Ceramic microparticles and capsules via microfluidic processing of a preceramic polymer

We have developed a robust technique to fabricate monodispersed solid and porous ceramic particles and capsules from single and double emulsion drops composed of silsesquioxane preceramic polymer. A microcapillary microfluidic device was used to generate the monodispersed drops. In this device, two round capillaries are aligned facing each other inside a square capillary. Three fluids are needed to generate the double emulsions. The inner fluid, which flows through the input capillary, and the middle fluid, which flows through the void space between the square and inner fluid capillaries, form a coaxial co-flow in a direction that is opposite to the flow of the outer fluid. As the three fluids are forced through the exit capillary, the inner and middle fluids break into monodispersed double emulsion drops in a single-step process, at rates of up to 2000 drops s−1. Once the drops are generated, the silsesquioxane is cross-linked in solution and the cross-linked particles are dried and pyrolysed in an inert atmosphere to form oxycarbide glass particles. Particles with diameters ranging from 30 to 180 µm, shell thicknesses ranging from 10 to 50 µm and shell pore diameters ranging from 1 to 10 µm were easily prepared by changing fluid flow rates, device dimensions and fluid composition. The produced particles and capsules can be used in their polymeric state or pyrolysed to ceramic. This technique can be extended to other preceramic polymers and can be used to generate unique core–shell multimaterial particles.

[1]  M. Edirisinghe,et al.  Preparation of Polymeric and Ceramic Porous Capsules by a Novel Electrohydrodynamic Process , 2008 .

[2]  L. Archer,et al.  Platinum-functionalized octahedral silica nanocages: synthesis and characterization. , 2006, Angewandte Chemie.

[3]  Jung-Hye Eom,et al.  Fabrication of silicon oxycarbide foams from extruded blends of polysiloxane, low-density polyethylene (LDPE), and polymer microbead , 2007 .

[4]  M. Edirisinghe,et al.  Engineering a material for biomedical applications with electric field assisted processing , 2009 .

[5]  C. Balan,et al.  Amorphous Si(Al)OC ceramic from polysiloxanes: bulk ceramic processing, crystallization behavior and applications , 2004 .

[6]  Seth T. Taylor,et al.  Self-assembly of an organic-inorganic block copolymer for nano-ordered ceramics. , 2007, Nature nanotechnology.

[7]  Caruso,et al.  Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating , 1998, Science.

[8]  Loïc J Blum,et al.  Applications of the luminol chemiluminescent reaction in analytical chemistry , 2006, Analytical and bioanalytical chemistry.

[9]  Xuanyong Liu,et al.  In vivo evaluation of plasma-sprayed wollastonite coating. , 2005, Biomaterials.

[10]  L. Rayleigh On the Capillary Phenomena of Jets , 1879 .

[11]  E. Bernardo,et al.  Development of multiphase bioceramics from a filler-containing preceramic polymer , 2009 .

[12]  P. Greil,et al.  Complex-shaped ceramic composites obtained by machining compact polymer-filler mixtures , 2005 .

[13]  Patrick S Doyle,et al.  Permeation-driven flow in poly(dimethylsiloxane) microfluidic devices. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[14]  G. Zank,et al.  Silicon Oxycarbide Glasses Derived from Polymer Precursors , 1998 .

[15]  D. Weitz,et al.  Monodisperse Double Emulsions Generated from a Microcapillary Device , 2005, Science.

[16]  E Stride,et al.  Preparation of polymeric and ceramic porous capsules by a novel electrohydrodynamic process. , 2008, Pharmaceutical development and technology.

[17]  A. Shakoori,et al.  A new technique for the isolation of nucleoli from animal cells. , 1972, Hoppe-Seyler's Zeitschrift fur physiologische Chemie.

[18]  Michael J Sailor,et al.  Biomolecular screening with encoded porous-silicon photonic crystals , 2002, Nature Materials.

[19]  T. Hu,et al.  Porous-wall hollow glass microspheres as novel potential nanocarriers for biomedical applications. , 2010, Nanomedicine : nanotechnology, biology, and medicine.

[20]  P. Colombo Polymer derived ceramics : from nano-structure to applications , 2010 .

[21]  A. Imhof,et al.  Synthesis of Monodisperse Colloidal Spheres, Capsules, and Microballoons by Emulsion Templating , 2005 .

[22]  R. K. Shah,et al.  Monodisperse stimuli-responsive colloidosomes by self-assembly of microgels in droplets. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[23]  Robert F Shepherd,et al.  Microfluidic assembly of homogeneous and Janus colloid-filled hydrogel granules. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[24]  L. J. Bellamy The infra-red spectra of complex molecules , 1962 .

[25]  Carlo G. Pantano,et al.  Silicon Oxycarbide Glasses , 1999 .

[26]  M. Scheffler,et al.  Fabrication of polymer derived ceramic parts by selective laser curing , 2005 .

[27]  Yong Wang,et al.  Template‐Free Synthesis of SnO2 Hollow Nanostructures with High Lithium Storage Capacity , 2006 .

[28]  John Evans,et al.  Solid Freeforming of Silicon Carbide by Inkjet Printing Using a Polymeric Precursor , 2004 .

[29]  Zhibing Hu,et al.  Fabrication of monodisperse gel shells and functional microgels in microfluidic devices. , 2007, Angewandte Chemie.

[30]  Ilke Akartuna,et al.  General route for the assembly of functional inorganic capsules. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[31]  I. Chen,et al.  Encapsulation of protein molecules in transparent porous silica matrices via an aqueous colloidal sol–gel process , 1999 .

[32]  M. Scheffler,et al.  Centrifugal Casting of Thin‐Walled Ceramic Tubes from Preceramic Polymers , 2003 .

[33]  R. Riedel,et al.  Al2O3-SiC composites prepared by warm pressing and sintering of an organosilicon polymer-coated alumina powder , 2007 .

[34]  E. Vogler,et al.  Silicon oxycarbide glasses for blood-contact applications. , 2005, Acta biomaterialia.

[35]  Wei Li,et al.  Janus and ternary particles generated by microfluidic synthesis: design, synthesis, and self-assembly. , 2006, Journal of the American Chemical Society.

[36]  Joe K. Cochran,et al.  Ceramic hollow spheres and their applications , 1998 .

[37]  A. Boccaccini,et al.  Biodegradable and bioactive porous polymer/inorganic composite scaffolds for bone tissue engineering. , 2006, Biomaterials.

[38]  A. R. Bausch,et al.  Colloidosomes: Selectively Permeable Capsules Composed of Colloidal Particles , 2002, Science.

[39]  E. Laborde,et al.  Investigations on thermal reactivity of Si/C/N nanopowders produced by laser aerosol or gas interactions , 2001 .

[40]  E. Bernardo,et al.  Electrohydrodynamic forming of porous ceramic capsules from a preceramic polymer , 2009 .

[41]  P. Greil,et al.  Injection moulding of polysiloxane/filler mixtures for oxycarbide ceramic composites , 1996 .

[42]  謙爾 鈴木,et al.  有機-無機変換プロセスによる SiC 系セラミック繊維の合成 (総説) , 2006 .

[43]  M. Schulz Polymer derived ceramics in MEMS/NEMS – a review on production processes and application , 2009 .

[44]  Hui Zhang,et al.  Gold nanocages: bioconjugation and their potential use as optical imaging contrast agents. , 2005, Nano letters.

[45]  I. Song,et al.  Processing and properties of polysiloxane-derived porous silicon carbide ceramics using hollow microspheres as templates , 2008 .

[46]  P. Colombo Engineering porosity in polymer-derived ceramics , 2008 .

[47]  Steve Semancik,et al.  Porous tin oxide nanostructured microspheres for sensor applications. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[48]  H. Weber,et al.  Enzymatic hydroxylation reactions. , 2000, Current opinion in biotechnology.

[49]  S. Kato,et al.  Fabrication and pressure testing of a gas-turbine component manufactured by a preceramic-polymer-impregnation method , 1999 .

[50]  F. Shutov Syntactic polymer foams , 1986 .

[51]  Minseok Seo,et al.  Polymer particles with various shapes and morphologies produced in continuous microfluidic reactors. , 2005, Journal of the American Chemical Society.

[52]  E. Maire,et al.  Characterization of the morphology of cellular ceramics by 3D image processing of X-ray tomography , 2007 .

[53]  S. Asher,et al.  Synthesis and utilization of monodisperse hollow polymeric particles in photonic crystals. , 2004, Journal of the American Chemical Society.

[54]  Mohamed Rachik,et al.  Identification of the elastic properties of an artificial capsule membrane with the compression test: effect of thickness. , 2006, Journal of colloid and interface science.

[55]  Toru Torii,et al.  Controlled production of monodisperse double emulsions by two-step droplet breakup in microfluidic devices. , 2004, Langmuir : the ACS journal of surfaces and colloids.