Ice growth has attracted great attention for its capability of fabricating hierarchically porous microstructure. However, the formation of tilted lamellar microstructure during freezing needs to be reconsidered due to the limited control of ice orientation with respect to thermal gradient during in-situ observations, which can greatly enrich our insight into architectural control of porous biomaterials. This paper provides an in-situ study of solid/liquid interface morphology evolution of directionally solidified single crystal ice with its C-axis (optical axis) perpendicular to directions of both thermal gradient and incident light in poly (vinyl alcohol, PVA) solutions. Misty morphology and V-shaped lamellar morphology were clearly observed in-situ for the first time. Quantitative characterizations on lamellar spacing, tilt angle and tip undercooling of lamellar ice platelets provide a clearer insight into the inherent ice growth habit in polymeric aqueous systems and are suggested exert significant impact on future design and optimization in porous biomaterials.
Freezing of ice has been largely reported from many aspects, especially its complex pattern formation. Ice grown from liquid phase is usually characteristic of lamellar morphology which plays a significant role in various domains. However, tilted growth of ice via transition from coplanar to non-coplanar growth in directional solidification has been paid little attention in previous studies and there is misleading explanation of the formation of tilted lamellar ice. Here, we in-situ investigated the variations of tilting behavior of lamellar ice tip under different conditions within a single i…
Formation mechanism of speed-dependent ice bandings in freezing colloidal suspensions, of significance in frost heaving and materials science, remains a mystery. With quantitative experiments, we propose a possible mechanism of speed-dependent ice bandings by focusing on the particle packing density and dynamic interface undercooling. The particle packing density ahead of the freezing interface decreases with increasing pulling speeds, attributed to the speed-dependent packing of particles. Through affecting the curvature undercooling of pore ices, the speed-dependent packing of particles can …
We have investigated the formation of 10-50 mm long ``ice spikes'' that sometimes appear on the free surface of water when it solidifies. By freezing water under different conditions, we measured the probability of ice spike formation as a function of: 1) the air temperature in the freezing chamber, 2) air motion in the freezing chamber (which promotes evaporative cooling), 3) the quantity of dissolved salts in the water, and 4) the size, shape, and composing material of the freezing vessel. We found that the probability of ice spike formation is greatest when the air temperature is near -7 C,…
Ice-templating is a well-established processing route for porous ceramics. Because of the structure/properties relationships, it is essential to better understand and control the solidification microstructures. Ice-templating is based on the segregation and concentration of particles by growing ice crystals. What we understand so far of the process is based on either observations by optical or X-ray imaging techniques, or on the characterization of ice-templated materials. However, in situ observations at particle-scale are still missing. Here we show that confocal microscopy can provide multi…
We have studied spin freezing in the diluted spin ice compound Dy2-xYxTi2O7 where the non-magnetic Y ions replace the magnetic Dy ions on the frustrated pyrochlore lattice. Magnetic a.c. and d.c. susceptibility data are presented with an analysis of relaxation times for dilutions of x = 0, 0.1, 0.2, and 0.4. Site dilution apparently decreases the relative number of spins participating in the ice-like freezing near 16 K while leaving the freezing temperature unchanged. Correspondingly the distribution of relaxation times associated with the freezing is broadened only slightly with increasing di…
The formation mechanism of ice banding in the system of freezing colloidal suspensions, which is of significance in frost heaving, ice-templating porous materials and biological materials, still remains a mystery. Recently, the theory of secondary nucleation and growth of ice has been proposed to explain the emergence of a new ice lens. However, this theory has not been quantitatively examined. Here, we quantitatively measured the initial interfacial undercooling of a new ice lens and the nucleation undercoolings of suspensions. We found that the interfacial undercooling can not satisfy the nu…
Ice growth from liquid phase has been extensively investigated in various conditions, especially for ice freely grown in undercooled water and aqueous solutions. Although unidirectional ice growth plays a significant role in sea ice and freeze casting, the detailed pattern formation of unidirectionally grown ice in an aqueous solution remains elusive. For the first time, we in situ proved a crossover from lamellar to spongy ice morphologies of a single ice crystal via unidirectional freezing of an aqueous solution. The spongy ice morphology originates from the intersect of tilted lamellar ice …
We report a study of the low temperature bulk magnetic properties of the spin ice compound Dy2Ti2O7 with particular attention to the (T < 4 K) spin freezing transition. While this transition is superficially similar to that in a spin glass, there are important qualitative differences from spin glass behavior: the freezing temperature increases slightly with applied magnetic field, and the distribution of spin relaxation times remains extremely narrow down to the lowest temperatures. Furthermore, the characteristic spin relaxation time increases faster than exponentially down to the lowest temp…
We demonstrate a facile and scalable technique, rotational freezing, to produce porous tubular ceramic supports with radially aligned porosity. The method is based on a conventional ice-templating process in a rotatory mold and demonstrated here with yttria-stabilized zirconia (YSZ). We investigated the effects of solid loading, freezing temperature, and volume of the slurry on the microstructure, strength (o-ring test and four-point bending), and air permeability. The results show that pore volume and pore size can be controlled by the solid loading and freezing temperature respectively, and …
I consider the kinetics of water freezing and show that, at small sub-zero temperatures, (i) the time of ice nucleation within the bulk water environment is enormous and therefore cannot take place either in lakes of in living cells; (ii) that the ice nucleation needs some ice-binding surfaces to occur, but (iii) even this kind of ice nucleation can take place, as a rule, only at the temperatures that are a few degrees below 0oC. Further, I discuss factors that can drastically reduce the ice nucleation time at nearly-zero temperatures both in open reservoirs, where water contacts with air, and…
Freezing colloidal suspensions widely exists in nature and industry. Interface instability has attracted much attention for the understandings of the pattern formation in freezing colloidal suspensions. However, the interface instability modes, the origin of the ice banding or ice lamellae, are still unclear. In-situ experimental observation of the onset of interface instability is still absent up to now. Here, by directly imaging the initial transient stage of planar interface instability in directional freezing colloidal suspensions, we proposed three interface instability modes, Mullins-Sek…
An approximate theory is presented describing the propagation of the ice-water front that develops in droplets of water that are deposited on a planar surface at a temperature below the melting point of ice. A calculation based on this theory is compared with our experimental observations of the time evolution of this front. The results of calculations of this front by Schultz et al7, obtained by integrating numerically the exact differential equations for this problem, were published graphically, but only for the time-dependent velocity of this front. Unfortunately, these theoretical results …
The unique anisotropy of ice has endowed sea ice growth a peculiar and attractive subject from both fundamental and applied viewpoints. The distinct growth behaviors between edge and basal plane of ice are one of the central topics in ice growth. And the unidirectional freezing pattern stems from perturbations of both basal and edge planes. To date there is no direct comparison of unidirectional freezing behavior between basal and edge plane ice. Here, we in-situ investigate the planar instability as well as the unidirectional freezing pattern of basal and edge planes of ice by a design of par…
Freezing interface interacting with soft cells is a core issue in cryopreservation. However, most of existing cryopreservation approaches face challenges such as complex processing and poor controllability. Herein we report a new, nanotechnology-based method to modulate interfacial interactions between ice and cells via the premelting theory. Through the interfacial design by controllably modifying biocompatible nanoshells on the surface of cells, the effective Hamaker constant between cells and ice can be modified. The thickness of premelted films between cells and ice is further regulated, a…
Antifreeze proteins (AFPs) evolved in cold-adapted organisms and serve to protect them against freezing in cold conditions by arresting ice crystal growth. Recently, we have shown quantitatively that adsorption of AFPs not only prevents ice from growing but also from melting. This melting inhibition by AFPs, which results in superheated ice (Celik et al, PNAS 2010), is not a well-known phenomenon. Here we present our recent findings in which the Ca2+ - dependent hyperactive AFP from Marinomonas primoryensis (MpAFP) clearly displays this property. Additionally, we found that an ice crystal that…
We explore the Casimir-Lifshitz free energy theory for surface freezing of methane gas hydrates near the freezing point of water. The theory enables us to explore different pathways, resulting in anomalous (stabilising) ice layers on methane hydrate surfaces via energy minimization. Notably, we will contrast the gas hydrate material properties, under which thin ice films can form in water vapor, with those required in the presence of liquid water. It is predicted that methane hydrates in water vapor near the freezing point of water nucleate ice films but not water films.
We report on the crossover from the thermal to athermal regime of an artificial spin ice formed from a square array of magnetic islands whose lateral size, 30~nm~$\times$~70~nm, is small enough that they are superparamagnetic at room temperature. We used resonant magnetic soft x-ray photon correlation spectroscopy (XPCS) as a method to observe the time-time correlations of the fluctuating magnetic configurations of spin ice during cooling, which are found to slow abruptly as a freezing temperature $T_0 = 178 \pm 5$~K is approached. This slowing is well-described by a Vogel-Fulcher-Tammann law,…
We herein present the spin freezing dynamics of stuffed polycrystalline compound Dy$_2$Ti$_{1.8}$Mn$_{0.2}$O$_7$. In Dy$_2$Ti$_2$O$_7$, spin freezes with ice-like spin relaxations at a temperature around 3 K (T$_i$) along with another spin freezing at a temperature around 0.7 K (T\textless T$_i$). These relaxations can be observed prominently with an application of varying DC magnetic field bias and applied AC-field. We show here that with fractional inclusion of Mn at the Ti site in Dy$_2$Ti$_2$O$_7$, there is a significant shift in these temperatures. In Dy$_2$Ti$_{1.8}$Mn$_{0.2}$O$_7$ the T…
Freezing of polymer solutions has been extensively investigated from many aspects, especially the complex pattern formation. The cell/dendrite micro-structures are believed to be in the type of diffusion-induced M-S instability. However, the presence of polymer as an impurity in water is significantly different from that of small ions. The quantitative transient investigation on directional freezing of polymer solutions remains lack due to some challenges. For the first time, we observed the planar instability behaviors during unidirectional freezing of a polymer solution together with a typic…
Dy$_{2}$Zr$_{2}$O$_{7}$ a disordered pyrochlore system, exhibits the spin ice freezing under the application of magnetic field. Our studies suggest the stabilization of pyrochlore phase in Dy$_{2-x}$La$_{x}$Zr$_{2}$O$_{7}$ with the substitution of nonmagnetic La, along with the biphasic mixture for the intermediate compositions. We observed that the higher La compositions (1.5 $\leq$ x $\leq$ 1.9), show spin freezing (T $\sim$ 17 K) similar to the field induced spin ice freezing for low La compositions (0 $\leq$ x $\leq$ 0.5), and the well known spin ice systems Dy$_{2}$Ti$_{2}$O$_{7}$ and Ho$…
The formation of regular patterns is a common feature of many solidification processes involving cast materials. We describe here how regular patterns can be obtained in porous alumina by controlling the freezing of ceramic slurries followed by subsequent ice sublimation and sintering, leading to multilayered porous alumina structures with homogeneous and well-defined architecture. We discuss the relationships between the experimental results, the physics of ice and the interaction between inert particles and the solidification front during directional freezing. The anisotropic interface kinet…
Most ice in nature forms thanks to impurities which boost the exceedingly low nucleation rate of pure supercooled water. However, the microscopic details of ice nucleation on these substances remain largely unknown. Here, we have unraveled the molecular mechanism and the kinetics of ice formation on kaolinite, a clay mineral playing a key role in climate science. We find that the formation of ice at strong supercooling in the presence of this clay is twenty orders of magnitude faster than homogeneous freezing. The critical nucleus is substantially smaller than that found for homogeneous nuclea…
Spin ice materials are the model systems that have a zero-point entropy as \textit{T} $\rightarrow$ 0 K, owing to the frozen disordered states. Here, we chemically alter the well-known spin ice Ho$_{2}$Ti$_{2}$O$_{7}$ by replacing Ti sites with isovalent but larger Zr ion. Unlike the Ho$_{2}$Ti$_{2}$O$_{7}$ which is a pyrochlore material, Ho$_{2}$Zr$_{2}$O$_{7}$ crystallizes in disordered pyrochlore structure. We have performed detailed structural, ac magnetic susceptibility and heat capacity studies on Ho$_{2}$Zr$_{2}$O$_{7}$ to investigate the interplay of structural disorder and frustrated …
Freezing of a deformable water-saturated porous medium. Part I: THM formulation, OpenGeoSys-6 implementation and benchmarking
BGE Technology GmbH（BGE技术有限公司）；UFZ Leipzig（莱比锡赫尔姆霍兹环境研究中心）；Technische Universität Bergakademie Freiberg（弗莱贝格矿业技术大学）；Technische Universität Dresden（德累斯顿工业大学）
We have studied the low temperature a.c. magnetic susceptibility of the diluted spin ice compound Dy(2-x)MxTi2O7, where the magnetic Dy ions on the frustrated pyrochlore lattice have been replaced with non-magnetic ions, M = Y or Lu. We examine a broad range of dilutions, 0 <= x <= 1.98, and we find that the T ~ 16 K freezing is suppressed for low levels of dilution but re-emerges for x > 0.4 and persists to x = 1.98. This behavior can be understood as a non-monotonic dependence of the quantum spin relaxation time with dilution. The results suggest that the observed spin freezing is fundamenta…
The formation of regular patterns is a common feature of many solidification processes involving cast materials. We describe here how regular patterns can be obtained in porous alumina and hydroxyapatite (HAP) by controlling the freezing of ceramic slurries followed by subsequent ice sublimation and sintering, leading to multilayered porous ceramic structures with homogeneous and well-defined architecture. These porous materials can be infiltrated with a second phase of choice to yield biomimetic nacre-like composites with improved mechanical properties, which could be used for artificial bone…
Premelting describes the confluence of phenomena that are responsible for the stable existence of the liquid phase of matter in the solid region of its bulk phase diagram. Here we develop a theoretical description of the premelting of water ice contained in a porous matrix, made of a material with a melting temperature substantially larger than ice itself, to predict the amount of liquid water in the matrix at temperatures below its bulk freezing point. Our theory combines the interfacial premelting of ice in contact with the matrix, grain boundary melting in the ice, and impurity and curvatur…
Biological antifreezes protect cold-water organisms from freezing. An example are the antifreeze proteins (AFPs) that attach to the surface of ice crystals and arrest growth. The mechanism for growth arrest has not been heretofore understood in a quantitative way. We present a complete theory based on a kinetic model. We use the `stones on a pillow' picture. Our theory of the suppression of the freezing point as a function of the concentration of the AFP is quantitatively accurate. It gives a correct description of the dependence of the freezing point suppression on the geometry of the protein…
Ice templating of colloidal suspension is gaining interest in material science because it offers the possibility to shape advanced materials, and in particular porous ceramics. Recent investigations on this peculiar process show that a correlation between the morphology of the frozen suspension and the velocity of the freezing front do exist. The dynamics of the freezing front of a colloidal suspension of alumina is investigated in the present study by experimental tests, finite element numerical analysis and theoretical analytical calculations. The experimental tests are carried out by in sit…
Materials that are strong, ultra-light weight and tough are in demand for a range of applications, requiring architectures and components carefully designed from the micrometer down to nanometer scales. Nacre-a structure found in many molluscan shells-and bone are frequently used as examples for how nature achieves this through hybrid organic-inorganic composites. Unfortunately, it has proven extremely difficult to transcribe nacre-like clever designs into synthetic materials, partly because their intricate structures need to be replicated at several length scales. We demonstrate how the physi…
Methanol is a potentially important impurity in subsurface oceans on Titan and Enceladus. We report measurements of the freezing of methanol-water samples at pressures up to 350~MPa using a volumetric cell with sapphire windows. For low concentrations of methanol, the liquidus temperature is typically a few degrees below the corresponding ice freezing point, while at high concentrations it follows the pure methanol trend. In the Ice-III regime, we observe several long-lived metastable states. The results suggest that methanol is a more effective antifreeze than previously estimated, and might …
Controlling anisotropy in self-assembled structures enables engineering of materials with highly directional response. Here, we harness the anisotropic growth of ice walls in a thermal gradient to assemble an anisotropic refractory metal structure, which is then infiltrated with Cu to make a composite. Using experiments and simulations, we demonstrate on the specific example of tungsten-copper composites the effect of anisotropy on the electrical and mechanical properties. The results are compared to isotropic tungsten-copper composites fabricated by standard powder metallurgical methods. Our …
Cryopreservation is the only fully established procedure to extend the lifespan of living cells and tissues, a key to activities spanning from fundamental biology to clinical practice. Despite its prevalence and impact, central aspects of cryopreservation, such as the cell's physico-chemical environment during freezing, remain elusive. Here we address that question by coupling in situ microscopic directional freezing to visualize cells and their surroundings during freezing with the freezing medium phase diagram. We extract the freezing medium spatial distribution in cryopreservation, providin…
The disordered pyrochlore oxide Dy$_{2}$Zr$_{2}$O$_{7}$ shows the signatures of field-induced spin freezing with remnant zero-point spin-ice entropy at 5 kOe magnetic field. We have performed zero-field and longitudinal field Muon spin relaxation ($μ$SR) studies on Dy$_{2}$Zr$_{2}$O$_{7}$. Our zero field studies reveal the absence of both long-range ordering and spin freezing down to 62 mK. The $μ$SR relaxation rate exhibits a temperature-independent plateau below 4 K, indicating a dynamic ground state of fluctuating spins similar to the well-known spin ice system Dy$_{2}$Ti$_{2}$O$_{7}$. The …
It is surprisingly difficult to freeze water. Almost all ice that forms under "mild" conditions (temperatures > -40 degrees Celsius) requires the presence of a nucleating agent - a solid particle that facilitates the freezing process - such as clay mineral dust, soot or bacteria. In a computer simulation, the presence of such ice nucleating agents does not necessarily alleviate the difficulties associated with forming ice on accessible timescales. Nevertheless, in this work we present results from molecular dynamics simulations in which we systematically compare homogeneous and heterogeneous i…
High performance lead zirconate titanate (PZT) ceramics with aligned porosity for sensing applications were fabricated by an ice-templating method. To demonstrate the enhanced properties of these materials and their potential for sensor and hydrophone applications, the piezoelectric voltage constants hydrostatic parameters and AC conductivity as a function of the porosity in directions both parallel and perpendicular to the freezing temperature gradient were studied. As the porosity level was increased, PZT poled parallel to the freezing direction exhibited the highest coefficients, and hydros…
