Size and morphology-controlled synthesis of mesoporous hydroxyapatite nanocrystals by microwave-assisted hydrothermal method

We report the rapid microwave-assisted hydrothermal synthesis of mesoporous hydroxyapatite (HAp) nanocrystals with controlled size, morphology, and surface area using various organic modifiers as regulators. The products were analyzed for their crystalline nature, phase purity, morphology, particle size and pore size distribution. Results indicated that ascorbic acid, cetyltrimethyl ammonium bromide (CTAB) and polyvinylpyrrolidone (PVP) play an important role to obtain needle like, rod like and fiber like mesoporous HAp nanocrystals with different specific surface area by controlling growth habit of HAp along c-axis. In addition, the prepared samples were B-type carbonated HAp similar to bone minerals. Therefore, the present approach can be a promising way to obtain precursor for making tissue engineering scaffolds, drug/protein delivery carriers and bone fillers with tunable characteristics.     

Relation between microstructure and glass transition temperature of poly[(methyl methacrylate)‐co‐(ethyl acrylate)]

The glass transition temperature of a series of samples of the poly[(methyl methacrylate)‐co‐(ethyl acrylate)] copolymer, synthesized at low conversion, were calculated theoretically using the equations of Barton and Johnston. The values obtained are more precise when the probabilities of the compositional diads are derived from the ¹³C NMR data instead of the classical method utilizing reactivity ratios. This can be observed more clearly when the copolymer samples are synthesized at high conversion. Introduction of configuration (tacticity) at the diad level confirms the above observations and slightly improves the calculated values of T_g compared to the initial formulae which were only taking into account the compositional sequences of the copolymer. © 2001 Society of Chemical Industry     

Mechanical Behavior of Nanostructured and Microstructured Explosives

Nanostructured hexolites (40/60), (60/40), (80/20) and microstructured hexolite (60/40) powders are pressed by uniaxial compression to obtain explosive charges. This kind of composition is often used for the synthesis of detonation nanodiamonds. The morphology, density and cohesion of the resulting pellets are analyzed in the light of the different used compression parameters. This study allows optimizing the compression parameters to obtain well suited explosive charges from nanostructured explosive components. A good cohesion of the nanostructured explosive pellets could be obtained with increasing the temperature used for the compression. Another very important point is that the nanostructuring of the composites is maintained for every compression.     

A Binary Gas Transport Model Improves the Prediction of Mass Transfer in Freeze Drying

Monitoring partial vapor pressure in the freeze-drying chamber is a cheap, global, and non-intrusive way to assess the end of the primary drying stage. Most existing dynamic freeze-drying models which predict this partial pressure describe mass transfer between the product and the condenser via a mass transfer resistance or a mass transfer coefficient. Experimental evidence suggests that such models can be significantly in error for some values of the sublimation flux, leading to physically inconsistent predictions and possibly incorrect assessment of primary drying termination, with potential risk of product damage if moving to secondary drying and increasing shelf temperature while some ice is still present. Assuming a binary gas transport model for vapor and inert gas leads to improved and consistent predictions and explains the apparent variation of the mass transfer resistance with total pressure, shelf temperature, and product sublimation area.     

On the use of a powder rheometer to characterize the powder flowability at low consolidation with torque resistances

The Anton Paar Powder Cell was used to measure the torque necessary to rotate an impeller in beds of glass beads, sand and alumina powders aerated between no aeration to the minimum for fluidization. Measured torque values depend on the material tested, on the air flow rate applied, on the impeller depth and on the height of the impeller blade. The effect of the impeller depth is linear for low impeller depth and is less than linear at high depth values. A model was developed for the interpretation of the experimental results based on the idea that the material is shearing on the surface described by the impeller rotation. The model allows to estimate an effectiveness of the impeller in the torque determination and also to predict the torque for the impeller at the at deepest positions at which the wall effects have to be considered. © 2017 American Institute of Chemical Engineers AIChE J, 2017     

Concentration effects in the base-catalyzed hydrolysis of oligo(ethylene glycol)- and amine-containing methacrylic monomers

Concentration effects in the base-catalyzed hydrolysis of water-soluble methacrylates (3-(N,N-dimethylaminoethyl) methacrylate (DMAEMA), 2-hydroxyethyl methacrylate (HEMA) and oligo(ethylene glycol) methacrylates (OEGMAs)) have been studied. These monomers are rapidly hydrolyzed in the presence of bases at the room temperature in dilute aqueous solutions, but the reaction rate decreases sharply in highly concentrated solutions. A clear correlation was found between a form of the viscosity isotherm for DMAEMA solutions and the concentration dependence of the autocatalytic hydrolysis rate which indicates the connection of process kinetics with the structure of solutions. These data should be considered when carrying out homo- and copolymerization of the previously mentioned monomers in aqueous solutions.     

Additively patterned ferroelectric thin films with vertical sidewalls

The functional properties of electroceramic thin films can be degraded by subtractive patterning techniques used for microelectromechanical (MEMS) applications. This work explores an alternative deposition technique, where lead zirconate titanate (PZT) liquid precursors are printed onto substrates in a desired geometry from stamp wells (rather than stamp protrusions). Printing from wells significantly increased sidewall angles (from ~1 to >35 degrees) relative to printing solutions from stamp protrusions. Arrays of PZT features were printed, characterized, and compared to continuous PZT thin films of similar thickness. Three‐hundred‐nanometer‐thick printed PZT features exhibit a permittivity of 730 and a loss tangent of 0.022. The features showed remanent polarizations of 26 μC/cm², and coercive fields of 95 kV/cm. The piezoelectric response of the features produced an e_31,f of ?5.2 C/m². This technique was also used to print directly atop prepatterned substrates. Optimization of printing parameters yielded patterned films with 90° sidewalls. Lateral feature sizes ranged from hundreds of micrometers down to one micrometer. In addition, several device designs were prepatterned onto silicon on insulator (SOI) wafers (Si/SiO₂/Si with thicknesses of 0.35/1/500 μm). The top patterned silicon was released from the underlying material, and PZT was directly printed and crystallized on the free‐standing structures.     

On shrinkage and structure changes of pure and blended Portland concretes

This research investigates the long‐term shrinkage and Relative Mass Loss (RML) of mature Portland concretes (pure CEMI and blended CEMV/A), at temperatures of 20°C and 80°C. When placed at 80°C and at relative humidities (RH) below 50‐60%, concrete shrinkage increases with very slow stabilization kinetics by several hundreds of μm/m, while RML remains of about 0.2%. The origins of this continued shrinkage, simultaneously with limited RML, are investigated through the changes in (i) the pore structure of the concretes (by Mercury Intrusion Porosimetry and nitrogen adsorption) and in (ii) their solid phases (by TGA/DTA, FTIR spectroscopy coupled to DVS, quantitative X‐Ray Diffraction by Rietveld analysis, and ²⁹Si and ²⁷Al MAS NMR). While the pore structure coarsens during continued shrinkage, several phase transformations occur, namely ettringite decomposition and changes in the silicate chain length of the C–A–S–H. While these structural changes are documented, their relationship with shrinkage/RML and to the pore structure is novel.     

Synthesis and characterization of rubbery highly fluorinated siloxane–imide segmented copolymers

The synthesis and characterization of a series of poly(siloxane–imide) block (or segmented) copolymers obtained by copolymerization of amine‐terminated polydimethylsiloxane with fluorinated aromatic compounds containing anhydride and amine functionality are reported. New fluorinated block copolymers have been synthesized to obtain organophilic polyimides potentially interesting for molecular membrane separations. The new aspects of this work relative to the literature are (1) a comparison of solution and solid‐state approaches in the imidization step to generate the target poly(siloxane–imide) copolymers and (2) exploration of new compositions involving fluorinated aromatic polymers derived from added diamine compounds. It is shown that the copolymer properties can be tailored from glassy to rubbery materials by varying the amount and the type of oligosiloxane used; the transition between glassy and rubbery properties is characterized at a siloxane content of 60 wt%. As a main result, it is shown that the solid‐state approach for inducing the cyclo‐imidization step is the more efficient one for synthesizing polymers with good mechanical properties, when the amount of siloxane block is increased in the copolymer series. Physical and chemical methods (thermogravimetric analysis, Fourier transform infrared spectroscopy, viscosity measurements) were used to characterize the copolymer properties obtained according to the two different synthesis routes. The obtained siloxane–imide copolymers are well soluble in a large variety of moderately polar solvents and exhibit very good thermal stability up to 400 °C. Hence the prepared copolyimides would seem to be promising candidates as organophilic membranes as well as gas permeation membranes. © 2012 Society of Chemical Industry