An origin-of-life reactor to simulate alkaline hydrothermal vents.

Chemiosmotic coupling is universal: practically all cells harness electrochemical proton gradients across membranes to drive ATP synthesis, powering biochemistry. Autotrophic cells, including phototrophs and chemolithotrophs, also use proton gradients to power carbon fixation directly. The universality of chemiosmotic coupling suggests that it arose very early in evolution, but its origins are obscure. Alkaline hydrothermal systems sustain natural proton gradients across the thin inorganic barriers of interconnected micropores within deep-sea vents. In Hadean oceans, these inorganic barriers should have contained catalytic Fe(Ni)S minerals similar in structure to cofactors in modern metabolic enzymes, suggesting a possible abiotic origin of chemiosmotic coupling. The continuous supply of H2 and CO2 from vent fluids and early oceans, respectively, offers further parallels with the biochemistry of ancient autotrophic cells, notably the acetyl CoA pathway in archaea and bacteria. However, the precise mechanisms by which natural proton gradients, H2, CO2 and metal sulphides could have driven organic synthesis are uncertain, and theoretical ideas lack empirical support. We have built a simple electrochemical reactor to simulate conditions in alkaline hydrothermal vents, allowing investigation of the possibility that abiotic vent chemistry could prefigure the origins of biochemistry. We discuss the construction and testing of the reactor, describing the precipitation of thin-walled, inorganic structures containing nickel-doped mackinawite, a catalytic Fe(Ni)S mineral, under prebiotic ocean conditions. These simulated vent structures appear to generate low yields of simple organics. Synthetic microporous matrices can concentrate organics by thermophoresis over several orders of magnitude under continuous open-flow vent conditions.

Rapid automated materials synthesis instrument: exploring the composition and heat-treatment of nanoprecursors toward low temperature red phosphors.

We report on the commissioning experimental run of the rapid automated materials synthesis instrument (RAMSI), a combinatorial robot designed to manufacture, clean, and print libraries of nanocrystal precursor solid compositions. The first stage of RAMSI, parallel synthesis, uses a fully automated high throughput continuous hydrothermal (HiTCH) flow reactor for automatic metal salt precursor mixing, hydrothermal flow reaction, and sample slurry collection. The second stage of RAMSI provides integrated automated cleanup, and the third section is a ceramic printing function. Nanocrystal precursor solid ceramics were synthesized from precursor solutions and collected into 50 mL centrifuge tubes where they were cleaned by multiple centrifugation and redispersion cycles (monitored by intelligent scanning turbidimetry) and printed with an automated pipette. Eight unique compositions of a model phosphor library comprising pure nano-Y(OH)(3) and Eu(3+) doped-yttrium hydroxide, Y(OH)(3):Eu(3+) nanocrystal precursor solid were synthesized (with 2 centrifuge tubes' worth collected per composition), processed, and printed in duplicate as 75, 100, and 125 microL dots in a 21.6 ks (6 h) experiment (note: the actual time for synthesis of each sample tube was only 12 min so up to 60 compositions could easily be synthesized in 12 h if one centrifuge tube per composition was collected instead). The Y(OH)(3):Eu(3+) samples were manually placed in a furnace and heat-treated in air for 14.4 ks (4 h) in the temperature range 200-1200 at 100 degrees C intervals (giving a total of 84 samples plus one as-prepared pure Y(OH)(3) sample). The as-prepared and heat-treated ceramic samples were affixed to 4 mm wide hemispherical wells in a custom-made aluminum well-plate and analyzed using a fluorescence spectrometer. When the library was illuminated with a 254 nm light source (and digitally imaged and analyzed), the 3 mol % Eu(3+) sample heat-treated at 1200 degrees C gave the most intense fluorescence (major red peak at 612 nm); however, an identical nanocrystal precursor heat-treated at only 500 degrees C (identified as Y(2)O(3):Eu(3+) after heat treatment) was the brightest phosphor under illumination of the samples heat-treated at or below 1000 degrees C.

Biological evaluation of solid freeformed, hard tissue scaffolds for orthopedic applications.

PURPOSE: Hydroxyapatite (HA) lattices were made by extrusion freeforming, a rapid prototyping process, and sintered to produce hard tissue scaffolds for bone regeneration. These highly reticulated lattice structures can be built directly from a computer design file which decides and controls their macroscopic shape, pore structure and size distribution. They are therefore defect-specific and show potential in tissue engineering for non-load bearing sites. METHODS: Using a commercial human osteoblast-like cell line (HOS TE 85), biocompatibility was evaluated in an in vitro study. A high level of cell adhesion was evident by scanning electron microscopy on both convex and concave surfaces and the cell attachment was revealed at different depths into the scaffold. An AlamarBlue(R) assay was carried out to assess cell proliferation, which was further confirmed by quantifying total DNA concentration and total protein content. RESULTS: The cell proliferation was significant and the pattern was comparable to that of the tissue culture control, ThermanoxTM. ALP activity and osteocalcin were quantified to evaluate the extent of cell differentiation, which confirmed the retention of the phenotype for the period studied. Mineralization of the matrix was determined via formation of nodules. CONCLUSIONS: HA scaffolds are non-toxic, able to maintain cell viability and support cell growth, proliferation, differentiation, and nodule formation.

High-throughput continuous hydrothermal synthesis of an entire nanoceramic phase diagram.

A novel High-Throughput Continuous Hydrothermal (HiTCH) flow synthesis reactor was used to make directly and rapidly a 66-sample nanoparticle library (entire phase diagram) of nanocrystalline Ce(x)Zr(y)Y(z)O(2-delta) in less than 12 h. High resolution PXRD data were obtained for the entire heat-treated library (at 1000 degrees C/1 h) in less than a day using the new robotic beamline I11, located at Diamond Light Source (DLS). This allowed Rietveld-quality powder X-ray diffraction (PXRD) data collection of the entire 66-sample library in <1 day. Consequently, the authors rapidly mapped out phase behavior and sintering behaviors for the entire library. Out of the entire 66-sample heat-treated library, the PXRD data suggests that 43 possess the fluorite structure, of which 30 (out of 36) are ternary compositions. The speed, quantity and quality of data obtained by our new approach, offers an exciting new development which will allow structure-property relationships to be accessed for nanoceramics in much shorter time periods.

Segregation in multicomponent ceramic colloids during drying of droplets.

Studies of drying of colloidal droplets focus on unary particle systems. We report here the drying of binary and ternary powder suspensions. When multicomponent ceramic suspensions are deposited in the form of small drops (5 microl), particle segregation can occur on drying so that the upper surface of the powder residue does not match that of the bulk composition. We show that the segregation effect and the shape of the droplet residues are both related to the participation of particles in two types of flow during drying; radial flow toward the rim where the three-phase boundary becomes locked by a pile up of particles and secondly, recirculation flows in the remaining liquid driven by Marangoni stresses. Methods to control both shape and segregation are described. The phenomenon described is general and independent of the method of preparing the drops but the motivation is to obtain uniform drop shape and composition in thick film ceramic libraries in combinatorial ink-jet printing.

Fine ceramic lattices prepared by extrusion freeforming.

Fine ceramic lattices with spatial resolution <100 microm and having precise dimensions and intricate hierarchical structure are fabricated by extrusion freeforming, a rapid prototyping technique, which allows overall shape and structure to be controlled by computer. The procedure can be used for any fine ceramic powder and can therefore find applications as diverse as microwave and terahertz metamaterials (artificial crystals), hard tissue scaffolds, microfluidic devices, and metal matrix composite preforms. The examples presented here are calcium phosphate lattices with three structure levels: submicron pores, which enhance cell-surface interactions, pores of tens of microns to encourage bone ingrowth, and corridors (hundreds of microns) for vascularization. With controlled pore structures on these scales, the lattices are expected to provide customized biological, mechanical, and geometrical requirements.

Morphologies developed by the drying of droplets containing dispersed and aggregated layered double hydroxide platelets.

Despite much interest in the structures formed from droplets of suspension as they dry, there are few studies involving plate-like particles. Layered double hydroxide suspensions were prepared with pH adjusted to give well-dispersed and flocculated variants that were characterised by sedimentation and rheology measurements. In the well-dispersed suspension, the three-phase boundary was pinned and radial flow created a peripheral wall. The platelet structure involved local flat packing but was replete with scrolls that result from the recirculation flows in the droplets as they dry. In contrast, the flocculating suspension produced flatter droplet relics and the microstructure consisted of ordered domains which were disoriented with respect to each other. Although of scientific interest, the control of these structures will make it possible to use direct ink-jet printing to build 3D shapes for the preparation of aligned, ordered nanocomposites based on plate-like particles in which platelet preferred orientation mimics the structures found in nacre.

Drying of colloidal droplets on superhydrophobic surfaces.

Recent research on the flow patterns during the drying of droplets of solutions or suspensions has revealed a characteristic flow of dissolved or suspended material to the droplet periphery to produce the 'coffee ring' phenomenon. This effect was used to make ceramic well-plates by spontaneous manufacturing. Here we demonstrate that when a colloidal droplet dries on a superhydrophobic surface, the effect is rather different. Evaporation from the region adjacent to the three phase line becomes so restricted that the interior flows, and hence the final destination of particles, changes and the characteristic bowl-shape becomes inverted.

Arched structures created by colloidal droplets as they dry.

When a sessile drop containing colloidal particles or solute dries, the well-known "coffee ring" forms at the periphery because of radial flows. Here we demonstrate for the first time that if such drops are in close proximity to each other they form arches as they dry. The interaction between adjacent drops causes spatial variations in humidity so that drying from neighboring regions slows down and particles pile up in places where drying is most rapid. This discovery shows that the deceptively simple process of droplet drying still has more to reveal, and the effect probably influences all droplet technologies in an environment of locally nonuniform humidity.

Microfeeding with different ultrasonic nozzle designs.

Microfeeding of dry powder excited by ultrasonic vibration makes use of relatively simple equipment and can be applied to solid freeforming and pharmaceutical dosing. The nozzle was a vertical glass capillary and four configurations for ultrasonic actuation were investigated: Type I had a piezoelectric transducer ring bonded to the base of a cylindrical water-containing vessel containing an axial nozzle; Type II had a piezoelectric transducer ring attached to the sidewall of the vessel; Type III used direct mechanical connection to the glass wall of the capillary to give nominally longitudinal vibration; and Type IV also used direct connection to the glass tube but arranged to give progressive wave vibration. The experimental results show that all four configurations realized powder microfeeding and dosing but the characteristics, in terms of minimum flow rate, dependence on voltage amplitude and uniformity of dose varied considerably. The discharge of particles was observed by a high-speed camera.

Ordered assemblies of clay nano-platelets.

We demonstrate five methods of arranging smectite clay tactoids into layered arrangements as a part of the quest for the biomimetic simulation of nacre. Provided the clay is not fully exfoliated, the tactoids retain sufficient rigidity for alignment and we present micrographs which demonstrate these ordered structures. This paves the way for exploration of the high mineral filler end of polymer-clay nanocomposites which can approach the high aragonite volume fraction of nacre. The clay was dispersed in water without additives by ultrasonic agitation, cleaned by partial sedimentation and the resulting suspension was subjected to controlled phase separation by sedimentation, centrifugation, controlled rate slip casting, filtration and electrophoresis. Well-aligned parallel layers of platelets were obtained from all the five methods, the best stacking being associated with slip cast layers. Polyethylene oxide was incorporated into these well-aligned tactoids.

A critical appraisal of polymer-clay nanocomposites.

The surge of interest in and scientific publications on the structure and properties of nanocomposites has made it rather difficult for the novice to comprehend the physical structure of these new materials and the relationship between their properties and those of the conventional range of composite materials. Some of the questions that arise are: How should the reinforcement volume fraction be calculated? How can the clay gallery contents be assessed? How can the ratio of intercalate to exfoliate be found? Does polymerization occur in the clay galleries? How is the crystallinity of semi-crystalline polymers affected by intercalation? What role do the mobilities of adsorbed molecules and clay platelets have? How much information can conventional X-ray diffraction offer? What is the thermodynamic driving force for intercalation and exfoliation? What is the elastic modulus of clay platelets? The growth of computer simulation techniques applied to clay materials has been rapid, with insight gained into the structure, dynamics and reactivity of polymer-clay systems. However these techniques operate on the basis of approximations, which may not be clear to the non-specialist. This critical review attempts to assess these issues from the viewpoint of traditional composites thereby embedding these new materials in a wider context to which conventional composite theory can be applied. (210 references).

London University Search Instrument: a combinatorial robot for high-throughput methods in ceramic science.

This paper describes the design, construction, and operation of the London University Search Instrument (LUSI) which was recently commissioned to create and test combinatorial libraries of ceramic compositions. The instrument uses commercially available powders, milled as necessary to create thick-film libraries by ink-jet printing. Multicomponent mixtures are prepared by well plate reformatting of ceramic inks. The library tiles are robotically loaded into a flatbed furnace and, when fired, transferred to a 2-axis high-resolution measurement table fitted with a hot plate where measurements of, for example, optical or electrical properties can be made. Data are transferred to a dedicated high-performance computer. The possibilities for remote interrogation and search steering are discussed.

Novel thermoplastic starch-clay nanocomposite foams.

Novel thermoplastic starch (TPS)-clay nanocomposite foams were prepared by melt-processing. The use of urea as plasticizer avoids the cracking of TPS during storage and enhances the dispersion of ammonium-treated clay in TPS. X-ray diffraction shows an increase in the basal plane spacings of both natural and treated clays, suggesting formation of nanocomposites. Scanning electron microscopy shows spontaneously formed regular foam structures with 84% porosity in TPS-ammonium-treated clay. This does not form in TPS or TPS-natural clay nanocomposites. This result implies that the regular foam formation is due to the ammonium surfactant of clay, which produces ammonia gas acting as an internal blowing agent. Thermogravimetric analysis confirms this deduction.

Device for preparing combinatorial libraries in powder metallurgy.

This paper describes a powder-metering, -mixing, and -dispensing mechanism that can be used as a method for producing large numbers of samples for metallurgical evaluation or electrical or mechanical testing from multicomponent metal and cermet powder systems. It is designed to make use of the same commercial powders that are used in powder metallurgy and, therefore, to produce samples that are faithful to the microstructure of finished products. The particle assemblies produced by the device could be consolidated by die pressing, isostatic pressing, laser sintering, or direct melting. The powder metering valve provides both on/off and flow rate control of dry powders in open capillaries using acoustic vibration. The valve is simple and involves no relative movement, avoiding seizure with fine powders. An orchestra of such valves can be arranged on a building platform to prepare multicomponent combinatorial libraries. As with many combinatorial devices, identification and evaluation of sources of mixing error as a function of sample size is mandatory. Such an analysis is presented.

A drop-on-demand ink-jet printer for combinatorial libraries and functionally graded ceramics.

A printer has been designed and built for the preparation of combinatorial libraries of ceramics and for solid freeforming of functionally graded ceramics with three-dimensionally programmable spatial variation in composition. Several ceramic suspensions (as inks) can be subjected to micromixing behind the nozzle and printed at precise positions. Both mixing and positioning are computer-controlled. The machine consists of an XY table to control the geometry, a set of electromagnetic valves that manage the mixing, a combined electromagnetic valve and sapphire nozzle that form the print head, and a computer that controls the whole system. The mixing valves can eject as little as 1 mg/s ink into the mixing chamber. The printer has been controlled, run, calibrated and tested; the composition and geometry of printed mixtures can be controlled precisely. This method for the controlled mixing of powders facilitates the advance of combinatorial methods within the materials sciences.