中环境温度对液滴质量损失率的影响最大。     

In Situ X-Ray Radiography and Tomography Observations of the Solidification of Aqueous Alumina Particle Suspensions—Part I: Initial Instants

This paper investigates by in situ high-resolution X-ray radiography and tomography the behavior of colloidal suspensions of alumina partic les during directional solidification by freezing. The combination of these techniques provided both qualitative and quantitative information about the propagation kinetic of the solid/liquid interface, the particle redistribution between the crystals and a particle-enriched phase, and the three-dimensional organization of the ice crystals. In this first part of two companion papers, the precursor phenomena leading to directional crystallization during the first instants of solidification are studied. Mullins–Sekerka instabilities are not necessary to explain the dynamic evolution of the interface pattern. Particle redistribution during these first instants is dependent on the type of crystals growing into the suspension. The insights gained into the mechanisms of solidification of colloidal suspensions may be valuable for the materials processing routes derived for this type of directional solidification (freeze-casting), and of general interest for those interested in the interactions between solidification fronts and inert particles.     

Hierarchical structure and unique impact behavior of polypropylene/ethylene-octene copolymer blends as obtained via dynamic packing injection molding

Controlling the hierarchical structure of melt-processed polymers is vital to “structuring” processing and tailoring properties of the product. In this work, polypropylene (PP)/octene-ethylene copolymer (POE) blends were injection-molded using so-called dynamic packing injection technique, which imposed oscillatory shear on the gradually cooled melt during the packing solidification stage. In this way, samples with highly oriented PP matrix and elongated POE particles were obtained. Most interestingly, it was found for the first time that the elongated POE particles could not improve any impact toughness of oriented PP, which is completely different from that for the isotropic ones. Polarized optical microscope, scanning electron microscope, micro-Fourier transform infrared spectroscopy and differential scanning calorimetry were used to characterize the microstructures along sample thickness. The crack-initiation term, impact fractured surface and cross-section of the impact surface were inspected to understand the difference in impact behavior between the oriented PP/POE blends and their isotropic counterparts. The results show that massive crazing or plastic flow of the matrix could not be effectively initiated in the oriented blends. Our work provides a good example for better understanding structure–property relationship of polymers via well controlling their internal hierarchical structure.     

Fabrication of lamellar porous alumina with regular structure via directional solidification with multiple cold sources

Porous ceramics obtained with aqueous slurries by directional solidification have randomly distributed lamellar pore channels and thus have unstable mechanical properties. According to the anisotropic principle of ice crystal growth, the growth of lamellar ice crystals is regular when multiple cold sources are used, and porous ceramics with regular pore channels are then obtained after drying. Multiple cold sources are formed with a bottom cold plate and copper sides in rectangular molds. The copper sides are in contact with the bottom cold plate, thus forming the side cold source with temperature gradient distribution by heat transfer. The interaction between the side cold source and the bottom cold plate facilitates the regular distribution and continuous growth in parallel of ice crystals. The use of parallel copper sides of the mold results in porous ceramics with an axisymmetric pore structure and high aspect ratios of pore channel in porous alumina. The positive compressive strength of fabricated porous ceramics with an axisymmetric structure is similar with those of conventional directional solidification, but the lateral side direction compressive strength of fabricated porous ceramics with an axisymmetric structure is significantly increased.     

Preparation of Mullite-Zirconia Composites from Glass Powder

Glass powders with the composition mullite/5 wt% ZrO₂, prepared by rapid solidification, were used to prepare a poly-crystalline ceramic by hot-pressing to 1040°C. The as-prepared structure consisted of a fine-grain-sized (∼0.1 μm) solid solution of ZrO₂ in a tetragonal form of mullite. Heat treatment between 1300° and 1660°C resulted in a range of microstructures consisting of tetragonal ZrO₂ particles dispersed in mullite. Transformable tetragonal ZrO₂ was observed only after heat treatment at 1600°C.     

Microstructural Development of Coherent Tetragonal Precipitates in Magnesium-Partially-Stabilized Zirconia: A Computer Simulation

A new computer simulation technique for modeling morphological pattern formation during nucleation, growth, and coarsening of coherent misfitting particles is developed. Microstructure evolution during precipitation of tetragonal phase from Mg-partially-stabilized cubic zirconia is investigated. Our computer simulation shows that during the initial stage of precipitation, the tetragonal particles formed by homogeneous nucleation display strong alignment along certain crystallographic directions, forming the so-called "tweed" pattern. During subsequent growth of the spatially correlated nuclei, an alternating band structure is observed, with each individual band consisting of lens-like-shaped tetragonal phase particles of the same orientation variant dispersed in the cubic matrix. The particles in the neighboring bands are twin-related. The microstructures obtained in our computer simulation seem to agree well with the experimental observations.     

Dynamics of segregation and fluidization of binary mixtures in a cylindrical fluidized bed

Dynamics of segregation and fluidization of unary particles and binary mixtures in a cylindrical fluidized bed is investigated using temporally– and spatially–resolved measurements of solids volume fraction (α_s) performed using Electrical Capacitance Tomography (ECT). Through the comparison with high-speed imaging, we have shown that ECT can be used to measure the segregation behavior in cylindrical fluidized beds quantitatively. ECT measurements have been used further to quantify the effects of mixture composition, particle–diameter ratio, and superficial gas velocity on the bed segregation behavior. Dynamics of fluidization behavior is characterized using the time–evolution of local α_s fluctuations, corresponding frequency distribution, and bubble size distribution. Further, a relation between the measured variance of α_s fluctuations at different radial locations and corresponding flow structures under different fluidization conditions is established. The present work helps to understand dynamics of segregation and fluidization of binary mixtures and to provide a database for validation of Eulerian multifluid CFD models.     

Simulation and modeling of segregating rods in quasi‐2D bounded heap flow

Many products in the chemical and agricultural industries are pelletized in the form of rod‐like particles that often have different aspect ratios. However, the flow, mixing, and segregation of non‐spherical particles such as rod‐like particles are poorly understood. Here, we use the discrete element method (DEM) utilizing super‐ellipsoid particles to simulate the flow and segregation of rod‐like particles differing in length but with the same diameter in a quasi‐2D one‐sided bounded heap. The DEM simulations accurately reproduce the segregation of size bidisperse rod‐like particles in a bounded heap based on comparison with experiments. Rod‐like particles orient themselves along the direction of flow, although bounding walls influence the orientation of the smaller aspect ratio particles. The flow kinematics and segregation of bidisperse rods having identical diameters but different lengths are similar to spherical particles. The segregation velocity of one rod species relative to the mean velocity depends linearly on the concentration of the other species, the shear rate, and a parameter based on the relative lengths of the rods. A continuum model developed for spherical particles that includes advection, diffusion, and segregation effects accurately predicts the segregation of rods in the flowing layer for a range of physical control parameters and particle species concentrations. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1550–1563, 2018