Stretching Micro Metal Particles into Uniformly Dispersed and Sized Nanoparticles in Polymer.

There is a longstanding challenge to disperse metal nanoparticles uniformly in bulk polymers for widespread applications. Conventional scale-down techniques often are only able to shrink larger elements (such as microparticles and microfibers) into micro/nano-elements (i.e. nanoparticles and nanofibers) without much altering their relative spatial and size distributions. Here we show an unusual phenomenon that tin (Sn) microparticles with both poor size distribution and spatial dispersion were stretched into uniformly dispersed and sized Sn nanoparticles in polyethersulfone (PES) through a stack and draw technique in thermal drawing. It is believed that the capillary instability plays a crucial role during thermal drawing. This novel, inexpensive, and scalable method overcomes the longstanding challenge to produce bulk polymer-metal nanocomposites (PMNCs) with a uniform dispersion of metallic nano-elements

MECHANISM OF THICK METAL WALLS PENETRATION BY HIGH-SPEED MICROPARTICLES

Purpose. Analysis and estimation of physical parameters which create conditions for microparticles penetration into metal microstructure to abnormally big depth. Methodology. Quantum mechanical three­site model has been used for studying the regularities of electron motion in the field of two Coulomb centres and numerical solution for the problem of the effect of external electrical charge on stability of the chemical bond. Solution was found for the equation of heat conductivity for estimating the temperature of microparticles heating under compression and acceleration by explosively driven accelerator. Stokes’s law was used for estimating viscosity of hypothetical medium which can be penetrated by microparticle at a great speed and to a great depth. The research was done with the help of X­ray microanalysis, X­ray crystallography, micrographic investigation, mass­spectrometry and electronic spectroscopy. Findings. Solution of the quantum mechanical model testifies that electric charges serve as catalysts responsible for the significant reduction of the energy barrier of chemical reactions. To ensure super deep penetration, it is necessary to achieve acceleration of a great number of microparticles in a special explosively driven accelerator. Heating, intensive stirring and friction result in electrification of the surface of the particles, which is known as triboelectric effect. The hypothesis about physical and chemical mechanism of particles penetration into metals resulting from high­speed impact has been put forward. Originality. The research has established relationship between the sizes of microparticles accelerated by explosion and the density of electric charges on their surfaces, as well as the depth of their penetration into the metal barrier. By experimental research, it was proven that maximum depth of microparticles penetration is directly proportional to the maximum density of surface charges for the particles of the 50…80 µm size. It is assumed that particles penetration into metals to greater depths is conditioned by the reduction of the barrier material viscosity in the zone of particle­barrier contact due to quantum mechanical effects in the solid­state plasma. Practical value. The value of the work includes creating a new generation of metal composites as well as new prospective technologies of reactive materials utilization

Tailoring Organic-Organic Poly(vinylpyrrolidone) Microparticles and Fibers with Multiwalled Carbon Nanotubes for Reinforced Composites

Polymeric-based microparticles and fibers are tailorable for a wide range of common industrial and biomedical applications, while multiwalled carbon nanotubes (MWCNTs) are among the most useful macromolecules based on their outstanding electronic, mechanical, and optical properties at the nanoscale. If one combines these nanostructures with various polymeric precursors, their range of potential applications becomes even greater. One of the simplest and most affordable methods for fabricating micro- and nanostructures is electrospinning. Herein we demonstrate how MWCNTs may be used to produce tailor-made organic-organic poly(vinylpyrrolidone) (PVP) microparticles and fibers via electrospinning by studying their structural, vibrational, rheological, and mechanical properties' dependence on their solvent (ethanol (EtOH) or dimethylformamide (DMF)) and resulting morphology. Specifically, we find clear differences in morphologies from perfectly spherical and isolated microparticles to fibers mats, or a combination of fibers with entangled beads, with solvent type and concentration. On the basis of our findings, we propose that the mechanism governing the shape and size of the particles is a competition between the solvent's surface tension, dielectric constant, and viscoelastic properties. We show, based on both our experimental results and density functional theory (DFT) calculations, that OH functionalization of the MWCNTs is essential for achieving high PVP coverages and promoting the stability of the resulting PVP/MWCNT nanocomposite. Finally, by fabricating PVP/MWCNT fiber mats, we demonstrate that low concentrations (0.01-0.1 wt %) of MWCNTs led to a qualitative improvement (â250%) in the resulting mechanical properties, i.e., a reinforced composite. These results show how by controlling the solvent's dielectric constant, surface tension, and polymer concentration, one may produce tailor-made polymeric nanomaterials in combination with other organic/inorganic nanoparticles, i.e., silver, gold, or carbon allotropes, for next-generation applications

Remote control of diffusion from magnetic hollow silica microspheres

Composite hollow core silica/iron oxide microparticles with the ability to store an encapsulated payload and release a defined quantity “on demand” by the application of a radiofrequency magnetic field were prepared. The microparticles possessed a mesoporous silica shell with iron oxide nanoparticles bound to the external silica surface by electrostatic interaction. The size, morphology and stability of the composite particles were systematically investigated and the effect of iron oxide:silica ratio on their heating rate and the release kinetics of a model compound (vitamin B12) was determined. The composite particles were stable in time and had a high heating ability in the radiofrequency magnetic field, achieving a temperature rise of several 10’s °C per minute. Thanks to the high heating rate, external radiofrequency field was shown to be an effective trigger mechanism for externally controlled diffusion of encapsulated material from within the hollow core at an arbitrary on-off sequence

Remotely Controlled Diffusion from Magnetic Liposome Microgels

The reversible, temperature-dependent change in the permeability of a phospholipid bilayer has been used for controlling the diffusion rate of encapsulated molecular payload from liposomes. Liposomes were preloaded with a fluorescent dye and immobilized in calcium alginate hydrogel microparticles that also contained iron oxide nanoparticles. The composite microparticles were produced by a drop-on-demand inkjet method. The ability of iron oxide nanoparticles to locally dissipate heat upon exposure to a radio-frequency (RF) alternating magnetic field was used to control the local temperature and therefore diffusion from the liposomes in a contactless way using an RF coil. Several different release patterns were realized, including repeated on-demand release. The internal structure of the composite alginate–liposome–magnetite microparticles was investigated, and the influence of microparticle concentration on the heating rate was determined. In order to achieve a temperature rise required for the liposome membrane melting, the concentration of alginate beads should be at least 25% of their maximum packing density for the nanoparticle concentration and specific absorption rate used

Controlled release properties and final macroporosity of a pectin microspheres–calcium phosphate composite bone cement

The use of calcium phosphate cements (CPC) is restricted by their lack of macroporosity and poor drug release properties. To overcome these two limitations, incorporating degradable polymer microparticles into CPC is an attractive option, as polymer microparticles could help to control drug release and induce macroporosity after degradation. Although few authors have yet tested synthetic polymers, the potentiality of polysaccharides’ assuming this role has never been explored. Low-methoxy amidated pectins (LMAP) constitute valuable candidates because of their biocompatibility and ionic and pH sensitivity. In this study, the potentiality of a LMAP with a degree of esterification (DE) of 30 and a degree of amidation (DA) of 19 was explored. The aim of this study was to explore the influence of LMAP microspheres within the composite on the cement properties, drug release ability and final macroporosity after microspheres degradation. Three LMAP incorporation ratios, 2%, 4% and 6% w/w were tested, and ibuprofen was chosen as the model drug. In comparison with the CPC reference, the resulting composites presented reduced setting times and lowered the mechanical properties, which remained acceptable for an implantation in moderate-stress-bearing locations. Sustained release of ibuprofen was obtained on at least 45 days, and release rates were found to be controlled by the LMAP ratio, which modulated drug diffusion. After 4 months of degradation study, the resulting CPC appeared macroporous, with a maximum macroporosity of nearly 30% for the highest LMAP incorporation ratio, and interconnectivity between pores could be observed. In conclusion, LMAP appear as interesting candidates to generate macroporous bone cements with tailored release properties and macroporosity by adjusting the pectin content within the composites

Injectable Hydrogels Based on Pluronic/Water Systems Filled with Alginate Microparticles for Biomedical Applications

A (model) composite system for drug delivery was developed based on a thermoresponsive hydrogel loaded with microparticles. We used Pluronic F127 hydrogel as the continuous phase and alginate microparticles as the dispersed phase of this composite system. It is well known that Pluronic F127 forms a gel when added to water in an appropriate concentration and in a certain temperature range. Pluronic F127 hydrogel may be loaded with drug and injected, in its sol state, to act as a drug delivery system in physiological environment. A rheological characterization allowed the most appropriate concentration of Pluronic F127 (15.5 wt%) and appropriate alginate microparticles contents (5 and 10 wt%) to be determined. Methylene blue (MB) was used as model drug to perform drug release studies in MB loaded Pluronic hydrogel and in MB loaded alginate microparticles/Pluronic hydrogel composite system. The latter showed a significantly slower MB release than the former (10 times), suggesting its potential in the development of dual cargo release systems either for drug delivery or tissue engineering

DEFORMATION BEHAVIOR OF NANO/MICRO REINFORCED PMMA

Práce sleduje vliv velikosti částic na elastický modul a deformační chování za mezí kluzu. Bylo pozorováno, že jak elastická oblast, tak oblast za mezí kluzu ukazuje silnou závislost chování na velikosti částic. Cílem této práce je korelovat experimentální data a teoretické předpoklady které bylo odvozeny pro deformační chování v elastické oblasti a v oblasti za mezí kluzu pro amorfní polymery a konkrétně pro PMMA. Vše je motivováno propojit zatím oddělené oblasti kontinuální mikromechaniky a diskrétní nanomechaniky. Deformační chovaní PMMA plněného nano a mikro plnivem bylo pozorováno v elastické a plastické oblasti. Byl zkoumán vliv velikosti částic na velikost modulu a deformačního zpevnění. Mechanizmus vyztužení je interpretován s použitím teorie imobilizace řetězců, nanočástice mají silný vliv na molekulární dynamiku a kinetiku zapletenin. Mým příspěvkem k tomuto tématu je ukázat výraznou závislost na mechanizmu vyztužení v závislosti na velikosti částic. A to jak pod teplotou skelného přechodu tak nad teplotou skelného přechodu. Ačkoli pro velikost modulu byla publikována značná množství dat, která byla následně i interpretována, vliv částic na deformační zpevnění je poskrovnu. Během elastické deformace je primární struktura materiálu neměnná, jedná se o elastickou deformaci, za mezí kluzu již toto neplatí a primární struktura je zde nevratně poškozena. Bylo ukázáno, že obsah nano částic vede ke zvýšení meze kluzu a vyššímu deformačnímu zpevnění. Tento nárůst deformačního zpevnění je v korelaci s Guth-Gold rovnicí. Je předpokládáno, že nanočástice slouží jako další fyzikální zapleteniny a vedou k fyzikálně více zapletenému systému. Stejný efekt jako v elastické oblast tj. vliv velikosti částic na modul, byla pozorována i během deformačního zpevnění.The effect of particle size on magnitude of modulus and the post-yield response is highlighted. It is shown that both regions show a pronounced particle size dependence. The object of this work is to correlate a number of experimental facts and theoretical considerations regarding the mechanism of elastic and plastic deformation of amorphous polymers in general and of glassy PMMA particularly. Deformation behavior of PMMA filled with spherical particles will be observed in elastic and plastic region. The effect of particle size dependence on the modulus and strain hardening response was observed. The interpretation of reinforcing effect in nanocomposites is building up with the concept of immobilization, the nanoparticles show significant affect on the molecular dynamics and the kinetics of the disentanglement. While for the modulus measurement a large extent of data were published trying to interpret the observed trends, the strain-hardening region is somehow omitted. In an elastic region, the structure of the material maintains the same as prepared, but after passing the yield point, the primary structure is destroyed. It is shown that incorporation of the nanoparticles yields to the increase of strain hardening slope and that this slope is in a good correlation with Guth-Gold equation. It is assumed that the particles can serve as physical crosslinks yielding to physically denser entangled network.

Quantification of metallic copper and nickel in their binary mixtures by voltammetry of immobilized microparticles

We report the use of voltammetry of immobilized microparticles for the quantification of metallic copper and nickel in their binary mixtures. Twenty-two electrolytes were investigated in order to obtain well-separated oxidation peaks. An experimental design strategy was employed to study the effect of the electrolyte concentration and the scan rate on the resolution of the oxidation peaks. With the optimum experimental parameters, a quantification was performed and the linear results of percentage of anodic currents in term of their relative amount in the binary mixture were obtained. Finally, the prediction of two mixture samples was performed and gave satisfactory results

Apatite-Polymer Composites for the Controlled Dual Delivery of BMP-2 and BMP-6 for Bone Tissue Engineering

The release of growth factors from tissue engineering scaffolds provides signals that influence the migration, differentiation, and proliferation of cells. The incorporation of a drug delivery platform that is capable of tunable release will give tissue engineers greater versatility in the direction of tissue regeneration. We have prepared a novel composite of two biomaterials with proven track records - apatite and poly(lactic-co-glycolic acid) (PLGA) – as a drug delivery platform with promising controlled release properties. These composites have been tested in the delivery of a model protein, bovine serum albumin (BSA), as well as therapeutic proteins, recombinant human bone morphogenetic protein-2 (rhBMP-2) and rhBMP-6. The controlled release strategy is based on the use of a polymer with acidic degradation products to control the dissolution of the basic apatitic component, resulting in protein release. Therefore, any parameter that affects either polymer degradation or apatite dissolution can be used to control protein release. We have modified the protein release profile systematically by varying the polymer molecular weight, polymer hydrophobicity, apatite loading, apatite particle size, and other material and processing parameters. Biologically active rhBMP-2 was released from these composite microparticles over 100 days, in contrast to conventional collagen sponge carriers, which were depleted in approximately 2 weeks. The released rhBMP-2 was able to induce elevated alkaline phosphatase and osteocalcin expression in pluripotent murine embryonic fibroblasts. To augment tissue engineering scaffolds with tunable and sustained protein release capabilities, these composite microparticles can be dispersed in the scaffolds in different combinations to obtain a superposition of the release profiles. We have loaded rhBMP-2 into composite microparticles with a fast release profile, and rhBMP-6 into slow-releasing composite microparticles. An equi-mixture of these two sets of composite particles was then injected into a collagen sponge, allowing for dual release of the proteins from the collagenous scaffold. The ability of these BMP-loaded scaffolds to induce osteoblastic differentiation in vitro and ectopic bone formation in a rat model is being investigated. We anticipate that these apatite-polymer composite microparticles can be extended to the delivery of other signalling molecules, and can be incorporated into other types of tissue engineering scaffolds.Singapore-MIT Alliance (SMA