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Polymeric nanoparticles have important applications in drug delivery, biotechnology, diagnostics and energy harvesting. We report a new technique named electrospray nanoprecipitation, which combines electrospray with agitated solvent displacement. The process enables one-step formation of polymeric nanoparticles

The preparation of capsules for medical and industrial use can be achieved via several conventional routes, yielding either hard or soft receptacles, depending on the type and the content of the material to be encapsulated. Together with tablets, capsules are amongst the most commonly used means of administering medication and this makes progress in capsule preparation technology a key area of drug delivery research. Here we uncover new technology for the preparation of capsules with porous chambers. The novelty is signified in the use of an electrohydrodynamic process engineering route and its potential is elucidated using a polymeric material; polymethylsilsesquioxane, which can be converted into an identical ceramic form by means of simple pyrolysis. Thus, both polymeric and ceramic capsules have been prepared. The effects of process control parameters such as the applied voltage and flow rate, on the characteristics of the capsules prepared are discussed.

Porous polymeric near-spherical capsules, ~ 3.6 mm in diameter, were prepared using an electrodydrodynamic process. These capsules were pyrolysed to porous ceramics, ~ 3 mm in diameter. The ceramic capsules had interconnected pores of ~ 1.3 μm in size, and large cells with a mean size of 28 μm. The larger pores resemble the cells in a typical ceramic foam and were evenly distributed throughout the structure. A large proportion of the ceramic capsules contained 65-70% porosity, and their compressive strength was 0.2-0.4 MPa. © 2008 Elsevier B.V. All rights reserved.

Electrospraying and electrospinning are amongst the common methods of forming polymeric micro- and nano-scaled structures using electrically driven polymer processing. Utilising a co-axial flow of materials has been successful in enabling encapsulated structures to be generated by these techniques. However, with both of these methods, including their respective co-axial forms, there is limited control over the deposition of the resultant structures. Recently, an electrically driven direct-writing method has been developed which is based upon the same fundamental principles, but with the ability to deposit and form structures in an ordered manner, which has previously been restricted largely to single needle flow processing. In this paper, using selected polymeric materials, we demonstrate two novel methods of this direct-write system. The first method shows how the shape of formed structures can be varied in-situ using a single needle flow direct-write process. Secondly, we demonstrate how co-axial flows can be utilised to write and form encapsulated structures. We envisage that while the use of electrospinning and electrospraying methods will continue to expand, these novel areas will offer much greater control over the forming of a plethora of micro- and nano-scaled structures and will be essential for topographic studies (e. g. of living cells), novel particle preparation methods, coatings and direct writing of polymeric biomaterials. © 2011 Springer-Verlag France.

The selection of a desirable solvent or solvent system as the carrier of a particular polymer is fundamental for the optimisation of electrospinning. Solvent selection is pivotal in determining the critical minimum solution concentration to allow the transition from electrospraying to electrospinning, thereby significantly affecting solution spinnability and the morphology of the electrospun fibres. 28 solvents diversely positioned on the Teas graph were studied for their solubility and electrospinnability for making polymethylsilsesquioxane (PMSQ) solutions. The results are combined and mapped on the Teas graph using different colour codes. Based on this new spinnability–solubility map, various solvent systems for PMSQ are methodically developed. Solvents are selected to produce binary solvent systems that have solvent parameters close to a good single solvent for electrospinning of the polymer solution. This work shows that solvents of high solubility do not necessarily produce solutions good for electrospinning. Polymethylsilsesquioxane solutions of the same concentration in solvents of partial solubility showed better spinnability than solutions in solvents of high solubility. A methanol–propanol binary solvent system produced electrospun fibres with high surface porosity, showing that high volatility and high vapour pressure difference among solvents mixed can induce phase separation in electrospinning. It is noteworthy that the binary solvent system mixing 2-nitropropane (high solubility) and dimethylsulphoxide (non-solvent), neither of which exhibited high volatility, also produced highly porous electrospun fibres. This demonstrates that phase separation can be induced by solubility difference in the electrospun polymer solution.

A suspension of 15nm diameter gold nanoparti-cles has been deposited along a line on a silicon substrate with the assistance of a jet generated in an electric field. In order to control the evaporation of the solvent used to suspend the gold nanoparticles, a heating device was used to change the substrate temperature. Layer-by- layer deposition enabled the direct writing of gold tracks having an electrical resistivity of 1.8 × 10-7 Ωm, only about an order of magnitude above the electrical resistivity of bulk gold.

Two types of polymeric precursors for silicon carbide (SiC) were dissolved in dichloromethane. Subsequently, between 10–80 wt% of silicon nitride (Si3N4) and titanium carbide (TiC) powder were added separately into the solutions to make SiC-Si3N4 and SiC-TiC suspensions. Cubes of polyurethane (PU) foams were soaked in precursor solution and suspensions and pyrolyzed in flowing nitrogen to produce SiC, SiC-Si3N4 and SiC-TiC composite foams. Some foams were heated further in nitrogen to 1600°C. Shrinkage observed after pyrolysis and further heating the foams was measured and can be reduced by varying the concentration of polymeric precursor, Si3N4 and TiC content. The foams produced have porosities in the range 85–96%. The average compressive strength of the foams is in the range of 1.1–1.6 MPa.

A polysilane solution used as a silicon carbide (SiC) precursor was mixed with different amounts of titanium carbide (TiC) powder and open cell polyurethane (PU) foams were dipped in these suspensions. The resulting pre-foams were pyrolyzed at 900°C in nitrogen and then heated further at various temperature between 1100 and 1600°C in the same atmosphere to produce SiC–TiC composite foams. The evolution of the composite foams has been studied using thermogravimetry and X-ray diffraction. The PU foam, pre-foams and the SiC–TiC composite foams were characterized by optical and scanning electron microscopy. These studies show that the pre-foams retained their shape well during pyrolysis and the composite foams produced consist of an open cell structure and hole-free solid struts. Prevention of cracking in the foams were dependent on the TiC content. The shrinkage observed during the conversion of the pre-foams to the composite ceramic foams can be controlled by varying the TiC content and the sintering temperature.

A polysilane was used as the precursor for silicon carbide (SiC) and different amounts of it was dissolved in dichloromethane. Subsequently, between 10 to 80 %wt of alumina (Al2O3) powder was added into the solutions to make SiC-Al2O3 suspensions. Cubes of polyurethane (PU) foams with open cells in the size range 500-1200μm were soaked in these suspensions and pyrolysed in flowing nitrogen to produce SiC-Al2O3 composite foams. Some foams were heated further in nitrogen to 1300°C. The foams produced consist of an open cell structure and hole-free solid struts which were also cracks free in the polysilane-Al2O3 80:2Owt% formulation. The retention of shape during processing was excellent. Shrinkage observed after pyrolysis and further heating the foams was measured and can be controlled by varying the Al2O3 content. The foams produced have porosities in the range 87 to 95%. The maximum compressive strength of the pyrolysed foams prepared using the polysilane-Al2O3 80:20 wt% formulation was 2.3MPa.

A new method of forming silicon carbide–silicon nitride composite foams is presented. These are prepared by immersing a polyurethane foam in a polysilane precursor solution mixed with Si3N4 powder to form a pre-foam followed by heating it in nitrogen at >900°C. X-ray diffraction patterns indicate that a SiC–Si3N4 composite was formed after sintering the ceramic foam at >1500°C. Micrographs show that most of these foams have well-defined open-cell structures and macro-defect free struts. The shrinkage is reduced considerably due to the addition of Si3N4 particles.

A simple method was developed to produce silicon carbide foams using polysilane polymeric precursors. Polyurethane foams were immersed in polysilane precursor solutions to prepare pre-foams. Subsequently, these were heated in nitrogen at different temperatures in the range of 900°C to 1300°C. The silicon carbide foams produced in this manner showed well-defined open-cell structures and the struts in the foams were free of voids. The shrinkage which accompanies pyrolysis of the pre-foams was reduced with increasing the concentration of the polymeric precursor solutions.

Several polysilanes with different overall functionalities have been synthesized and pyrolyzed to produce porous silicon carbide. The polysilanes and their ceramic products have been characterized using gel permeation chromatography, Fourier transform-infrared spectroscopy, thermogravimetry, X-ray diffractometry and microscopy. Some products were foams while others were micro-porous ceramics. The effect of the final pyrolytic yield on the Type of ceramic produced, its pore structure and shape retention are discussed. Two polysilanes were blended in various ratios to control the pyrolysis process more precisely. This allowed the Type, shape and pore-structure of the silicon carbide produced to be controlled more efficiently. There exists a relationship between the composition and structure of the precursors and their final pyrolytic yield and this determines the Type, shape retainability and pore structure of the ceramics produced. In this work, precursors or their blends which gave a final pyrolytic yield of 50–60 wt % produced the best silicon carbide foams.

Several polyurethane solutions of the same composition but varying temperature (25, 50, 75 and 100 °C), were subjected to an electric field whilst flowing through a conducting nozzle. All other typical electrospinning parameters (applied voltage, medium infusion rate and collecting distance) were kept constant. The effects of processing solution temperature on the resulting fibre morphologies were assessed using optical and scanning electron microscopy, and were also correlated with solution properties (surface tension, viscosity, electrical conductivity and density). It was observed that increasing the solution temperature leads to a significant reduction in the mean diameter and size distribution of the resulting fibres. Increasing the temperature from 25 to 100 °C enabled the reduction of the mean fibre diameter from 2.5 μm to 1.2 μm. The T m value of resulting fibres generally increased as the solution processing temperature increased suggesting a change to the orientation of polymer chains in the overall structure. © 2011 Elsevier B.V. All rights reserved.

Co-flowing media of a polymeric solution (30 wt% polymethylsilsesquioxane in ethanol) and a ceramic suspension (10 wt% alumina in glycerol) were subjected to an electric field. The flow rates of the media (10-30 microL min(-1)) and the applied voltage (0-11 kV) were varied systematically during the experimentation by making gradual increments to each variable, which enabled the construction of a mode selection map. Under co-flowing conditions, with the flow rate of polymer solution (outer needle) twice that of the ceramic suspension (inner needle), encapsulated droplets of polymer-coated alumina were produced within stable cone-jet mode. These were collected in a thin film of water and the resultant particle size varied between 1 and 38 microm. Encapsulation was confirmed with scanning electron microscopy and element analysis.

The use of polymeric precursors to produce ceramics is generating considerable interest . Owing to distinct advantages in processability, polymeric precursors have found applications in many areas such as ceramic fibers, foams and coatings. Ceramic coatings, in particular, are of immediate value in industry as a means of providing wear and corrosion resistance for articles used in adverse environments. The coating of engineering parts with ceramics using polymeric precursors is a relatively easy, quick and low-cost process compared with other processing methods such as chemical vapor deposition and plasma-coating.

During the last decade porous ceramic materials have been finding increasing applications due to their favorable properties such as high temperature stability, high permeability, low mass, low specific heat capacity and low thermal conductivity. These characteristics are essential for many technological applications such as catalyst supports, filters for molten metals and hot gases, refractory linings, thermal and fire insulators and porous implants [1, 2]. Ceramic foams can be produced by different methods, principally impregnation of polymer foams with slurries containing appropriate binders and ceramic particles followed by pressureless sintering at elevated temperatures [2–5]. This involves coating an open-cell polymeric sponge with a ceramic slurry several times, pyrolysis of the polymer to form a ceramic skeleton followed by sintering. Ceramic foams produced by this method are generally of low strength as their struts are thin and can contain a hole in the center [2, 6–8]. Recently, a new method to produce silicon carbide (SiC) foams using polymeric precursor solutions was developed by Bao et al. [9] where a polyurethane foam was immersed in a polymeric precursor solution to form a pre-foam which was pyrolyzed in nitrogen. The main advantages of this new approach are the simplicity and ease of control of structure of the final product. This new process was exploited further to prepare silicon carbide-silicon nitride (SiC-Si3N4) composite foams [10]. In this letter we provide microstructural evidence of the improvements in structure of the ceramic foams produced by our method. The polysilane precursor discussed in this study was synthesized by the alkali dechlorination of a combination of chlorinated silane monomers in refluxing toluene/tetrahydrofuran with molten sodium as described previously [11, 12]. The structure of the SiC polysilane precursor synthesized is given below. Ph indicates a phenyl group.

In this work, using multiple co-flows we demonstrate in-situ encapsulation of nano-particles, liquids and/or gases in different structural morphologies, which can also be deposited in a designated pattern by a direct write method and surface modification can be controlled to release encapsulated material. The range of possibilities offered by exposing a material solution to an applied electric field can result in a plethora of structures which can accommodate a whole host of biomedical applications from microfluidic devices (microchannels, loaded with various materials), printed 3D structures and patterns, lab-on-a-chip devices to encapsulated materials (capsules, tubes, fibres, dense multi-layered fibrous networks) for drug delivery and tissue engineering. The structures obtained in this way can vary in size from micrometer to the nanometer range and the processing is viable for all states of matter. The work shown demonstrates some novel structures and methodologies for processing a biomaterial. © 2009 Springer-Verlag.

Electrohydrodynamic processing of a pre-ceramic polymer solution (polysiloxane) was used to fabricate various micro-components. With a single needle experimental set-up, sub-micrometer fibers and millimeter-size porous capsules were produced, while using two co-axial needles further enhanced the shaping versatility of the process, leading to the formation of micro-tubes and sub-micrometer hollow capsules. The polymeric samples were cross-linked and then pyrolyzed at 1200 degrees C in N-2 producing ceramic micro-parts that retained the morphological features present in the components in the polymeric state.