Chemical composition from photos: Dried solution drops reveal a morphogenetic tree.

Under nonequilibrium conditions, inorganic systems can produce a wealth of life-like shapes and patterns which, compared to well-formed crystalline materials, remain widely unexplored. A seemingly simple example is the formation of salt deposits during the evaporation of sessile droplets. These evaporites show great variations in their specific patterns including single rings, creep, small crystals, fractals, and featureless disks. We have explored the patterns of 42 different salts at otherwise constant conditions. Based on 7,500 images, we show that distinct pattern families can be identified and that some salts (e.g., Na2SO4 and NH4NO3) are bifurcated creating two distinct motifs. Family affiliations cannot be predicted a priori from composition alone but rather emerge from the complex interplay of evaporation, crystallization, thermodynamics, capillarity, and fluid flow. Nonetheless, chemical composition can be predicted from the deposit pattern with surprisingly high accuracy even if the set of reference images is small. These findings suggest possible applications including smartphone-based analyses and lightweight tools for space missions.

Coiling of Secondary Tubes Formed from the Colloidal Exhaust of Primary Chemical Gardens.

Chemical gardens are self-organized precipitate structures such as thin-walled tubes and membrane-bound cells reminiscent of biological shapes. These usually inorganic precipitates compartmentalize the reaction system and allow the study of materials synthesis in very steep concentration gradients. We create such tubes by steadily injecting a mixture of MnCl2 and CuSO4 solutions into a large reservoir of sodium silicate solution. The growing tube is open at its tip and ejects a stream of colloidal particles that aggregate to form a secondary tube above the original one. This secondary tube can coil into a tightly wound nest-like structure, freely suspended underneath the solution-air interface. Using three-dimensional image reconstruction, we analyze the onset of coiling and show that the structure is helical with a helix radius that increases in the vertical direction. The height at which the coiling begins is lowered with each successive repeat of the growth experiment, suggesting that coiling is induced by small variations in the density of the silicate solution.

Nonclassical Crystallization Causes Dendritic and Band-Like Microscale Patterns in Inorganic Precipitates.

The self-organization of complex solids can create patterns extending hierarchically from the atomic to the macroscopic scale. A frequently studied model is the chemical garden system which consists of life-like precipitate shapes. In this study, we examine the thin walls of chemical gardens using microfluidic devices that yield linear Ni(OH)2 precipitate membranes. We observe distinct light-scattering patterns within the compositionally pure membranes, including disorganized spots, dendrites, and parallel bands. The bands are tilted with respect to the membrane axis and their spacing (20-100 µm) increases with increasing flow rates. Scanning electron microscopy reveals that the bands consist of submicron particles embedded in a denser material and these particles are also found in the reactant stream. We propose that dendrites and bands arise from the attachment of solution-borne nanoparticles. The bands are generated by particle-aggregation zones moving upstream along the slowly advancing membrane surface. The speed of the aggregation zones is proportional to the band distance and defines the system's dispersion relation. This speed-wavelength dependence and the flow-opposing motion of the aggregation zones are likely caused by low particle concentrations in the wake of the zones that only slowly recover due to Brownian motion and particle nucleation.

Pattern selection by material aging: Modeling chemical gardens in two and three dimensions.

Chemical gardens are complex, often macroscopic, structures formed by precipitation reactions. Their thin walls compartmentalize the system and adjust in size and shape if the volume of the interior reactant solution is increased by osmosis or active injection. Spatial confinement to a thin layer is known to result in various patterns including self-extending filaments and flower-like patterns organized around a continuous, expanding front. Here, we describe a cellular automaton model for this type of self-organization, in which each lattice site is occupied by one of the two reactants or the precipitate. Reactant injection causes the random replacement of precipitate and generates an expanding near-circular precipitate front. If this process includes an age bias favoring the replacement of fresh precipitate, thin-walled filaments arise and grow-like in the experiments-at the leading tip. In addition, the inclusion of a buoyancy effect allows the model to capture various branched and unbranched chemical garden shapes in two and three dimensions. Our results provide a model of chemical garden structures and highlight the importance of temporal changes in the self-healing membrane material.

Shape Evolution of Precipitate Membranes in Flow Systems.

Chemical gardens are macroscopic structures that form when a salt seed is submerged in an alkaline solution. Their thin precipitate membranes separate the reactant partners and slow down the approach toward equilibrium. During this stage, a gradual thickening occurs, which is driven by steep cross-membrane gradients and governed by selective ion transport. We study these growth dynamics in microfluidic channels for the case of Ni(OH)2 membranes. Fast flowing reactant solutions create thickening membranes of a nearly constant width along the channel, whereas slow flows produce wedge-shaped structures that fail to grow along their downstream end. The overall dynamics and shapes are caused by the competition of reactant consumption and transport replenishment. They are reproduced quantitatively by a two-variable reaction-diffusion-advection model which provides kinetic insights into the growth of precipitate membranes.

Perovskite chemical gardens: highly fluorescent microtubes from self-assembly and ion exchange.

We report the shape-preserving conversion of self-assembled CaCO3 microtubes to PbCO3 and MAPbBr3 perovskite. The first step induces the growth of cerussite needles on the outer surface. When further converted, these hedgehog-like structures become fluorescent. Additional spatial control of the process yields Janus tubes of CaCO3 and perovskite segments.

Electricity on Rubber Surfaces: A New Energy Conversion Effect.

This work describes the conversion of mechanical energy to electricity, by periodically stretching rubber tubing and allowing it to relax. The rubber surface shows periodic and reversible electrostatic potential variations, in phase with the tubing length. The potential change depends on the elastomer used: silicone loses charge when stretched and becomes strongly negative when relaxed, whereas the stretched natural rubber is positive, becoming negative when relaxed. Every other elastomeric material that was tested also showed periodic potential but followed different patterns. When the motion stops, the potential on the resting samples decreases quickly to zero. The potential oscillation amplitude decreases when the relative humidity decreases from 65 to 27%, but it is negligible when the rubber tubing is previously swollen with water or paraffin oil. Elastomer charging patterns do not present the well-known characteristics of piezo-, flexo-, or triboelectricity, and they are discussed considering rubber rheology, wear, and surface properties, including the possibility of surface piezoelectricity. The following mechanism is suggested: rubber stretching provokes chemical and morphology changes in its surface, followed by a change in the surface concentration of H+ and OH- ions adsorbed along with water. The possibility of the occurrence of similar variations in other systems (both inert and biological) is discussed, together with its implications for energy scavenging from the environment.

Pressure Controlled Chemical Gardens.

The dissolution of metal salts in silicate solution can result in the growth of hollow precipitate tubes. These "chemical gardens" are a model of self-organization far from the equilibrium and create permanent macroscopic structures. The reproducibility of the growth process is greatly improved if the solid salt seed is replaced by a salt solution that is steadily injected by a pump; however, this modification of the original experiment eliminates the membrane-based osmotic pump at the base of conventional chemical gardens and does not allow for analyses in terms of the involved pressure. Here we describe a new experimental method that delivers the salt solution according to a controlled hydrostatic pressure. In one form of the experiment, this pressure slowly decreases as zinc sulfate solution flows into the silicate-containing reaction vessel, whereas a second version holds the respective solution heights constant. In addition to three known growth regimes (jetting, popping, budding), we observe single tubes that fill the vessel in a horizontally undulating but vertically layered fashion (crowding). The resulting, dried product has a cylindrical shape, very low density, and one continuous connection from top to bottom. We also present phase diagrams of these growth modes and show that the flow characteristics of our experiments follow a reaction-independent Hagen-Poiseuille equation.

Chemical gardens without silica: the formation of pure metal hydroxide tubes.

Contrary to common belief, hollow precipitation tubes form in the absence of silicate if sodium hydroxide solution is injected into solutions of various metal ions. In many cases, the growth speed has a power law dependence on the flow rate. For vanadyl, we observe damped oscillations in the tube height.

Self-Alignment of Beads and Cell Trapping in Precipitate Tubes.

Propagating reaction fronts allow the formation of materials in self-sustained, steep concentration gradients, which would otherwise rapidly decay. These conditions can result in macroscopic, noncrystallographic structures, such as tubes with large aspect ratios. For hollow silica/Zn(OH)2 tubes, we report the inclusion of diverse mesoscopic building blocks ranging from polymer beads to biological cells. For agarose beads, we observe spontaneous alignment along vertical tracks; the nearly periodic spacing of the beads along these tracks follows a log-normal distribution. We interpret this patterning in terms of hydrodynamic recruitment and discuss similarities to the adhesion dynamics of leukocytes in blood vessels. For diatoms and other cells, we observe novel surface textures, and yeast tagged with a green fluorescent protein shows strong fluorescence activity after trapping. The inclusion of these guest units should improve the possibilities for the application of these tubes in microfluidics and biotechnology.

From hydrodynamic plumes to chemical gardens: the concentration-dependent onset of tube formation.

Many inorganic precipitation reactions self-organize macroscopic tubes known as chemical gardens. We study the nonequilibrium formation of these structures by injecting aqueous sodium sulfide solution into a reservoir of iron(II) chloride solution. Our experiments reveal a distinct, concentration-dependent transition from convective plumes of reaction-induced, colloidal particles to mechanically connected, hollow tubes. The transition concentration (0.1 mol/L) is widely independent of the injection rate and causes a discontinuous change from the radius of the plume stalk to the radius of the tube. In addition, tubes have lower growth speeds than plumes. At the transition concentration, one observes the initial formation of a plume followed by the growth of a mechanically weak tube around a jet of upward-moving precipitation particles. We find that the plumes' morphology and geometric scaling are similar to that of laminar starting plumes in nonreactive systems. The characterization of dried tubes by X-ray diffraction indicates the presence of greigite and lepidocrocite.

Long-lasting oscillations in the electro-oxidation of formic acid on PtSn intermetallic surfaces.

Even when in contact with virtually infinite reservoirs, natural and manmade oscillators typically drift in phase space on a time-scale considerably slower than that of the intrinsic oscillator. A ubiquitous example is the inexorable aging process experienced by all living systems. Typical electrocatalytic reactions under oscillatory conditions oscillate for only a few dozen stable cycles due to slow surface poisoning that ultimately results in destruction of the limit cycle. We report the observation of unprecedented long-lasting temporal oscillations in the electro-oxidation of formic acid on an ordered intermetallic PtSn phase. The introduction of Sn substantially increases the catalytic activity and retards the irreversible surface oxidation, which results in the stabilization of more than 2200 oscillatory cycles in about 40 h; a 30-40-fold stabilization with respect to the behavior of pure Pt surfaces. The dynamics were modeled and numerical simulations point to the surface processes underlying the high stability.

Experimental assessment of the sensitiveness of an electrochemical oscillator towards chemical perturbations.

In this study we address the problem of the response of a (electro)chemical oscillator towards chemical perturbations of different magnitudes. The chemical perturbation was achieved by addition of distinct amounts of trifluoromethanesulfonate (TFMSA), a rather stable and non-specifically adsorbing anion, and the system under investigation was the methanol electro-oxidation reaction under both stationary and oscillatory regimes. Increasing the anion concentration resulted in a decrease in the reaction rates of methanol oxidation and a general decrease in the parameter window where oscillations occurred. Furthermore, the addition of TFMSA was found to decrease the induction period and the total duration of oscillations. The mechanism underlying these observations was derived mathematically and revealed that inhibition in the methanol oxidation through blockage of active sites was found to further accelerate the intrinsic non-stationarity of the unperturbed system. Altogether, the presented results are among the few concerning the experimental assessment of the sensitiveness of an oscillator towards chemical perturbations. The universal nature of the complex chemical oscillator investigated here might be used for reference when studying the dynamics of other less accessible perturbed networks of (bio)chemical reactions.

The impact of the alkali cation on the mechanism of the electro-oxidation of ethylene glycol on Pt.

By means of in situ IR spectroscopy we investigate the effect of dissolved alkali cations on the electro-oxidation of ethylene glycol on platinum in alkaline media. The results revealed that the increase in the oxidation currents (Li(+) < Na(+) < K(+)) is reflected in the increase in the ratio between carbonate and oxalate produced.

Autocatalysis in the open circuit interaction of alcohol molecules with oxidized Pt surfaces.

We studied the open circuit interaction of methanol and ethanol with oxidized platinum electrodes using in situ infrared spectroscopy. For methanol, it was found that formic acid is the main species formed in the initial region of the transient and that the steep decrease of the open circuit potential coincides with an explosive increase in the CO2 production, which is followed by an increase in the coverage of adsorbed CO. For ethanol, acetaldehyde was the main product detected and only traces of dissolved CO2 and adsorbed CO were found after the steep potential decay. In both cases, the transients were interpreted in terms of (a) the emergence of sub-surface oxygen in the beginning of the transient, where the oxide content is high, and (b) the autocatalytic production of free platinum sites for lower oxide content during the steep decay of the open circuit potential.