James P. Kelly

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.

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.

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.

Shock Wave Response of Iron-based In Situ Metallic Glass Matrix Composites

The response of amorphous steels to shock wave compression has been explored for the first time. Further, the effect of partial devitrification on the shock response of bulk metallic glasses is examined by conducting experiments on two iron-based in situ metallic glass matrix composites, containing varying amounts of crystalline precipitates, both with initial composition Fe49.7Cr17.7Mn1.9Mo7.4W1.6B15.2C3.8Si2.4. The samples, designated SAM2X5-600 and SAM2X5-630, are X-ray amorphous and partially crystalline, respectively, due to differences in sintering parameters during sample preparation. Shock response is determined by making velocity measurements using interferometry techniques at the rear free surface of the samples, which have been subjected to impact from a high-velocity projectile launched from a powder gun. Experiments have yielded results indicating a Hugoniot Elastic Limit (HEL) to be 8.58 ± 0.53 GPa for SAM2X5-600 and 11.76 ± 1.26 GPa for SAM2X5-630. The latter HEL result is higher than elastic limits for any BMG reported in the literature thus far. SAM2X5-600 catastrophically loses post-yield strength whereas SAM2X5-630, while showing some strain-softening, retains strength beyond the HEL. The presence of crystallinity within the amorphous matrix is thus seen to significantly aid in strengthening the material as well as preserving material strength beyond yielding.

Effect of Powder Characteristics on Nanosintering

If all other things are equal, nanopowders will sinter faster and at lower temperatures than larger powders. However, the increased surface area to volume ratio of these materials presents additional processing challenges that correspond to greater difficulty in achieving the goal of sintering for finer powders. This is not related to the “nano” effects as described in previous chapters, but to powder characteristics that can strongly influence the sintering behavior. These characteristics can be seen as the “real life” parameters, such as agglomeration state and contaminations that if not addressed properly can confuse sintering tendencies and complicate sintering effects at the nanoscale. This chapter presents the effects that may contribute to nanosintering and the importance of adequate processing of nanopowders for achieving optimum sintering behavior.

Shock Wave Response of Iron-Based Metallic Glass Matrix Composites

The response of amorphous steels to shock wave compression has been explored for the first time. Further, the effect of the presence of partial crystallinity on the shock response of bulk metallic glasses is examined by conducting experiments on two iron-based in situ metallic glass matrix composites, containing varying amounts of crystalline precipitates, both with initial composition Fe49.7Cr17.7Mn1.9Mo7.4W1.6B15.2C3.8Si2.4. The samples, designated SAM2X5-630 and SAM2X5- 600, are partially crystalline and X-ray amorphous, respectively, due to differences in sintering parameters during sample preparation. Shock response is determined by making velocity measurements at the rear free surface of the samples, which have been subjected to impact from a high-velocity projectile. Experiments have yielded results indicating a Hugoniot Elastic Limit (HEL) to be about 12.5 GPa for SAM2X5-630 and 8 GPa for SAM2X5-600. The former HEL result is higher than elastic limits for any BMG reported in the literature thus far. Both SAM2X5-630 and SAM2X5-600 undergo strain-softening beyond the HEL but seem to recover post-yield strength at a certain higher threshold peak stress. The presence of crystallinity within the amorphous matrix is thus seen to significantly aid in strengthening the material as well as preserving material strength beyond yielding.

Bulk Mechanical Properties Testing of Metallic Marginal Glass Formers

We developed a unique three-point bend testing apparatus to measure bulk mechanical properties of a model metallic glass alloy (SAM2X5 with nominal composition Fe49.7Cr17.1Mn1.9Mo7.4W1.6B15.2C3.8Si2.4) prepared by spark plasma sintering. The relatively large sample sizes in the present work allowed for the preparation of test specimens with a macroscale cross section (in the millimeter range) with well-controlled sample dimensions closer to standardized tests. Wire saw cutting allowed for a relatively sharp notch radius (3x smaller than previous studies) and minimal sample damage. We determined that Young’s modulus and notch fracture toughness measured by our three-point bending apparatus are 230 GPa and 4.9 MPam1/2. Also, Vickers indentation and flexure testing provided consistent results for Young’s modulus. Indentation fracture toughness measured by Vickers indentation produced values at least 50% lower than by flexure. The microscale mechanical properties testing technique presented in this work and subsequent analyses are applicable to specimens of other compositions or ones prepared by other methods.