Bruno Escribano

From Chemical Gardens to Chemobrionics

Chemical gardens in laboratory chemistries ranging from silicates to polyoxometalates, in applications ranging from corrosion products to the hydration of Portland cement, and in natural settings ranging from hydrothermal vents in the ocean depths to brinicles beneath sea ice. In many chemical-garden experiments, the structure forms as a solid seed of a soluble ionic compound dissolves in a solution containing another reactive ion. In general any alkali silicate solution can be used due to their high solubility at high pH. The cation should not precipitate with the counterion of the metal salt used as seed. A main property of seed chemical-garden experiments is that initially, when the fluid is not moving under buoyancy or osmosis, the delivery of the inner reactant is diffusion controlled. Another experimental technique that isolates one aspect of chemical-garden formation is to produce precipitation membranes between different aqueous solutions by introducing the two solutions on either side of an inert carrier matrix. Chemical gardens may be grown upon injection of solutions into a so-called Hele-Shaw cell, a quasi-two-dimensional reactor consisting in two parallel plates separated by a small gap.

Chemical-Garden Formation, Morphology, and Composition. I. Effect of the Nature of the Cations

We have grown chemical gardens in different sodium silicate solutions from several metal-ion salts--calcium chloride, manganese chloride, cobalt chloride, and nickel sulfate--with cations from period 4 of the periodic table. We have studied their formation process using photography, examined the morphologies produced using scanning electron microscopy (SEM), and analyzed chemical compositions using X-ray powder diffraction (XRD) and energy dispersive X-ray analysis (EDX) to understand better the physical and chemical processes involved in the chemical-garden reaction. We have identified different growth regimes in these salts that are dependent on the concentration of silicate solution and the nature of the cations involved.

Spiral and target patterns in bivalve nacre manifest a natural excitable medium from layer growth of a biological liquid crystal

Nacre is an exquisitely structured biocomposite of the calcium carbonate mineral aragonite with small amounts of proteins and the polysaccharide chitin. For many years, it has been the subject of research, not just because of its beauty, but also to discover how nature can produce such a superior product with excellent mechanical properties from such relatively weak raw materials. Four decades ago, Wada [Wada K (1966) Spiral growth of nacre. Nature 211:1427] proposed that the spiral patterns in nacre could be explained by using the theory Frank [Frank F (1949) The influence of dislocations on crystal growth. Discuss Faraday Soc 5:48–54] had put forward of the growth of crystals by means of screw dislocations. Franks mechanism of crystal growth has been amply confirmed by experimental observations of screw dislocations in crystals, but it is a growth mechanism for a single crystal, with growth fronts of molecules. However, the growth fronts composed of many tablets of crystalline aragonite visible in micrographs of nacre are not a molecular-scale but a mesoscale phenomenon, so it has not been evident how the Frank mechanism might be of relevance. Here, we demonstrate that nacre growth is organized around a liquid-crystal core of chitin crystallites, a skeleton that the other components of nacre subsequently flesh out in a process of hierarchical self-assembly. We establish that spiral and target patterns can arise in a liquid crystal formed layer by layer through the Burton–Cabrera–Frank [Burton W, Cabrera N, Frank F (1951) The growth of crystals and the equilibrium structure of their surfaces. Philos Trans R Soc London Ser A 243:299–358] dynamics, and furthermore that this layer growth mechanism is an instance of an important class of physical systems termed excitable media. Artificial liquid crystals grown in this way may have many technological applications.

Brinicles as a case of inverse chemical gardens

Brinicles are hollow tubes of ice from centimeters to meters in length that form under floating sea ice in the polar oceans when dense, cold brine drains downward from sea ice to seawater close to its freezing point. When this extremely cold brine leaves the ice, it freezes the water it comes into contact with: a hollow tube of ice-a brinicle-growing downward around the plume of descending brine. We show that brinicles can be understood as a form of the self-assembled tubular precipitation structures termed chemical gardens, which are plantlike structures formed on placing together a soluble metal salt, often in the form of a seed crystal, and an aqueous solution of one of many anions, often silicate. On one hand, in the case of classical chemical gardens, an osmotic pressure difference across a semipermeable precipitation membrane that filters solutions by rejecting the solute leads to an inflow of water and to its rupture. The internal solution, generally being lighter than the external solution, flows up through the break, and as it does so, a tube grows upward by precipitation around the jet of internal solution. Such chemical-garden tubes can grow to many centimeters in length. In the case of brinicles, on the other hand, in floating sea ice we have porous ice in a mushy layer that filters out water, by freezing it, and allows concentrated brine through. Again there is an osmotic pressure difference leading to a continuing ingress of seawater in a siphon pump mechanism that is sustained as long as the ice continues to freeze. Because the brine that is pumped out is denser than the seawater and descends rather than rises, a brinicle is a downward-growing tube of ice, an inverse chemical garden.

Chemical-Garden Formation, Morphology, and Composition. II. Chemical Gardens in Microgravity

We studied the growth of metal-ion silicate chemical gardens under Earth gravity (1 g) and microgravity (μg) conditions. Identical sets of reaction chambers from an automated system (the Silicate Garden Habitat or SGHab) were used in both cases. The μg experiment was performed on board the International Space Station (ISS) within a temperature-controlled setup that provided still and video images of the experiment downlinked to the ground. Calcium chloride, manganese chloride, cobalt chloride, and nickel sulfate were used as seed salts in sodium silicate solutions of several concentrations. The formation and growth of osmotic envelopes and microtubes was much slower under μg conditions. In 1 g, buoyancy forces caused tubes to grow upward, whereas a random orientation for tube growth was found under μg conditions.

THE MESOSCALE MORPHOLOGIES OF ICE FILMS: POROUS AND BIOMORPHIC FORMS OF ICE UNDER ASTROPHYSICAL CONDITIONS

We present the results of experiments in which we grow submicrometer- to millimeter-thick ice films at temperatures of 6-220 K at low pressures in situ in a cryo environmental scanning electron microscope. We find that ice films show pronounced morphologies at the mesoscale similar to those previously described in films of ceramics, semiconductors, and metals; materials with quite different material properties to ice. Our experiments are aimed at revealing the mesoscale morphologies of amorphous and crystalline ice with regard to astrophysical environments, as the conditions in which the ice films grow in our experiments are those under which exists most extraterrestrial ice. The porosity on the mesoscale of many of the morphologies is notable in this regard; a further intriguing finding is that these ice films can emulate biological forms.

Crystal growth as an excitable medium

Crystal growth has been widely studied for many years, and, since the pioneering work of Burton, Cabrera and Frank, spirals and target patterns on the crystal surface have been understood as forms of tangential crystal growth mediated by defects and by two-dimensional nucleation. Similar spirals and target patterns are ubiquitous in physical systems describable as excitable media. Here, we demonstrate that this is not merely a superficial resemblance, that the physics of crystal growth can be set within the framework of an excitable medium, and that appreciating this correspondence may prove useful to both fields. Apart from solid crystals, we discuss how our model applies to the biomaterial nacre, formed by layer growth of a biological liquid crystal.

Runaway electrification of friable self-replicating granular matter.

We establish that the nonlinear dynamics of collisions between particles favors the charging of an insulating, friable, self-replicating granular material that undergoes nucleation, growth, and fission processes; we demonstrate with a minimal dynamical model that secondary nucleation produces a positive feedback in an electrification mechanism that leads to runaway charging. We discuss ice as an example of such a self-replicating granular material: We confirm with laboratory experiments in which we grow ice from the vapor phase in situ within an environmental scanning electron microscope that charging causes fast-growing and easily breakable palmlike structures to form, which when broken off may form secondary nuclei. We propose that thunderstorms, both terrestrial and on other planets, and lightning in the solar nebula are instances of such runaway charging arising from this nonlinear dynamics in self-replicating granular matter.

Nacre: A Unique Biomaterial Patterned by Liquid Crystals

The sequence of formation of the organic and inorganic components of nacre in bivalves and gastropods is re-studied. We reach the conclusion that interlamellar membranes are formed well in advance of the other elements. In this way, we support and refine the compartment theory for the formation of nacre. We explain the arrangement of chitin crystallites within a single interlamellar membrane and the layering of interlamellar membranes as a process of formation of a liquid crystal.

Microstructures in the Formation of Chemical Gardens

Chemical gardens are biomimetic plantlike growths formed by a mixture of salts which precipitate by a combination of convection forced by osmosis, free convection and chemical reactions. Chemical gardens may be implicated in other phenomena of industrial interest which involve precipitation across a colloidal gel membrane that separates two different aqueous solutions, for example, in cement technology and metal corrosion processes. However, the variation in chemical composition, morphology and mechanical properties of the different surfaces of these formations is not well known. Several salts in different concentrations and conditions have been explored under terrestrial gravity and microgravity. The chemical garden structures have been characterised by morphology analysis, scanning electron microscopy, chemical analysis and X-ray diffraction, correlating these data with the biomimetic growth and the physical-chemical nanoprocesses involved in it. This approach may also be useful for the analysis of biomaterials with interesting biomechanical properties.