Olivia A. Graeve

3D printing of composite calcium phosphate and collagen scaffolds for bone regeneration.

Low temperature 3D printing of calcium phosphate scaffolds holds great promise for fabricating synthetic bone graft substitutes with enhanced performance over traditional techniques. Many design parameters, such as the binder solution properties, have yet to be optimized to ensure maximal biocompatibility and osteoconductivity with sufficient mechanical properties. This study tailored the phosphoric acid-based binder solution concentration to 8.75 wt% to maximize cytocompatibility and mechanical strength, with a supplementation of Tween 80 to improve printing. To further enhance the formulation, collagen was dissolved into the binder solution to fabricate collagen-calcium phosphate composites. Reducing the viscosity and surface tension through a physiologic heat treatment and Tween 80, respectively, enabled reliable thermal inkjet printing of the collagen solutions. Supplementing the binder solution with 1-2 wt% collagen significantly improved maximum flexural strength and cell viability. To assess the bone healing performance, we implanted 3D printed scaffolds into a critically sized murine femoral defect for 9 weeks. The implants were confirmed to be osteoconductive, with new bone growth incorporating the degrading scaffold materials. In conclusion, this study demonstrates optimization of material parameters for 3D printed calcium phosphate scaffolds and enhancement of material properties by volumetric collagen incorporation via inkjet printing.

Luminescence variations in hydroxyapatites doped with Eu2+ and Eu3+ ions.

We present a detailed analysis of the luminescence behavior of europium-doped hydroxyapatite (HAp) and calcium-deficient hydroxyapatite (Ca-D HAp) nanopowders. The results show that, while both powders are similar in crystallite size, particle size, and morphology, the luminescence behavior differs significantly. For the HAp:Eu powders, the emission is clearly from Eu(3+) ions and corresponds to typical (5)D(0) --> (7)F(J) emissions, whereas for the Ca-D HAp:Eu powders, we also see a broad emission with two peaks at 420 and 445 nm, corresponding to the 4f(6)5d(1) --> 4f(7) ((8)S(7/2)) transition of Eu(2+). The powders are weakly luminescent in the as-synthesized state, as expected for combustion-synthesized materials and have higher emission intensities as the heat treatment temperature is increased. Luminescence spectra obtained using an excitation wavelength of 254 nm are weak for all samples. Excitation wavelengths of 305, 337, and 359 nm, are better at promoting the Eu(3+) and Eu(2+) emissions in hydroxyapatites. We propose that fluorescence measurements are an excellent way of qualitatively determining the phase composition of europium-doped hydroxyapatite powders, since powders that exhibit a blue emission contain substantial amounts of Ca-D HAp, allowing the determination of the presence of this phase in mixed-phase hydroxyapatites.

A comparative study of thermal behavior of iron and copper nanofluids

Nanofluids consist of nanoparticles dispersed in heat transfer carrier fluid and are typically used for enhancing thermal conductivity in devices and systems. This study investigated the synthesis of iron and copper nanoparticle-based thermal fluids prepared using a two-step process. Chemical precipitation was used for the synthesis of the powders, and ultrasonic irradiation was used to disperse the nanoparticles in the carrier fluid (ethylene glycol). The size distributions of the nanopowders in the carrier fluid were determined using dynamic light scattering resulting in average particle sizes of around 500 nm. The crystallite sizes of the powders were below 20 nm. Thus, both types of nanofluids are comparable with regard to crystallite size, particle size, and morphology resulting in a direct comparison of material properties and their effect on thermal conductivity of the nanofluids. A guarded hot parallel-plate method and dynamic tests were used to compare the thermal conductivities of the nanofluids. It was shown that thermal conductivity can be enhanced by up to 70% for copper nanofluids. It was also demonstrated that for a given particle concentration, copper nanofluids are superior in thermal conductivity compared to iron nanofluids.Nanofluids consist of nanoparticles dispersed in heat transfer carrier fluid and are typically used for enhancing thermal conductivity in devices and systems. This study investigated the synthesis of iron and copper nanoparticle-based thermal fluids prepared using a two-step process. Chemical precipitation was used for the synthesis of the powders, and ultrasonic irradiation was used to disperse the nanoparticles in the carrier fluid (ethylene glycol). The size distributions of the nanopowders in the carrier fluid were determined using dynamic light scattering resulting in average particle sizes of around 500 nm. The crystallite sizes of the powders were below 20 nm. Thus, both types of nanofluids are comparable with regard to crystallite size, particle size, and morphology resulting in a direct comparison of material properties and their effect on thermal conductivity of the nanofluids. A guarded hot parallel-plate method and dynamic tests were used to compare the thermal conductivities of the nanofluids...

Particle size effects in the thermal conductivity enhancement of copper-based nanofluids

We present an analysis of the dispersion characteristics and thermal conductivity performance of copper-based nanofluids. The copper nanoparticles were prepared using a chemical reduction methodology in the presence of a stabilizing surfactant, oleic acid or cetyl trimethylammonium bromide (CTAB). Nanofluids were prepared using water as the base fluid with copper nanoparticle concentrations of 0.55 and 1.0 vol.%. A dispersing agent, sodium dodecylbenzene sulfonate (SDBS), and subsequent ultrasonication was used to ensure homogenous dispersion of the copper nanopowders in water. Particle size distribution of the copper nanoparticles in the base fluid was determined by dynamic light scattering. We found that the 0.55 vol.% Cu nanofluids exhibited excellent dispersion in the presence of SDBS. In addition, a dynamic thermal conductivity setup was developed and used to measure the thermal conductivity performance of the nanofluids. The 0.55 vol.% Cu nanofluids exhibited a thermal conductivity enhancement of approximately 22%. In the case of the nanofluids prepared from the powders synthesized in the presence of CTAB, the enhancement was approximately 48% over the base fluid for the 1.0 vol.% Cu nanofluids, which is higher than the enhancement values found in the literature. These results can be directly related to the particle/agglomerate size of the copper nanoparticles in water, as determined from dynamic light scattering.

Ionic Concentration Effects on Reverse Micelle Size and Stability: Implications for the Synthesis of Nanoparticles

We present a systematic investigation and analysis of the structure and stability of reverse micelle systems with the addition of NH(4)OH, ZrOCl(2), and Al(NO(3))(3) salts. We demonstrate that the reverse micelle size decreases with increasing salt additions until one reaches a critical concentration, which characterizes the onset of system destabilization. The concept of an electrical double layer, as it applies to reverse micelles, is considered for explaining features of destabilization, including the initial decrease in reverse micelle size, the destabilization concentration, and the effect of cation valence. We propose that the reduction in size prior to instability is caused by compression of the reverse micelle electrical double layers, as higher concentrations of salts are present. The reduced thickness of the electrical double layers allows the decaying potentials to move into closer proximity to each other before generating enough repulsion to balance the forces for reverse micelle formation and form a new equilibrium average reverse micelle size. The point of reverse micelle instability has been related to the formation of a two-phase system as a result of the inability to further compress the salt co-ions in the core of the reverse micelles, which would cause an excessive repulsive force between the overlapping potentials. We have extracted a critical potential of -89 nV between the two overlapping potentials for the AOT/water/isooctane (ω(0) = 10) systems studied. All these effects have important implications for the preparation of nanopowders by reverse micelle synthesis. If the reverse micelles are unstable before the precipitates are formed, then the advantage of reverse micelle synthesis is immediately lost.

Modeling solution for electric field-activated combustion synthesis

Abstract A computer model of the effect of an electric field on self-propagating high-temperature synthesis (SHS) reactions is presented. Using the synthesis of SiC as a model, the analysis showed that, in addition to the chemical heat release, the combustion zone also includes heat release from an electric source, a value equivalent to σE2, where σ is the conductivity and E is the field. Using a two-dimensional Fourier heat balance equation and accounting for the field contribution in terms of Joule heating, a set of equations were developed. Solutions of these were made by a finite difference scheme, coupling the nonlinear partial differential equations. The imposition of this electric field results in a highly localized distribution of the current density. The current is primarily located at the reaction front where the temperature is the highest. This is consistent with the fact that the electrical conductivity increases with increasing temperature. From the dependence of the degree of conversion to the product on the applied voltage, it is shown that the velocity of the combustion wave is linearly proportional to the field.

Reverse micelle synthesis of oxide nanopowders: Mechanisms of precipitate formation and agglomeration effects

We present an analysis of reverse micelle stability in four model systems. The first two systems, composed of unstable microemulsions of isooctane, water, and Na-AOT with additions of either iron sulfate or yttrium nitrate, were used for the synthesis of iron oxide or yttrium oxide powders. These oxide powders were of nanocrystalline character, but with some level of agglomeration that was dependent on calcination temperature and cleaning procedures. Results show that even though the reverse micellar solutions were unstable, nanocrystalline powders with very low levels of agglomeration could be obtained. This effect can be attributed to the protective action of the surfactant on the surfaces of the powders that prevents neck formation until after all the surfactant has volatilized. A striking feature of the IR spectra collected on the iron oxide powders is the absence of peaks in the ~1715 cm(-1) to 1750 cm(-1) region, where absorption due to the symmetric C=O (carbonyl) stretching occurs. The lack of such peaks strongly suggests the carbonyl group is no longer free, but is actively participating in the surfactant-precipitate interaction. The final two microemulsion systems, containing CTAB as the surfactant, showed that loss of control of the reverse micelle synthesis process can easily occur when the amount of salt in the water domains exceeds a critical concentration. Both model systems eventually resulted in agglomerated powders of broad size distributions or particles that were large compared to the sizes of the reverse micelles, consistent with the notion that the microemulsions were not stable and the powders were precipitated in an uncontrolled fashion. This has implications for the synthesis of nanopowders by reverse micelle synthesis and provides a benchmark for process control if powders of the highest quality are desired.

Mechanisms of Combustion Synthesis and Magnetic Response of High-Surface-Area Hexaboride Compounds

We present an analysis of the combustion synthesis mechanisms for the preparation of hexaboride materials using three compounds as model systems: EuB(6), YbB(6), and YB(6). These three hexaborides were chosen because of the differences in ionic radii between Eu(3+), Yb(3+), and Y(3+), which is a factor in their stability. The powders were prepared using metal nitrates, carbohydrazide, and two different boron precursor powders. The resulting materials were analyzed by X-ray diffraction, which showed that combustion synthesis is effective for the synthesis of EuB(6), since the Eu(3+) ion has an ionic radius greater than ∼1 Å. The synthesis of YbB(6) and YB(6) is not as effective because of the small size of the Yb(3+) and Y(3+) ions, making the hexaborides of these metals less stable and resulting in the synthesis of borates due to the presence of oxygen during the combustion process. Scanning electron microscopy and dynamic light scattering of the EuB(6) powders shows that the particle size of the hexaboride product is dependent on the particle size of the boron precursor. The magnetic susceptibility of our EuB(6) powders manifests irreversible behavior at low applied fields, which disappears at higher fields. This behavior can be attributed to the increase in size and number of magnetic polarons with increasing magnetic field.

Development of Mesoporosity in Scandia-Stabilized Zirconia: Particle Size, Solvent, and Calcination Effects

We present the mechanisms of formation of mesoporous scandia-stabilized zirconia using a surfactant-assisted process and the effects of solvent and thermal treatments on the resulting particle size of the powders. We determined that cleaning the powders with water resulted in better formation of a mesoporous structure because higher amounts of surfactant were preserved on the powders after washing. Nonetheless, this resulted in agglomerate sizes that were larger. The water-washed powders had particle sizes of >5 μm in the as-synthesized state. Calcination at 450 and 600 °C reduced the particle size to ∼1-2 and 0.5 μm, respectively. Cleaning with ethanol resulted in a mesoporous morphology that was less well-defined compared to the water-washed powders, but the agglomerate size was smaller and had an average size of ∼250 nm that did not vary with calcination temperature. Our analysis showed that surfactant-assisted formation of mesoporous structures can be a compromise between achieving a stable mesoporous architecture and material purity. We contend that removal of the surfactant in many mesoporous materials presented in the literature is not completely achieved, and the presence of these organics has to be considered during subsequent processing of the powders and/or for their use in industrial applications. The issue of material purity in mesoporous materials is one that has not been fully explored. In addition, knowledge of the particle (agglomerate) size is essential for powder handling during a variety of manufacturing techniques. Thus, the use of dynamic light scattering or any other technique that can elucidate particle size is essential if a full characterization of the powders is needed for achieving postprocessing effectiveness.

MODELING STUDIES OF THE EFFECT OF THERMAL AND ELECTRICAL CONDUCTIVITIES AND RELATIVE DENSITY OF FIELD-ACTIVATED SELF-PROPAGATING COMBUSTION SYNTHESIS

The role of the electrical conductivity of the product and of the thermal conductivities of the reactants on self-propagating combustion synthesis was investigated through modeling studies. Similar studies were made to investigate the role of the relative density of the reactants. The effect of an imposed electric field on the results of the modeling analysis was considered. For any given imposed field, the wave velocity exhibited a maximum at a given normalized thermal conductivity, electrical conductivity, and relative density. The results are discussed in terms of the Joule heat contribution of the field and are compared with experimental observations.