Ceramic Synthesis and Functionalization Laboratory

Abstract Freeze‐casting, the templating of porous structures by the solidification of a solvent, have seen a great deal of efforts during the last few years. Of particular interest are the unique structure and properties exhibited by porous freeze‐casted ceramics, which opened new opportunities in the field of cellular ceramics. The objective of this review is to provide a first understanding of the process as of today, with particular attention being paid on the underlying principles of the structure formation mechanisms and the influence of processing parameters on the structure. This analysis highlights the current limits of both the understanding and the control of the process. A few perspectives are given, with regards of the current achievements, interests and identified issues.

Abstract Direct ink writing of dense and strong ceramic objects remains an important open challenge. We develop a universal dimensionless criterion for printing such objects. Boehmite, an Al 2 O 3 precursor, was used to assess the rheological properties leading to dense structures in ceramics manufactured by direct ink writing. Boehmite suspensions undergo time dependent gelation, thus providing a rheological laboratory of flow behaviours that can be correlated with printability requirements. We measured the evolution of rheological properties over several days and quantified the deformation of simple printed shapes at different aging times. We then identified the relevant physical parameters leading to printable suspensions. We defined a dimensionless number, Ξ, based on measured rheological properties, that predicts deformation of the printed object and determines the printability criterion. An important difference with this criterion is that Ξ necessarily accounts for capillary forces and gravitational slumping. We show that boehmite inks reach a printed shape fidelity > 90% when Ξ > 1, and that Al 2 O 3 bars printed under these conditions can be sintered to 97% density, without printing defects, and have flexural strengths (500–600 MPa) competitive with commercial aluminas. Using Ξ, researchers can rationally design inks for printing dense materials by tailoring their rheological properties such that Ξ ≈ 1.

The freeze-casting of porous materials has received a great deal of attention during the past few years. This simple process, where a material suspension is simply frozen and then sublimated, provides materials with unique porous architectures, where the porosity is almost a direct replica of the frozen solvent crystals. This review focuses on the recent results on the process and the derived porous structures with regards to the biomaterials applications. Of particular interest is the architecture of the materials and the versatility of the process, which can be readily controlled and applied to biomaterials applications. A careful control of the starting formulation and processing conditions is required to control the integrity of the structure and resulting properties. Further in vitro and in vivo investigations are required to validate the potential of this new class of porous materials.

The freezing of concentrated colloidal suspensions is a complex physical process involving a large number of parameters. These parameters provide unique tools to manipulate the architecture of freeze‐cast materials at multiple length scales in a single processing step. However, we are still far from developing predictive models to describe the growth of ice crystals in concentrated particle slurries. In order to exert reliable control over the microstructural formation of freeze‐cast materials, it is necessary to reach a deeper understanding of the basic relationships between the experimental conditions and the microstructure of the growing solid. In this work, we explore the role of several processing variables (e.g., composition of the suspension, freezing rate, and patterning of the freezing surface) that could affect the formulation strategies for the architectural manipulation of freeze‐cast materials. We also demonstrate, using freeze‐cast lamellar structures, that reducing the lamellar thickness by less than half increases the compressive strength by more than one order of magnitude.

Platinum nanoparticles dispersed on nanosized ceria are active for CO oxidation at room temperature after hydrogen pretreatment. High angular annular dark field scanning transmission electron microscopy (HAADF-STEM) analysis of the reduced catalyst shows spreading of the 1 nm sized platinum particles under the electron beam, characteristic for a two-dimensional strong metal–support interaction. In situ X-ray absorption fluorescence spectroscopy (XAFS) reveals a Pt–O distance of 2.1 Å, which is significantly longer than the Pt–O distance in PtO2 (2.0 Å). This elongated Pt–O distance can be related to interaction of the platinum species with cerium oxide in the form of a low-temperature active species–support interaction. These findings contribute to the general understanding of catalytic systems operating at low temperature.

A decline in mitochondrial respiration represents the root cause of a large number of inborn errors of metabolism. It is also associated with common age-associated diseases and the aging process. To gain insight into the systemic, biochemical consequences of respiratory chain dysfunction, we performed a case-control, prospective metabolic profiling study in a genetically homogenous cohort of patients with Leigh syndrome French Canadian variant, a mitochondrial respiratory chain disease due to loss-of-function mutations in LRPPRC. We discovered 45 plasma and urinary analytes discriminating patients from controls, including classic markers of mitochondrial metabolic dysfunction (lactate and acylcarnitines), as well as unexpected markers of cardiometabolic risk (insulin and adiponectin), amino acid catabolism linked to NADH status (α-hydroxybutyrate), and NAD(+) biosynthesis (kynurenine and 3-hydroxyanthranilic acid). Our study identifies systemic, metabolic pathway derangements that can lie downstream of primary mitochondrial lesions, with implications for understanding how the organelle contributes to rare and common diseases.

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.

Tissue engineering, gene therapy, drug screening, and emerging regenerative medicine therapies are fundamentally reliant on high-quality adherent cell culture, but current methods to cryopreserve cells in this format can give low cell yields and require large volumes of solvent "antifreezes". Herein, we report polyproline as a minimum (bio)synthetic mimic of antifreeze proteins that is accessible by solution, solid-phase, and recombinant methods. We demonstrate that polyproline has ice recrystallisation inhibition activity linked to its amphipathic helix and that it enhances the DMSO cryopreservation of adherent cell lines. Polyproline may be a versatile additive in the emerging field of macromolecular cryoprotectants.

Pt-based materials are widely used as heterogeneous catalysts, in particular for pollutant removal applications. The state of Pt has often been proposed to differ depending on experimental conditions, for example, metallic Pt poisoned with CO being present at lower temperature before light-off, while an oxidized Pt surface prevails above light-off temperature. In stark contrast to all previous reports, we show herein that both metallic and oxidized Pt are present in similar proportions under reaction conditions at the surface of ca. 1 nm nanoparticles showing high activity at 30 °C. The simultaneous presence of metallic and oxidized Pt enables a synergy between these phases. The main role of the metallic Pt phase is to provide strong adsorption sites for CO, while that of oxidized Pt supposedly supplies reactive oxygen. Our results emphasize the complex dual oxidic-metallic nature of supported Pt catalysts and platinum's evolving nature under reaction conditions.

We show that the honeycomb out-of-plane model derived by Gibson and Ashby can be applied to describe the compressive behavior of unidirectional porous materials. Ice-templating allowed us to process samples with accurate control over pore volume, size, and morphology. These samples allowed us to evaluate the effect of this microstructural variations on the compressive strength in a porosity range of 45-80%. The maximum strength of 286 MPa was achieved in the least porous ice-templated sample (P(%) = 49.9), with the smallest pore size (3 μm). We found that the out-of-plane model only holds when buckling is the dominant failure mode, as should be expected. Furthermore, we controlled total pore volume by adjusting solids loading and sintering temperature. This strategy allows us to independently control macroporosity and densification of walls, and the compressive strength of ice-templated materials is exclusively dependent on total pore volume.

The solidification behavior of suspensions of alumina particles during directional solidification is investigated here by in situ observations using X‐ray radiography and tomography. The objective of this study was to assess the influence of particle size on the solidification behavior of the suspensions during the early stages of solidification. Four powders with particle size in the range of 0.2–3.4 μm (median size) were investigated. Solidification is obtained by cooling at a constant rate, starting from room temperature. Attention is specifically paid to the nucleation and growth behavior of the ice crystals in these suspensions. We propose that the nucleation of ice crystals is controlled by the particle size, the surface of the particles acting as nucleation sites. Smaller particle size leads to a lower degree of supercooling because nucleation and growth can proceed at a higher temperature than with larger particles. The initial interface velocity is dependent on the degree of supercooling, and controls the extent of the initial structural gradient in the resulting porous materials.

International audience

The interaction of objects with a moving solidification front is a common feature of many industrial and natural processes such as metal processing, the growth of single crystals, the cryopreservation of cells, or the formation of sea ice. Interaction of solidification fronts with objects leads to different outcomes, from total rejection of the objects to their complete engulfment. We imaged the freezing of emulsions in five dimensions (space, time, and solute concentration) with confocal microscopy. We showed that the solute induces long-range interactions that determine the solidification microstructure. The local increase of solute concentration enhances premelting, which controls the engulfment of droplets by the front and the evolution of grain boundaries. Freezing emulsions may be a good analog of many solidification systems where objects interact with a solidification interface.

Sintering in air of a commercially available granulated zirconia powder has been investigated using vertical dilatometer tests. Using several heating rates and the formalism of the constant rate of heating method, it has been possible to determine the apparent activation energy for the mechanism controlling densification, for different values of the relative density. It is shown that the apparent activation energy does not have a single value but depends directly on the relative density.

The possibility to align and organize faceted particles in the bulk offers intriguing possibilities for the design and discovery of materials and architectures exhibiting novel functional properties. The growth of ice crystals can be used to trigger the self-assembly of large, anisotropic particles and consequently to obtain three-dimensional porous materials of large dimensions in a limited amount of time. These mechanisms have not been explored so far due to the difficulty to experimentally investigate these systems. Here we elucidate the self-assembly mechanisms of faceted particles driven by ice growth by a combination of X-ray holotomography and discrete element modeling, providing insights into both the dynamics of self-assembly and their final packing. The encapsulation of particles is the result of a delicate balance between the force exerted by the percolating network of concentrated particles and the force exerted by the moving interface. We illustrate the benefits of such self-assembly for thermal management composite materials.

The control of the growth morphologies of ice crystals is a critical issue in fields as diverse as biomineralization, medicine, biology, civil or food engineering. Such control can be achieved through the ice-shaping properties of specific compounds. The development of synthetic ice-shaping compounds is inspired by the natural occurrence of such properties exhibited by antifreeze proteins. We reveal how a particular zirconium acetate complex is exhibiting ice-shaping properties very similar to that of antifreeze proteins, albeit being a radically different compound. We use these properties as a bioinspired approach to template unique faceted pores in cellular materials. These results suggest that ice-structuring properties are not exclusive to long organic molecules and should broaden the field of investigations and applications of such substances.

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.

Sintering in air of a pure yttria powder was investigated on green samples shaped by slip casting. The “relative density/grain size” trajectory has been drawn and hypotheses concerning the mechanisms controlling grain growth and densification were formulated. Samples were fully densified by an additional hot isostatic pressing step on pre‐sintered samples. After optimal polishing, optical properties were measured in the UV, visible, and infrared ranges.

The control of ice nucleation and growth is critical in many natural and engineering situations. However, very few compounds are able to interact directly with the surface of ice crystals. Ice-structuring proteins, found in certain fish, plants, and insects, bind to the surface of ice, thereby controlling their growth. We recently revealed the ice-structuring properties of zirconium acetate, which are similar to those of ice-structuring proteins. Because zirconium acetate is a salt and therefore different from proteins having ice-structuring properties, its ice-structuring mechanism remains unelucidated. Here we investigate this ice-structuring mechanism through the role of the concentration of zirconium acetate and the ice crystal growth velocity. We then explore other compounds presenting similar functional groups (acetate, hydroxyl, or carboxylic groups). On the basis of these results, we propose that zirconium acetate adopts a hydroxy-bridged polymer structure that can bind to the surface of the ice crystals through hydrogen bonding, thereby slowing down the ice crystal growth.

Surface hydrophobization of cellulose nanomaterials has been used in the development of nanofiller-reinforced polymer composites and formulations based on Pickering emulsions. Despite the well-known effect of hydrophobic domains on self-assembly or association of water-soluble polymer amphiphiles, very few studies have addressed the behavior of hydrophobized cellulose nanomaterials in aqueous media. In this study, we investigate the properties of hydrophobized cellulose nanocrystals (CNCs) and their self-assembly and amphiphilic properties in suspensions and gels. CNCs of different hydrophobicity were synthesized from sulfated CNCs by coupling primary alkylamines of different alkyl chain lengths (6, 8, and 12 carbon atoms). The synthetic route permitted the retention of surface charge, ensuring good colloidal stability of hydrophobized CNCs in aqueous suspensions. We compare surface properties (surface charge, ζ potential), hydrophobicity (water contact angle, microenvironment probing using pyrene fluorescence emission), and surface activity (tensiometry) of different hydrophobized CNCs and hydrophilic CNCs. Association of hydrophobized CNCs driven by hydrophobic effects is confirmed by X-ray scattering (SAXS) and autofluorescent spectroscopy experiments. As a result of CNC association, CNC suspensions/gels can be produced with a wide range of rheological properties depending on the hydrophobic/hydrophilic balance. In particular, sol-gel transitions for hydrophobized CNCs occur at lower concentrations than hydrophilic CNCs, and more robust gels are formed by hydrophobized CNCs. Our work illustrates that amphiphilic CNCs can complement associative polymers as modifiers of rheological properties of water-based systems.