Morphological evolution on the surface of hydrothermally synthesized hydroxyapatite microspheres in the presence of EDTMP

Well-ordered and surface engineered hierarchical hydroxyapatite microspheres (HAM) were prepared via a template free hydrothermal process. Ethylene diamine tetra (methylene phosphonic acid) (EDTMP) was used as chelating or regulating agent for the first time in this study. The results indicated the formation of sheet-like particles in the absence of EDTMP. On the other hand, microspheres with radially grown nanorods (HAMNR) or nanosheets (HAMNS) on the surface were obtained (with average diameter of 5?µm) in the presence of EDTMP. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to characterize the crystalline phases in the synthesized samples. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that EDTMP concentration played an important part in regulating the morphology to form well organized microspheres with nanosheets or nanorods on the surface. Brunauer-Emmett-Teller (BET) revealed an increase in the specific surface area with the change in morphology from the HAMNS to HAMNR. Possible mechanisms are proposed to account for the formation of different morphologies based upon thermodynamic and kinetic theories.     

Monodispersed thermoresponsive hydrogel microspheres with a volume phase transition driven by hydrogen bonding

We report the synthesis and characterization of monodispersed thermoresponsive hydrogel microspheres with a volume phase transition driven by hydrogen bonding. The prepared microspheres, composed of poly(acrylamide-co-styrene) (poly(AAM-co-St)) cores and poly(acrylamide)/poly(acrylic acid) (PAAM/PAAC) based interpenetrating polymer network (IPN) shells, were featured with high monodispersity and positively thermoresponsive volume phase transition characteristics with tunable swelling kinetics, i.e. the particle swelling was induced by an increase rather than a decrease in temperature. The monodisperse poly(AAM-co-St) seeds were prepared by emulsifier-free emulsion polymerization, the PAAM or poly(acrylamide-co-butyl methacrylate) (poly(AAM-co-BMA)) shells were fabricated on the seeds by free radical polymerization, and the core-shell microspheres with PAAM/PAAC based IPN shells were finished by a method of sequential IPN synthesis. The microsphere size increased with increasing both AAM and BMA dosages. The increase of hydrophilic monomer AAM dosage resulted in a better monodispersity, but the increase of hydrophobic monomer BMA dosage led to a worse monodispersity. With increasing the crosslinker methylenebisacrylamide (MBA) dosage, the mean diameter of the microspheres decreased and the monodispersity became better. An equimolar composition of AAC and AAM in the IPN shells of the microspheres resulted in a more complete shrinkage for the microspheres at temperatures lower than the upper critical solution temperature. Both BMA and MBA additions depressed the swelling ratio of the hydrodynamic diameter of the microspheres.     

Composition and morphology of char particles of fly ashes from industrial burning of high-ash coals with different reactivity

A comparative investigation of the composition and the morphology of char particles was conducted: char particles were recovered from fly ashes of two power stations in Russia from burning of high- and low-reactivity high-ash coals; the known results of studies of char particles generated in laboratory conditions from coals characterized according to the ASTM D388-98a standard were also used. The composition of organic and mineral components of different fraction char particles was studied. An inverse correlation between the content of the organic substance and the iron content in char particles was identified. The morphology of the char particles for the three main types (Cenospheric, Network and Solid) and the influence of coal reactivity and temperature on char morphology were investigated. The morphology of the mineral component of char particles of the two varieties of coals was also studied. It was shown that the high-temperature of industrial burning of Ekibastuz coal results in melting of the mineral substance and forming of micron-scale microspheres located in the lamellar porous structure of the carbon matrix.     

Preparation and Characterization of Carboxymethyl Chitosan and β-Cyclodextrin Microspheres by Spray Drying

Three kinds of carboxymethyl chitosan/β-cyclodextrin microspheres loaded with theophylline were prepared by spray drying intended for pulmonary delivery. Mucociliotoxicity, permeation rate, and drug release characteristics of the product were investigated. The microspheres obtained by spray drying were found to be spherical with smooth or wrinkled surfaces. The mean particle size was between 3.39 and 6.06 µm. The microspheres demonstrated high product yield (43.7-50.2%), high drug loading (13.7-38.1%), and high encapsulation efficiency (86.9-92.8%). FT-IR indicated that there were interactions of theophylline with carboxymethyl chitosan matrix. Further studies on mucociliotoxicity and permeation confirmed that microspheres had better adaptability and high permeation rate. In vitro drug release from the microspheres was not related to the drug/polymer ratios.     

Spray drying conditions and encapsulating composition effects on formation and properties of sodium diclofenac microparticles

This paper reports the preparation and characterization of sustained release sodium diclofenac microparticles by spray drying. Aqueous dispersions of ethyl cellulose (Surelease®) and Eudragit RS 30 D® were evaluated as controlled release polymers. The product properties (product moisture, size distribution, particle morphology, flow properties, total drug load, in-vitro dissolution studies, and encapsulating efficiency) were determined as a function of inlet temperature of the spray drying, the feed flow rate and composition of the microencapsulating formulation. In general, lower values of the product moisture content were observed at higher drying temperatures. The spray-dried product was composed mainly by rounded-shape and multi-size particles. The mean particle diameters of the Eudragit based microparticles tended to be slight bigger than the Surelease based microparticles. The spray dried microparticles showed delayed drug dissolution rates, sustaining the drug release for several hours. These findings confirm the feasibility of the spray drying for preparation of microparticles with sustained release properties. The physical and chemical properties of the microparticles can be changed by varying the spray drying parameters as well as the microencapsulating formulation.     

Porous AlN ceramic substrates by reaction sintering

A novel approach was undertaken in producing porous AlN microelectronics tapes with high thermal conductivity and low dielectric constant. This method essentially utilised polymer micro-spherical powders that were used as a sacrificial mould to introduce controlled porosity into the green tapes during pyrolysis. The Al₂O₃-rich porous green tapes were then reaction sintered at 1680 °C for 12 h to achieve porous AlN tapes. This work builds upon the previously developed novel reaction sintering process that densified and converted Al₂O₃-rich tapes (Al₂O₃–20 wt.% AlN–5 wt.% Y₂O₃) to AlN tapes at a relatively low sintering temperature of 1680 °C. The sintering behaviour of the porous tapes was investigated, and the effects of the microspheres particle size and volume addition were studied. The microspheres successfully contributed to the significant reduction of tape density by porosity, and this contributed to lowering its dielectric constant. Dielectric constant of the AlN tapes were reduced to about 6.8–7.7 whilst thermal conductivity values were reasonable at about 46–60 W/m K. Coefficient of thermal expansion (CTE) values showed a linear trend according to phase composition, with the porous AlN tapes exhibiting CTE values of (4.4–4.8)×10⁻⁶ °C⁻¹, showing good CTE compatibility with silicon, at 4.0×10⁻⁶ °C⁻¹. The added porosity did not significantly affect the CTE values.     

Surface-initiated nitroxide-mediated radical polymerization of 2-(dimethylamino)ethyl acrylate on polymeric microspheres

2-(Dimethylamino)ethyl acrylate (DMAEA) was grafted from the surface of alkoxyamine-functionalized crosslinked poly(styrene-co-chloromethylstyrene) microspheres by nitroxide-mediated radical polymerization (NMRP). Latex particles (∼60 nm diameter) bearing chloromethyl groups were synthesized by emulsion polymerization. N-tert-butyl-N-(1-diethyl phosphono-2,2-dimethylpropyl)nitroxide (SG1) was then immobilized on the particle surface. Microspheres grafted with the homopolymer pDMAEA, as well as block copolymers poly(styrene-b-DMAEA) and poly(butyl acrylate-b-DMAEA) were prepared by surface-initiated NMRP in N,N-dimethylformamide at 112 °C, with the addition of free SG1 to ensure that control is maintained. Particle size increases with number average molecular weight (M_n) of untethered polymers. The polymerizations exhibit linear first order kinetic plots and slight curvature of evolution of M_n with conversion. The functional microspheres were analyzed by infrared spectroscopy, transmission electron microscopy and thermal analysis, as well as their dispersibility in water; the results support the formation of surface-grafted pDMAEA on the microspheres.