Freezing Front Velocity Research Articles

Structure and mechanical properties of anisotropic agar gels obtained via unidirectional freezing

The controllable formation of anisotropic gel structures is presently sought for the development of foods with novel textures. Here, we used unidirectional freezing to generate agar gels consisting of a honeycomb-like porous network of elongated and aligned pores. A custom-built Peltier system allowed for control of the freezing front velocity throughout the agar gels. A higher freezing velocity (10 µm/s) led to smaller pore sizes compared to the slower freezing velocity tested (2 µm/s). Texture analysis highlighted the significantly higher Young’s modulus in the gels when compressed in the axial vs. radial direction − a direct consequence of the unidirectional freezing. The proton spin–spin relaxation time revealed greater water mobility in the unidirectionally frozen gel with larger pores. This study serves as the basis for the development of anisotropic hydrocolloid gels with a tunable microstructure and texture.

Effects of solutes and freezing front velocity on ice morphology in frozen ovine milk

Ovine milk is sometimes stored frozen until processing, and deterioration has been observed during frozen storage. Mechanisms for degradation have been proposed involving morphology of the frozen product. Freezing is also integral to freeze-drying, sometimes applied to ovine milk. Knowledge of factors influencing the frozen morphology in ovine milk may help avoid degradation or aid freeze-drying.Fractions were prepared from ovine milk and used to build milks of decreasing complexity from whole milk, skim milk, skim milk less casein (removed centrifugally), ovine milk ultrafiltration permeate and finally water. Cryo-Scanning-Electron Microscopy, and optical microscopy with a custom-built Bridgman furnace format freezing stage, were used to investigate the static morphology of frozen milk and then the morphology of advancing freezing fronts in ovine milk. Milk frozen slowly showed a significantly different morphology in the frozen state to milk that was frozen rapidly. The morphology of the freezing front was observed to change as the velocity increased, and as the composition of the sample being frozen changed. Increased freezing front velocities lead to the formation of columnar and then dendritic ice morphologies, and the freezing front velocities that lead to transitions in morphology increased with decreasing fluid complexity. A phase diagram was generated showing ice morphology on axes representing solution complexity and ice front velocity.Knowledge gained from the observations was used to design rapid freezing processes that preserve fresh milk properties, which have since been patented.

Gradient-controlled freeze casting of preceramic polymers

Solidification is the foundation upon which freeze casting is built, and this work seeks to understand the solidification process in freeze casting, especially with respect to the growth of dendrites. To this end, two solidification parameters, freezing front velocity and temperature gradient, were independently controlled using a gradient-controlled freeze casting setup to investigate the effects of each parameter. Changes in dendritic pore size and morphology with solidification parameters were investigated by scanning electron microscopy and mercury intrusion porosimetry. The results agree with dendrite growth theory. The theory of constitutional supercooling is used to describe the morphological changes of dendritic pores to cellular pores by the control of freezing front velocity, temperature gradient, and preceramic polymer concentrations.

Retardation of freezing of precooled, impinged water droplets on glass surfaces with microgrooves and silane coating.

Freezing impinged water droplets on glass surfaces cause serious problems such as reduced visibility of traffic lights and surveillance cameras. Droplets in the air associated with these issues are often at subzero temperatures. However, experimental results on the freezing of precooled impinged droplets are limited. In this study, we measured the freezing of precooled and impinged water droplets on cold glass surfaces. Two types of lattice-patterned microscale grooves were formed on glass surfaces to reduce the contact area of droplets and growth of frosts, which contributed to droplet freezing. In addition, the surfaces were coated with a silane coupling agent to further reduce the contact area. We analyzed the images of droplets captured using a high-speed video camera. The results of the linear relationships between the frozen droplet height, freezing front velocity, and freezing time (for the impinged droplets) indicated that the grooves and coating were effective in retarding the freezing of impinged droplets. This retardation was more evident for frost-free glass surfaces, and it was less evident for precooled droplets. Moreover, a simple heat transfer analysis was conducted to effectively estimate the overall heat flux and freezing front velocity. The sublimation of frost (adjacent to the impinged droplets) and supercool elimination of the precooled droplets significantly contributed to the heat flux and caused an increase in the freezing front velocity.

Solute concentration effects on microstructure and the compressive strength of ice‐templated sintered lithium titanate

AbstractThis work investigated the role of sucrose and cationic dispersant (1‐hexadecyl)trimethylammonium bromide concentration on ice‐templated sintered lithium titanate microstructure and compressive strength, to enable a comprehensive understanding of composition selection and elucidate processing–microstructure–mechanical property relationships. Sucrose and dispersant concentrations were varied to change total solute concentration in suspensions and viscosity. Dispersant was more effective in reducing viscosity than sucrose; however, their combination had an even greater impact on reducing viscosity. Based on viscosity measurements, a total of 12 suspension compositions were developed, and materials were fabricated at two different freezing front velocity (FFV) regimes. Solute concentration greatly influenced ice‐templated microstructure and microstructure development improved with solute concentration. Depending on solute concentration, type of solute, viscosity, and FFV, a wide variety of microstructures were observed ranging from lamellar to dendritic morphologies. Solute concentration effect was rationalized based on solid–liquid planar interface instability. For suspensions with comparable viscosity, solute concentration can be varied to tune microstructure, whereas for suspensions with comparable solute concentration, viscosity variation can tune microstructure. Compressive strength of sintered materials generally increased with total solute concentration, sucrose concentration, viscosity, and FFV. Due to the wide variety of microstructure, strength also varied over a wide range, 23–128 MPa.

Coarsening of dendrites in solution-based freeze-cast ceramic systems

The morphologies of freeze-cast materials are typically controlled and tuned by adjusting the freezing front velocity and temperature gradient. Recently it has been demonstrated that coarsening, similar to that commonly practiced in alloy systems, is also effective for morphological control in freeze-cast materials. However, the underlying coarsening mechanisms and their effect on microstructure evolution are largely unknown. In this study, frozen preceramic polymer/cyclohexane solutions were coarsened at 2 °C and 4 °C for up to 5 h, and the resulting morphologies were characterized using scanning electron microscopy, mercury intrusion porosimetry, and X-ray computed tomography. During coarsening the microstructure evolved from dendritic (primary and secondary pores) to honeycomb-like (large open channels with flat walls). The size of both primary and secondary pores increased linearly with the cube root of coarsening time, consistent with dendritic coarsening in alloy systems. Other important metrics such as primary dendrite spacing, dendrite growth directionality, and the effect of coarsening on the pore-ceramic interface area are reported. These findings provide novel insights into coarsening of freeze-cast systems and can lead to new avenues for microstructure tailorability.

Role of Microstructure on Impact Response and Damage Morphology of Ice-Templated Porous Ceramics

The central focus of this study is to investigate the influence of microstructure and direction of impact (relative to the growth direction of ice crystals) on the impact behavior of ice-templated sintered alumina materials and understand the relationship between dynamic compressive strength and impact response. All materials were fabricated using alumina suspensions of the same solid loading but at three different freezing front velocity (FFV) regimes; very-high FFV, moderately-high FFV, and low FFV. Lamella wall thickness, pore size, and pore aspect ratio decreased, and wall connectivity increased with FFV. Materials also exhibited a structural gradient along the growth direction of ice crystals. As the templated microstructure became finer with FFV, the impact resistance of the materials increased, and radius of damage crater, depth-of-penetration, and mass loss decreased. Materials also exhibited radial cracking, and the materials fabricated at very-high FFV showed a greater propensity for radial cracking for impact along the growth direction. The impact process evolved in three phases; penetration phase, dwell phase and rebound phase. Analysis of high-speed videos revealed that modifying the microstructure affected not only the impact resistance but also the duration of these phases. Variation in microstructure caused a change in the mechanism of damage evolution during impact. Dynamic compressive strength increased with FFV, and the results revealed a direct relationship between impact response and strength. For both impact and dynamic compression, energy absorption per unit volume increased with FFV, further reinforcing the relationship between impact behavior and the dynamic compressive response of ice-templated materials.

Strength enhancement in ice-templated lithium titanate Li4Ti5O12 materials using sucrose

Ice-templating technique enables the synthesis of novel ceramic materials with directional, anisotropic pores, and the templated structure is highly tunable. Another factor that also drives interest in ice-templated ceramics is that for a comparable level of porosity, the uniaxial compressive strength of these materials can be significantly greater in comparison to that of the conventional open-cell foams. However, the strength advantage is significantly reduced in the materials templated from low solid loading suspensions. Toward this limitation, this study sheds insights into the influence of sucrose (a water-soluble additive) and freezing front velocity (FFV) on microstructure and the uniaxial compressive response of ice-templated sintered lithium titanate (LTO, composition Li4Ti5O12). This study used LTO as a model material. Materials were ice-templated from aqueous suspensions with 20 vol.% LTO powder and sucrose content was varied between 1–4 wt.%. The porosity of the sintered materials was in the range of 60–65 vol.%. Materials processed without sucrose exhibited lamellar morphology and low compressive strength. Sucrose had a marked influence on the connectivity between lamella walls, which significantly increased with sucrose content, and morphology became highly dendritic. The microstructural changes remarkably impacted compressive strength, which increased as high as eight-fold. Moreover, materials processed with sucrose exhibited a significant increase in strength in the continuous brittle crushing regime. By adjusting sucrose content in aqueous suspension and FFV, it is possible to synthesize ice-templated sintered LTO materials with tailored connectivity between lamella walls and harness compressive strength within a wide range of 4–80 MPa.

Assessing the role of loading direction on the uniaxial compressive response of multilayered ice-templated alumina-epoxy composites

This work is motivated by the structural gradient observed in natural materials to investigate the influence of the loading direction on the compressive response of ice-templated alumina-epoxy composites. Although this investigation is not on the development of multilayered composites with a structural gradient, the current results can help understand the mechanical behavior and design of such materials. Ice-templated alumina materials were developed from 20 vol% suspensions at high freezing-front velocity (FFV) and from 30 vol% suspensions at high and low FFVs. From porous ceramics, specimens were extracted at different orientations relative to the growth direction of ice crystals and infiltrated with epoxy. The resultant composites varied in ceramic fraction and morphology. For compression along the growth direction of ice crystals, specimens exhibited either high strength with brittle-like (catastrophic) failure or low strength with ductile-like (progressive) failure. Away from growth direction, strength decreased significantly, and failure was ductile-type. The strength exhibited a strong dependence on ceramic fraction and morphology. At each orientation, strength data of both porous ceramics and composites showed significant variability, and Weibull analysis suggested a connection between their strength. Direct visualization revealed the influence of loading orientation and morphology on deformation and failure in composites. Using the Tsai-Hill failure criterion, the role of competitive failure mechanisms on the compressive response of composites was evaluated. From the knowledge of composition, compressive and bend strength of ceramic phase, and yield strength of polymer phase, upper bound and lower bound of strength were predicted, which encompassed the strength of composites.

Unidirectional solution-based freeze cast polymer-derived ceramics: influence of freezing conditions and templating solvent on capillary transport in isothermal wicking

Porous SiOC monoliths were prepared by solution-based freeze casting of polysiloxane at constant freezing temperature or constant freezing front velocity. Dendritic and prismatic pore structures were obtained by using cyclohexane and tert-butyl alcohol as solvent, respectively. Gradients in freezing velocity lead to gradients in pore window size, whereas a constant freezing velocity (3.3–6.8 µm/s) generates homogeneous pore structures. The water permeability varies from 1.12 × 10−13 to 1.03 × 10−11 m2 and correlates with the pore window diameter (10–59 µm) and the porosity (51–82%). In wicking tests, the gradient in pore window size is clearly reflected by a pronounced decrease in the wicking speed. Contrary, a homogeneous pore structure results in wicking curves which are closer to the prediction according to the Lucas–Washburn equation. However, this theoretical approach based on the three parameters, pore window size, porosity and permeability, is insufficient to describe complex three-dimensional pore structures. Besides the porosity, the pore morphology was found to be a major influencing factor on the wicking. The filling of secondary dendrites slows down the wicking into the dendritic structure. Fastest wicking was observed for a prismatic pore structure at low freezing front velocity (6.6 µm/s) and high porosity (78%), whereas slowest wicking occurred into the dendritic structure with high porosity (76%) and constant freezing temperature (− 20 °C). The knowledge of the relationship between structural properties and the resulting wicking behavior can address a variety of pivotal applications in chemical engineering for capillary transport.

Functionally graded multi-material freeze-cast structures with continuous microchannels

We present the processing of functionally graded multi-material freeze-cast structures, i.e. structures with varying material properties but continuous and homogeneous microchannels. We demonstrate this for stepwise, continuous, highly viscous and gelation freezing to achieve freeze-cast structures of graded La0.66Ca0.24Sr0.09Mn1.05O3 (LCSM9) and La0.67Ca0.27Sr0.06Mn1.05O3 (LCSM6) ceramics.The two phases are successfully distinguished from one another by the addition of 10 wt% Ce0.9Gd0.1O2 (CGO) to the LCSM6 phase. The relative Ce-content facilitates tracking of the LCSM6 phase using energy-dispersive X-ray (EDS) elemental analysis. Coupled with scanning electron microscopy, we show well-defined interfaces with continuous microchannels between the two LCSM phases in both green and sintered samples.By implementing constant freezing rates of −1.5 K/min a consistent freezing front velocity of ∼13 μm/s is maintained, and we found that a structural continuity can be maintained across the LCSM9–LCSM6/CGO interface, however, with varying pore morphology depending on the various freezing procedures.

Freeze-cast alumina pore networks: Effects of processing parameters in steady-state solidification regimes of aqueous slurries

Aqueous alumina slurries with varying solids loading and particle size were freeze cast under seven freezing conditions to investigate the influence of these on pore network characteristics including pore size and geometric specific surface area. Slurry temperatures were recorded in situ to determine freezing front position and velocity during solidification, which were then analyzed via regression and modeled using solidification theory. Classic mathematical models for the time dependence of freezing front position and velocity were found to hold for freeze-cast slurries. Building on these, a one-phase Stefan problem was used to describe freezing kinetics. Models for freezing front velocity were combined with solidification theory to obtain predictions of microstructural feature size from freezing kinetics. Results showed that, while there may be a dependence on solids loading, the combination of mathematical modeling of solidification and classic solidification theory is applicable to freeze-cast ceramics and accurately describes pore network characteristics from processing parameters.

Analytical solution for the soil freezing process induced by an infinite line sink

One-dimensional soil freezing process induced by an infinite line sink is investigated, a problem that is generally encountered during the application of the artificial ground freezing technique. The special feature of the freezing process of soil is that the amount of liquid water in the soil pores decreases gradually with the soil temperature decreasing, and thus latent heat is continuously released. After approximating the continuous phase change process of the soil with a multi-step phase change process of a polymorphous material, the original problem is transformed to a cylindrical multiphase Stefan problem. Using the similarity transformation technique, an analytical solution for the problem is developed, in which there are coefficients that need to be determined by a group of non-linear equations. A theoretical proof is presented showing that these coefficients can be appropriately determined by the non-linear equations. The computational results of the analytical solution are compared with those of the numerical solution, and the two solutions are in good agreement. The effects of the variation of different parameters on the movement of freezing front are studied. The results show that neglecting the existence of unfrozen water will underestimate the freezing front velocity. The relative error of this underestimation under different conditions is also investigated and discussed. In situations that the unfrozen water content is given as a discrete function of the temperature, the analytical solution can be applied directly, and an illustrative example is presented.

Ice-templating of anisotropic structures with high permeability

Nutrient diffusion and cellular infiltration are important factors for tissue engineering scaffolds. Maximizing both, by optimizing permeability and scaffold architecture, is important to achieve functional recovery. The relationship between scaffold permeability and structure was explored in anisotropic scaffolds from a human collagen I based recombinant peptide (RCP). Using ice-templating, scaffold pore size was controlled (80–600μm) via the freezing protocol and solution composition. The transverse pore size, at each location in the scaffold, was related to the freezing front velocity, via a power law, independent of the freezing protocol. Additives which interact with ice growth, in this case 1wt% ethanol, altered ice crystallization and increased the pore size. Variations in composition which did not affect the freezing, such as 40wt% hydroxyapatite (HA), did not change the scaffold structure, demonstrating the versatility of the technique. By controlling the pore size, scaffold permeability could be tuned from 0.17×10−8 to 7.1×10−8m2, parallel to the aligned pores; this is several orders of magnitude greater than literature values for isotropic scaffolds: 10−9–10−12m2. In addition, permeability was shown to affect the migration of osteoblast-like cells, suggesting that by making permeability a design parameter, tissue engineering scaffolds can promote better tissue integration.

Influence of anisotropic grains (platelets) on the microstructure and uniaxial compressive response of ice-templated sintered alumina scaffolds

Ice-templated ceramics have unique lamellar pore morphology that offers better compressive mechanical properties in comparison to the typical ceramic foams with isotropic pore morphology. However, for very high-level porosity (>65 vol%) strength difference diminishes. This investigation reveals that by inducing anisotropic grains within the matrix of a fine-grained ceramic, uniaxial compressive response of the ice-templated sintered scaffolds can be markedly enhanced without causing any considerable modification of the total porosity. To address this innovative materials design strategy, we synthesized a series of microstructures by systematically varying the anisotropic grains content in an aqueous suspension and the freezing kinetics to investigate the process-microstructure correlations and understand the structure-property relationships. Microstructural investigations revealed the unique arrangements of the platelets within and out of the lamella walls, where the upward moving ice fronts aligned the platelets' in-plane direction to the ice-growth direction. In the low freezing front velocity regime, platelets were observed to be mainly within the lamella walls, whereas platelets started to develop lamellar bridges with the increasing velocity. As a result, a transition of the pore morphology occurred with the increasing platelets content and the freezing front velocity. A novel method based on the rigorous microstructural analysis is developed to estimate the distribution of the platelets within and out of the walls and the variation of the platelets distribution with the composition and freezing front velocity. A drastic improvement of the compressive mechanical properties (stiffness, strength, energy absorption capacity) was measured due to the platelets' addition, which has been related to the platelets' distribution within and out of the walls and the pore morphology modifications. Results are rationalized based on the role of the platelets during the compressive deformation.

A comparison of microstructure and uniaxial compressive response of ice-templated alumina scaffolds fabricated from two different particle sizes

This study investigates the effects of two different particle sizes (0.3μm vs. 0.9μm) on the microstructure and uniaxial compressive response of ice-templated sintered alumina scaffolds as a function of the solids loading of the ceramic suspensions and freezing front velocity (FFV). For a comparable solids loading and FFV, variation of the particle size is observed to have a significant effect on the microstructure of the fabricated scaffolds. Moreover, transition of the pore morphology with the increasing solids loading and FFV is observed to be more drastic for the scaffolds processed from the 0.9μm size powder particles compared to the scaffolds processed from the 0.3μm size powder particles. Similarly, particle size variation also influenced significantly the relative density and porosity of the scaffolds. Interestingly, in spite of the observed significant differences of the microstructure and relative density, uniaxial compressive stress-strain measurements revealed marginal effects of the particle size variation on the compressive strength. The measured comparable uniaxial compressive response of the sintered alumina scaffolds fabricated from two different particle sizes are rationalized based on the relative density, pore aspect ratio, and interlamellae bridge density.

Freeze-cast alumina pore networks: Effects of freezing conditions and dispersion medium

Alumina ceramics were freeze-cast from water- and camphene-based slurries under varying freezing conditions and examined using X-ray computed tomography (XCT). Pore network characteristics, i.e., porosity, pore size, geometric surface area, and tortuosity, were measured from XCT reconstructions and the data were used to develop a model to predict feature size from processing conditions. Classical solidification theory was used to examine relationships between pore size, temperature gradients, and freezing front velocity. Freezing front velocity was subsequently predicted from casting conditions via the two-phase Stefan problem. Resulting models for water-based samples agreed with solidification-based theories predicting lamellar spacing of binary eutectic alloys, and models for camphene-based samples concurred with those for dendritic growth. Relationships between freezing conditions and geometric surface area were also modeled by considering the inverse relationship between pore size and surface area. Tortuosity was determined to be dependent primarily on the type of dispersion medium.

Ice‐Templating of Alumina Suspensions: Effect of Supercooling and Crystal Growth During the Initial Freezing Regime

We investigate the ice‐templating behavior of alumina suspensions by in situ X‐ray radiography and tomography. We focus herein on the formation and structure of the transitional zone, occurring during the initial instants of freezing. For many applications, this zone is undesirable as the resulting porosity is heterogeneous in size, morphology, and orientation. We investigate the influence of the composition of alumina suspensions on the formation of the transitional zone. Alumina particles are dispersed by three different dispersants, in various quantities, or by hydrochloric acid. We show that the dimensions and the morphology of the transitional zone are determined by the growth of large dendritic ice‐crystals growing in a supercooled state much faster than the cellular freezing front. When the freezing temperature decreases, the degree of supercooling increases. This results in an initial faster freezing front velocity and increase in the dimensions of the transitional zone. It is therefore possible to adjust the dimensions of the transitional zone by changing the composition of alumina suspensions. The counter‐ion Na+ has the most dramatic effect on the freezing temperature of suspensions, yielding a predominance of cellular ice crystals instead of the usual lamellar crystals.

Dispersibility of freeze-dried poly(epsilon-caprolactone) nanocapsules stabilized by gelatin and the effect of freezing

A nanocapsule (NC)–gelatin suspension was freeze-dried to produce a sample of dry food. The obtained dried product was rehydrated, and the dispersibility of the nanocapsules was investigated. It was found that the prepared freeze-dried food had different dispersion characteristics at different positions in the dried bulk sample, and this heterogeneity was dependent on the cooling program used during the processing. A model mathematical calculation was carried out in order to obtain the thermal profiles of the sample during freezing. The freezing front velocity and the viscosity of the solution at/around the freezing front were estimated by using the simulated thermal profiles. The dispersibility of the prepared dry food was found to correlate with these values. This suggested that the gel network formation of NC–gelatin would be advantageous for producing excellent NC dispersion characteristics after drying. A slow cooling condition is favourable for promoting sol–gel transition in the solution. However, the large scale of ices formed during slow freezing would damage the gel networks, leading to poor dispersibility. The present work discusses key processing factors for controlling the dispersion characteristics of nanocapsules stabilized in a freeze-dried food sample.

Relação entre o comportamento reológico e a dinâmica do congelamento e descongelamento de polpa de morango adicionada de sacarose e pectina

Polpas de morango (Fragaria ananassa) adicionadas de sacarose (0; 2,91; 10,0; 17,09; 20% peso/peso) e pectina (0; 0,15; 0,50; 0,85 e 1,0% peso/peso) foram caracterizadas quanto as propriedades fisico-quimicas e reologicas. As relacoes entre o comportamento reologico, as dinâmicas de congelamento/descongelamento e microestrutura dos cristais de gelo foram estabelecidas. Caracterizacoes fisico-quimicas e reologicas das amostras foram feitas antes e depois do congelamento/descongelamento. O congelamento foi realizado em banho ultratermostatico a -20 oC em cilindro de aco inoxidavel com isolamento termico no fundo, assegurando congelamento unidimensional. A fracao de gelo nas amostras foi calculada usando modelos teoricos e durante o congelamento foi avaliada a concentracao polarizada das amostras a cada 60 minutos. O descongelamento foi avaliado a 19 oC pela relacao tempo x aumento de area sendo estas obtidas por edicao de fotografias e quantificadas em software analisador de imagens. As polpas apresentaram comportamento de fluido pseudoplastico e foi verificado um efeito sinergistico da sacarose e pectina em meio acido observado pela variacao da viscosidade. Os descongelamentos foram mais rapidos nas amostras mais concentradas de sacarose e pectina. Analises microestruturais mostraram que a adicao de sacarose e pectina aumenta a velocidade da frente de congelamento nas amostras mais concentradas.