Challenges and Opportunities for Integrating Dealloying Methods into Additive Manufacturing.

The physical architecture of materials plays an integral role in determining material properties and functionality. While many processing techniques now exist for fabricating parts of any shape or size, a couple of techniques have emerged as facile and effective methods for creating unique structures: dealloying and additive manufacturing. This review discusses progress and challenges in the integration of dealloying techniques with the additive manufacturing (AM) platform to take advantage of the material processing capabilities established by each field. These methods are uniquely complementary: not only can we use AM to make nanoporous metals of complex, customized shapes-for instance, with applications in biomedical implants and microfluidics-but dealloying can occur simultaneously during AM to produce unique composite materials with nanoscale features of two interpenetrating phases. We discuss the experimental challenges of implementing these processing methods and how future efforts could be directed to address these difficulties. Our premise is that combining these synergistic techniques offers both new avenues for creating 3D functional materials and new functional materials that cannot be synthesized any other way. Dealloying and AM will continue to grow both independently and together as the materials community realizes the potential of this compelling combination.

Mechanism of hollow nanoparticle formation due to shape fluctuations.

Shape fluctuations in nanoparticles strongly influence their stability. Here, we introduce a quantitative model of such shape fluctuations and apply this model to the important case of Pt-shell/transition metal-core nanoparticles. By using a Gibbs distribution for the initial shapes, we find that there is typically enough thermal energy at room temperature to excite random shape fluctuations in core-shell nanoparticles, whose amplitudes are sufficiently high that the cores of such particles are transiently exposed to the surrounding environment. If this environment is acidic and dissolves away the core, then a hollow shell containing a pinhole is formed; however, this pinhole quickly closes, leaving a hollow nanoparticle. These results favorably compare to experiment, much more so than competing models based on the room-temperature Kirkendall effect.

Apparent inverse Gibbs-Thomson effect in dealloyed nanoporous nanoparticles.

The Gibbs-Thomson effect (the reduction of local chemical potential due to nanoscale curvature) predicts that nanoparticles of radius r dissolve at lower electrochemical potentials than bulk materials, decreasing as 1/r. However, we show here that if the particle is an alloy--susceptible to selective dissolution (dealloying) and nanoporosity evolution--then complete selective electrochemical dissolution and porosity evolution require a higher electrochemical potential than the comparable bulk planar material, increasing empirically as 1/r. This is a kinetic effect, which we demonstrate via kinetic Monte Carlo simulation. Our model shows that in the initial stages of dissolution, the less noble particle component is easily stripped from the nanoparticle surface, but owing to an increased mobility of the more noble atoms, the surface of the particle quickly passivates. At a fixed electrochemical potential, porosity and complete dealloying can only evolve if fluctuations in the surface passivation layer are sufficiently long-lived to allow dissolution from percolating networks of the less-noble component that penetrate through the bulk of the particle.

Mechanism of coarsening and bubble formation in high-genus nanoporous metals.

Coarsening of crystalline nanoporous metals involves complex changes in topology associated with the reduction of genus via both ligament pinch-off and void bubble formation. Although void bubbles in metals are often associated with vacancy agglomeration, we use large-scale kinetic Monte Carlo simulations to show that both bubble formation and ligament pinch-off are natural results of a surface-diffusion-controlled solid-state Rayleigh instability that controls changes in the topology of the porous material during coarsening. This result is used to find an effective activation energy for coarsening in nanoporous metals that is associated with the reduction of topological genus, and not the reduction of local surface roughness.

Oxygen reduction in nanoporous metal-ionic liquid composite electrocatalysts.

The improvement of catalysts for the four-electron oxygen-reduction reaction (ORR; O(2) + 4H(+) + 4e(-) → 2H(2)O) remains a critical challenge for fuel cells and other electrochemical-energy technologies. Recent attention in this area has centred on the development of metal alloys with nanostructured compositional gradients (for example, core-shell structure) that exhibit higher activity than supported Pt nanoparticles (Pt-C; refs 1-7). For instance, with a Pt outer surface and Ni-rich second atomic layer, Pt(3)Ni(111) is one of the most active surfaces for the ORR (ref. 8), owing to a shift in the d-band centre of the surface Pt atoms that results in a weakened interaction between Pt and intermediate oxide species, freeing more active sites for O(2) adsorption. However, enhancements due solely to alloy structure and composition may not be sufficient to reduce the mass activity enough to satisfy the requirements for fuel-cell commercialization, especially as the high activity of particular crystal surface facets may not easily translate to polyfaceted particles. Here we show that a tailored geometric and chemical materials architecture can further improve ORR catalysis by demonstrating that a composite nanoporous Ni-Pt alloy impregnated with a hydrophobic, high-oxygen-solubility and protic ionic liquid has extremely high mass activity. The results are consistent with an engineered chemical bias within a catalytically active nanoporous framework that pushes the ORR towards completion.

Length scales in alloy dissolution and measurement of absolute interfacial free energy.

De-alloying is the selective dissolution of one or more of the elemental components of an alloy. In binary alloys that exhibit complete solid solubility, de-alloying of the less noble component results in the formation of nanoporous metals, a materials class that has attracted attention for applications such as catalysis, sensing and actuation. In addition, the occurrence of de-alloying in metallic alloy systems under stress is known to result in stress-corrosion cracking, a key failure mechanism in fossil fuel and nuclear plants, ageing aircraft, and also an important concern in the design of nuclear-waste storage containers. Central to the design of corrosion-resistant alloys is the identification of a composition-dependent electrochemical critical potential, Vcrit, above which the current rises dramatically with potential, signalling the onset of bulk de-alloying. Below Vcrit, the surface is passivated by the accumulation of up to several monolayers of the more noble component. The current understanding of the processes that control Vcrit is incomplete. Here, we report on de-alloying results of Ag/Au superlattices that clarify the role of pre-existing length scales in alloy dissolution. Our data motivated us to re-analyse existing data on critical potentials of Ag-Au alloys and develop a simple unifying picture that accounts for the compositional dependence of solid-solution alloy critical potentials.

Volume change during the formation of nanoporous gold by dealloying.

We report a macroscopic shrinkage by up to 30 vol % during electrochemical dealloying of Ag-Au. Since the original crystal lattice is maintained during the process, we suggest that the formation of nanoporous gold in our experiments is accompanied by the creation of a large number of lattice defects and by local plastic deformation.

Evolution of nanoporosity in dealloying.

Dealloying is a common corrosion process during which an alloy is 'parted' by the selective dissolution of the most electrochemically active of its elements. This process results in the formation of a nanoporous sponge composed almost entirely of the more noble alloy constituents. Although considerable attention has been devoted to the morphological aspects of the dealloying process, its underlying physical mechanism has remained unclear. Here we propose a continuum model that is fully consistent with experiments and theoretical simulations of alloy dissolution, and demonstrate that nanoporosity in metals is due to an intrinsic dynamical pattern formation process. That is, pores form because the more noble atoms are chemically driven to aggregate into two-dimensional clusters by a phase separation process (spinodal decomposition) at the solid-electrolyte interface, and the surface area continuously increases owing to etching. Together, these processes evolve porosity with a characteristic length scale predicted by our continuum model. We expect that chemically tailored nanoporous gold made by dealloying Ag-Au should be suitable for sensor applications, particularly in a biomaterials context.

Nonclassical smoothening of nanoscale surface corrugations.

We report the first experimental observation of nonclassical morphological equilibration of a corrugated crystalline surface. Periodic rippled structures with wavelengths of 290-550 nm were made on Si(001) by sputter rippling and then annealed at 650-750 degrees C. In contrast to the classical exponential decay with time, the ripple amplitude Alambda(t) followed an inverse linear decay, Alambda(t)=Alambda(0)/(1+klambdat), agreeing with a prediction of Ozdemir and Zangwill. We measure the activation energy for surface relaxation to be 1.6+/-0.2 eV, consistent with the fundamental energies of creation and migration on Si(001).

The crystal and molecular structure of ellagic acid dihydrate: a dietary anti-cancer agent.

The crystal and molecular structure of ellagic acid dihydrate has been determined by X-ray diffraction techniques. This acid inhibits the carcinogenic properties of a variety of chemical compounds including benzo[alpha]pyrene-7,8-diol-9,10-epoxide, aflatoxin B1, N-methyl-N-nitrosourea, 3-methyl-cholanthrene and 7,12-dimethylbenz[alpha]anthracene. Ellagic acid dihydrate forms triclinic crystals with unit cell dimensions: a = 7.656(1) A, b = 9.563(1)A, c = 4.623(1) A, alpha = 97.88(1) degrees, beta = 103.2(1) degrees, gamma = 102.22(1) degrees, V = 315.9 A3, space group = P1. There is a center of symmetry in the crystal coinciding with the center of the molecule, so that there is only one molecule in the unit cell. Ellagic acid is planar and molecules are interconnected by hydrogen bonds to water, giving rise to layers of molecules throughout the crystal. Its activity and anti-cancer properties are compared with those of a similar naturally occurring compound, quercetin.

Comparison of mitral valve dimensions and motion in mitral valve prolapse with severe mitral regurgitation to uncomplicated mitral valve prolapse and to mitral regurgitation without mitral valve prolapse.

To determine the mitral valve abnormalities associated with hemodynamically important mitral regurgitation (MR) among patients with mitral valve prolapse (MVP), computerized 2-dimensional echocardiographic measurements of mitral leaflet and anular dimensions and motion in 26 patients with MVP and MR were compared to those in 48 subjects with uncomplicated MVP, 16 patients with MR due to etiologies other than MVP (rheumatic in 8) and 35 normal adults. Compared to both uncomplicated MVP and normal subjects, patients with MVP plus MR were older (p less than 0.05), had strikingly large mitral leaflets and anulus (p less than 0.0005) and were more likely to have systolic billowing of mitral leaflets in the parasternal long-axis view (24 of 26 [92%] vs 24 of 48 subjects with uncomplicated MVP [50%], p less than 0.001). Overlap in anular and posterior leaflet dimensions in normal and uncomplicated MVP subjects occurred in the 20 MVP plus MR patients who continue to be followed medically but not in the 6 MVP plus MR patients who underwent mitral valve surgery during 22 +/- 14 months follow-up. Patients with MR due to rheumatic or other non-MVP etiologies had enlargement of mitral leaflets and anulus virtually identical to that in MVP plus MR patients. In conclusion, patients with severe MR due to MVP are older, have striking mitral valve enlargement and more frequently exhibit leaflet billowing compared with subjects with uncomplicated MVP. Similar mitral leaflet enlargement was found in patients with non-MVP etiologies of MR, suggesting that mitral anular and leaflet enlargement may play a more general role in the pathogenesis of MR than is currently appreciated.

Inappropriate ventricular blanking in a DDI pacemaker.

The DDI mode is a new pacing mode with potential advantages over DVI pacing. We describe anomalous post R wave ventricular pacing due to the presence of inappropriate ventricular blanking periods in a pacemaker programmed to the DDI mode. Although no adverse consequences were seen in our patients, potentially dangerous R-on-T pacing could occur, particularly if long atrioventricular delays are programmed. A method for eliminating this pacing anomaly is described. Patients programmed to the DDI mode with the pacemaker model described should be evaluated for post R wave ventricular pacing and corrective measures should be taken.

Effect of magnetic resonance imaging on DDD pacemakers.

A previous study suggested the safety of exposing patients with certain pacemakers models to magnetic resonance imaging (MRI). However, the function of a variety of more advanced DDD pacemakers and the effect of higher magnetic and radio-frequency (rf) field strengths has not been reported. In the present study 4 different DDD pacemakers (Cordis 233F, Intermedic 283-01, Medtronic 7000A, and Pacesetter 283) were tested in a saline phantom under several conditions and with various imaging sequences. Pacemaker output was monitored using electrocardiographic telemetry. All units paced normally in the static magnetic field. However, during imaging, all units malfunctioned, with total inhibition of atrial and ventricular output in 3 of the pacemakers. In the fourth pacemaker, ventricular backup pacing was activated at high rf pulse repetition rates. However, the MRI scanner could trigger atrial output in this pacemaker at rates of up to 800/minute. All malfunctions were a result of rf interference, whereas gradient and static magnetic fields had no effect. Thus, despite magnetic fields had no effect. Thus, despite magnetic field strengths adequate to close pacemaker reed switches, rf interference during MRI may cause total inhibition of atrial and ventricular output in DDD pacemakers, and can also cause dangerous atrial pacing at high rates. MRI should be avoided in patients with these DDD pacemakers.