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Ion (de)hydration is a key rate-determining step in interfacial processes from corrosion to electrochemical energy storage. However, predicting the kinetics of ion (de)hydration remains challenging, prompting the use of static proxies such as hydration energy and valence. While useful for assessing thermodynamic preferences, such descriptors cannot fully capture the dynamical softness of the hydration shell that dictates kinetics. Accordingly, we use first-principles molecular dynamics to analyze hydration shell softness for a diverse set of metal cations. Three dynamic metrics are introduced to intuitively describe the bond rigidity, shape deformability, and exchange fluidity of the solvation shell. Together, these metrics capture the relevant physics in the static descriptors, while offering a far more complete and efficient representation for the overall propensity for (de)hydration. Application to the hydrated ion set demonstrates a weak connection between dynamical softness and hydration energy, confirming that dynamical descriptors of hydration are key for correctly describing ion transfer processes.

We compare the 355 nm, 45o AOI p-pol 8 n-s laser damage performance of standing-wave hafnia single layers fabricated using argon and xenon as working gas. A suite of metrology tools has been employed to understand the structural, chemical and paramagnetic defect states in the two films. The resultant films from the xenon deposition process are highly dense and have high 3w laser damage performance.

Interactions between different types of additives with specific crystal surfaces of mineral phases found in biominerals were investigated at nanometer and micrometer scales by in situ atomic force microscopy (AFM). Firstly, the inhibitory effect of magnesium ion (Mg2+) and that of a peptide molecule, L-aspartic acid 6mer (L-Asp6) on the growth of a fast growing [−1 0 −1] step on the (−1 0 1) face of calcium oxalate monohydrate (COM) crystal are quantitatively compared by the step speed data. Differences in the inhibitory effect are explained based on a De Yoreo model of step kinetics in detail. The step speed data show that Mg2+ had a little inhibitory effect on the growth of the [−1 0 −1] step, approaching a limiting value of about 15% reduction in the step speed, whereas L-Asp6 was substantially more effective in inhibiting the step growth with an ability to stop the growth completely. Secondly, the effects of a protein molecule, bovine serum albumin (BSA) and a pseudo protein-like organic particle PSPMA30-PDPA47 micelle on the growth of calcite on its {1 0 4} faces are compared. Both BSA and PSPMA30-PDPA47 micelle temporarily pinned the passing steps without or negligibly inhibiting the step growth overall. The BSA molecule remained at the crystal surface without incorporation into the crystal because the steps passed through it, pushing it up and out. However, in contrast to the BSA, the micelle was incorporated into the crystal by the passing steps. These results together with other relevant studies suggest that the decisive factor in determining for macromolecules to be incorporated into growing minerals or to remain intact on the mineral surface with no incorporation is the magnitude of binding strength of the macromolecules to the growing step against the step’s propagation force.

Additively manufactured 316L stainless steels (316L SS) using laser powder bed fusion technique (L-PBF) exhibit an excellent combination of high strength and ductility compared to the conventional counterpart. The outstanding material mechanical properties originate from the sub-grain cellular structures developed during the rapid solidification inherent to L-PBF. These structures consist of elongated cells decorated by high density of dislocations, trapped solute, and fine precipitates at their boundaries. The impact of such cellular structures on corrosion resistances, however, remains incompletely understood. In addition, the L-PBF process leads to high surface roughness and usually around 0.1 to 0.5% of porosity. However, the pitting potential of the L-PBF 316L SS can be an order of magnitude higher than the conventional, well annealed counterpart. In this talk, we will first present a detailed multi-scale characterization of the microstructural features unique to L-PBF 316L SS. In a second part, we will present our experimental-simulation integration approach where we combine surface chemistry mapping and electron and atomic force microscopy with multi-scale simulations to understand the effect of local microstructure variations on pitting and metal dissolution rates in NaCl and HCl environments. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. Authors acknowledge the support of the Laboratory Directed Research and Development (LDRD) program (20-SI-004) at LLNL.

Surfaces of additively manufactured (AM) stainless steel (SS) by fusing metallic powders are known to be much rougher than those produced by conventionally fabrication methods. The measured surface roughness (Sa or Sq) can range from a few to tens of microns depending on the build angle. Recent studies have shown that the large surface roughness associated with printing conditions makes the AM SS surfaces susceptible to localized corrosion and open-circuit corrosion [1, 2]. Sa or Sq have also long been used to characterize the corrosion behavior of traditionally manufactured metals [3]. However, the open-circuit corrosion rate of the traditional metals has been mainly studied in the submicron-scale surface roughness, and some results have showed that changes in the roughness of hundreds of nanometers or more have little effect on the change in the corrosion rate [4]. In addition, when applied to AM materials, no consistent correlation between the pitting breakdown potential (Eb) and surface roughness has been observed. In this study, the dependence of the corrosion behavior on the electrochemically active surface area of AM 316L SS, defined as the total area of the curvilinear surface that is exposed to the electrolyte, has been explored. The localized corrosion susceptibility was evaluated under full immersion in 3.5 wt% NaCl solution through potentiodynamic polarization for testing articles with different surface roughness. While no correlation to Sa or Sq was displayed, the Eb values showed a clear statistical trend with respect to the electrochemically active surface area: the lager the active surface area, the smaller the Eb. The observed correlation fits well with a previously reported stochastic pitting model on metal surfaces [5]. In addition, by normalizing linear polarization resistance and electrochemical impedance spectra with the electrochemically active surface area, it can be confirmed that the as-printed surface roughness of AM 316L SS did not have a significant effect on the change of the open-circuit corrosion phenomenon under static immersion conditions. Our results suggest that electrochemically active surface area is an appropriate parameter to characterize the corrosion behavior of AM metal surfaces. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. References 1. Melia, M.A., et al., How build angle and post-processing impact roughness and corrosion of additively manufactured 316L stainless steel. Npj Materials Degradation, 2020. 4(1). 2. Ni, C., Y. Shi, and J. Liu, Effects of inclination angle on surface roughness and corrosion properties of selective laser melted 316L stainless steel. Materials Research Express, 2019. 6(3). 3. Walter, R. and M.B. Kannan, Influence of surface roughness on the corrosion behaviour of magnesium alloy. Materials & Design, 2011. 32(4): p. 2350-2354. 4. Li, W. and D.Y. Li, Influence of surface morphology on corrosion and electronic behavior. Acta Materialia, 2006. 54(2): p. 445-452. 5. Shibata, T., 1996 W R Whitney Award lecture: Statistical and stochastic approaches to localized corrosion. Corrosion, 1996. 52(11): p. 813-830.

Hydrogen interaction with metal oxides is an important phenomenon that affects all vital areas of industry such as aerospace, transportation, and commercial applications. The metal oxide provides a naturally forming protective layer against dissolution of the underlying metal. It has been reported that hydrogen is still able to percolate through this protective layer traveling all the way to the metal to form a corrosive brittle metal hydride. There have been many studies looking to understand the interaction of hydrogen at the surface but an in depth look at the surface to bulk transition of hydrogen through a metal oxide for all representative phases of an oxide is minimally represented in the literature. For the focus of our study, we employed a multi-scale approach combined with experimental studies to explore the different phases of titania (TiO2) which includes rutile, anatase, and an amorphous phase. A thermodynamic analysis of the stability for hydrogen was considered using density functional theory (DFT) starting at the low energy surface facets to the bulk. For the amorphous phase, the binding energy was analyzed as a function of the hydrogen content and oxygen coordination environment. Temperature programmed desorption (TPD) experiments provided a direct comparison with theory. Additionally, NMR simulations validified the generated amorphous phase which agreed well with experimental data. The material properties computed using DFT were used in combination with experimental results to parameterize a mesoscale model. Several environmental conditions were analyzed consisting of grain size, temperature, and grain boundary properties. Further work investigated crystalline titanium (Ti) in the bulk and at several grain boundaries to elucidate possible initiation stages of hydride formation. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

It is well known that dielectric coatings used in high energy laser systems for beam steering are susceptible to laser damage. The laser damage ensued in high refractive index materials, such as hafnia, is responsible for limiting the laser operation fluence and lifetime. Although hafnia is an ideal high refractive index material used in dielectric coatings for a broad range of laser wavelengths, defects developed during the deposition process leads to laser-induced damage. In order to increase the resistance to laser damage and improve laser performance, it is imperative to understand the underlying physics of laser damage in high index coating materials. Earlier work observed a substantial difference in laser damage thresholds for hafnia coatings produced by different deposition methods, yet the underlying mechanisms for the observed difference remains elusive. In this work we investigated the responses of single layer hafnia films produced by two deposition processes, electron beam (e-beam) evaporation and ion beam sputtering (IBS) methods upon UV ns-laser exposure. The films underwent laser damage testing using a 1-on-1 laser damage testing protocol with a beam size of 650 µm (1/e2) at 355 nm and 8 ns pulse duration. Both S and P polarizations were tested at a 45° angle of incidence. Chemical, structural and morphological characterizations of the films both pre- and post-laser damage were performed using Rutherford backscattering spectroscopy, glancing incidence X-Ray diffraction, and optical and scanning/transmission electron microscopy. We found that films deposited from the e-beam process had a higher damage onset threshold (4.4 +/- 0.1 J/cm2) than those deposited by IBS method (2.1 +/- 0.2 J/cm2). Furthermore, a polarization-dependent damage threshold onset was observed for the e-beam evaporated coatings but was not observed in IBS films. Although the typical size of the damage in general is larger for the e-beam produced films, the morphology shows similar foamy appearance in both films. The density of the damage sites, on the other hand, was much greater in the IBS produced films than that by the e-beam method. The observed difference can be attributed to their resulting structural/textural differences inherited in each method: porous in the e-beam films and dense with isolated nanobubbles in the IBS films, which can lead to a large difference in laser-defect coupling. The underlying physical mechanism will be discussed in detail. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. IM Release# LLNL-ABS-809117

We herein show the chiral recognition and separation of aspartic acid (Asp) enantiomers by achiral brushite due to the asymmetries of their dynamical steps in its nonequilibrium states. Growing brushite has a higher adsorption affinity to d-Asp, while l-Asp is predominant on the dissolving brushite surface. Microstructural characterization reveals that chiral selection is mainly attributed to brushite [101] steps, which exhibit two different configurations during crystal growth and dissolution, respectively, with each preferring a distinct enantiomer due to this asymmetry. Because these transition step configurations have different stabilities, they subsequently result in asymmetric adsorption. By varying free energy barriers through solution thermodynamic driving force (i.e., supersaturation), the dominant nonequilibrium intermediate states can be switched and chiral selection regulated. This finding highlights that the dynamic steps can be vital for chiral selection, which may provide a potential pathway for chirality generation through the dynamic nature.

We compare the distribution of hafnia chemistries as a function of sun and planet position in an ion beam sputtering system. Hafnia film chemistries were investigated both without and with planetary rotation. In the former case, the film thickness, stoichiometries and entrapped argon varied drastically as a function of sun position, with one sun position exhibiting high entrapped argon content. With full planetary rotation used during deposition, the film stoichiometry is nearly ideal with 6% entrapped argon content. It is observed that the center of the planets is an exception, with a slightly metallic stoichiometry and high entrapped argon. Interestingly, all hafnia optical films produced in this study exhibit an inverse relationship between oxygen content and entrapped argon.

Understanding the origin of laser damage-prone precursors in high index materials such as hafnia holds the key to the development of laser damage-resistant multilayer dielectric coated optics for high power and energy laser systems. In this study, we investigate the source of sub-stoichiometry, a potent laser damage precursor, in hafnia films produced by an ion beam sputtering (IBS) deposition method and the effect of such defects on the film performance upon ns ultraviolet (UV) laser (8 ns, 355 nm) exposure. Chemical analysis of data obtained via Rutherford backscattering spectroscopy (RBS) suggests that hafnia films deposited at two different planetary locations from the same deposition run exhibit anisotropic and location-dependent stoichiometries. While the oxygen-to-hafnium ratio is at the stoichiometric value of 2 for the hafnia film at the edge location, the ratio is significantly deviated and is 1.7 for that deposited at the planetary center. The sub-stoichiometric hafnia films display a much lower 1-on-1 damage onset at 1.6 ± 0.2 J/cm2 compared to 2.3 ± 0.2 J/cm2 in a stoichiometric film. The low damage performance films also have an over three times higher damage density at fluences above initiation. Coupled with Monte Carlo simulations, we reveal that sub-stoichiometry is primarily attributed to preferential removal of oxygen during film deposition by the bombardment of energetic reflected argon neutrals. The resulting oxygen deficiencies create the sub-bandgap states which facilitate the strong laser energy coupling and reduce the resistance to laser-induced damage in the hafnia single layer films.

There are 830 transport mirrors with a combined surface area of approximately 255 m2 of precision multilayer coatings deposited on 50 metric tons of BK7 glass in the high fluence transport section of the National Ignition Facility (NIF). With peak fluences over 20 J/cm2 at 1053 nm, less than five percent of these mirrors are exchanged annually due to laser damage since full system operations began in 2009. Multiple technologies have been implemented to achieve these low exchange rates. The coatings are complex dichroics designed to reflect the fundamental wavelength (1053 nm) and an alignment beam (374 nm) while suppressing target backscatter wavelengths (351 nm and 400-700 nm) from backward propagation up the beamlines. Each optic is off-line laser conditioned to nominally 50% over the average fluence and nominally 90% of the peak fluence allowing the final laser conditioning to occur on-line during NIF operations. Although the transport section of NIF is sealed in a clean argon environment, air knives were installed on upward facing transport mirrors to blow off particulates that could accumulate and initiate laser damage. Beam dumps were installed in between the final optics assembly and the final transport mirrors to capture ghost reflections from the anti-reflection coated surfaces on the transmissive optics used for polarization rotation, frequency conversion, and focusing the 192 laser beams on target. Spot blockers, normally used for the final optics, are sometimes used to project a shadow over transport mirror laser damage in an effort to arrest laser damage growth and extend transport mirror lifetime. Post analysis of laser-damaged mirrors indicates that the dominant causes of laser damage are from surface particulates and the 351-nm wavelength target backscatter.

The inhibitory effect of linear enantiomers of L- and D-Asp6 on the growth of calcium oxalate monohydrate crystal has been investigated using in situ atomic force microscopy. The inhibitory magnitude of D-Asp6 on the growth of the [00] step on the (010) face is about 10% larger than that of L-Asp6. While no chiral effect is observed or expected on the growth of the [0] step on the (01) face by both enantiomers, their inhibitory effect on this step is much stronger than that on the [00] step on the (010) face. In both cases, the step morphology indicates that these enantiomers create the impurity pinning along the steps, while the dependence of step speed on supersaturation shows that they also produce a reduction of the step kinetic coefficients. Analysis of the step speed data within the context of an existing model for step pinning and kink blocking shows that the major impact of Asp6 is to block active kink sites. The larger inhibition of the [00] step growth by D-Asp6 over L-Asp6 and the substantially larger inhibition of the [0] step over the [00] step by both enantiomers both result from larger affinity for adsorption to the (010) face and the (01) face, respectively. This is because the larger adsorption leads to a higher density of blocking kink sites along the steps. The estimated difference in binding energy of L- and D-Asp6 to the respective faces from the kinetics model is consistent with the trend predicted by our molecular modeling of the enantiomer binding to the faces.

Investigation of large-aperture laser damage at oblique incidence shows that the damage induced by laser contaminants on HR multilayer coatings depends on the thickness and thermal-mechanical properties of the protective capping materials

Minerals in organisms often exhibit chiral shapes. The physical mechanism by which chiral information is transferred from molecules to crystal morphology is still not well-defined. In this article,...

Calcite crystals were grown in the presence of full-length amelogenin and during its proteolysis by recombinant human matrix metalloproteinase 20 (rhMMP-20). Recombinant porcine amelogenin (rP172) altered the shape of calcite crystals by inhibiting the growth of steps on the {104} faces and became occluded inside the crystals. Upon co-addition of rhMMP-20, the majority of the protein was digested resulting in a truncated amelogenin lacking the C-terminal segment. In rP172-rhMMP-20 samples, the occlusion of amelogenin into the calcite crystals was drastically decreased. Truncated amelogenin (rP147) and the 25-residue C-terminal domain produced crystals with regular shape and less occluded organic material. Removal of the C-terminal diminished the affinity of amelogenin to the crystals and therefore prevented occlusion. We hypothesize that HAP and calcite interact with amelogenin in a similar manner. In the case of each material, full-length amelogenin binds most strongly, truncated amelogenin binds weakly and the C-terminus alone has the weakest interaction. Regarding enamel crystal growth, the prevention of occlusion into maturing enamel crystals might be a major benefit resulting from the selective cleavage of amelogenin at the C-terminus by MMP-20. Our data have important implications for understanding the hypomineralized enamel phenotype in cases of amelogenesis imperfecta resulting from MMP-20 mutations and will contribute to the design of enamel inspired biomaterials.

Aberrant protein aggregation causes numerous neurological diseases including Creutzfeldt-Jakob disease (CJD), but the aggregation mechanisms remain poorly understood. Here, we report AFM results on the formation pathways of β-oligomers and nonfibrillar aggregates from wild-type full-length recombinant human prion protein (WT) and an insertion mutant (10OR) with five additional octapeptide repeats linked to familial CJD. Upon partial denaturing, seeds consisting of 3-4 monomers quickly appeared. Oligomers of ~11-22 monomers then formed through direct interaction of seeds, rather than by subsequent monomer attachment. All larger aggregates formed through association of these β-oligomers. Although both WT and 10OR exhibited identical aggregation mechanisms, the latter oligomerized faster due to lower solubility and, hence, thermodynamic stability. This novel aggregation pathway has implications for prion diseases as well as others caused by protein aggregation.

Pathological mineralization is a common phenomenon in broad range of plants and animals. In humans, kidney stone formation is a well-known example that afflicts approximately 10% of the population. Of the various calcium salt phases that comprise human kidney stones, the primary component is calcium oxalate monohydrate (COM). Citrate, a naturally occurring molecule in the urinary system and a common therapeutic agent for treating stone disease, is a known inhibitor of COM. Understanding the physical mechanisms of citrate inhibition requires quantification of the effects of both background electrolytes and citrate on COM step kinetics. Here we report the results of an in situ AFM study of these effects, in which we measure the effect of the electrolytes LiCl, NaCl, KCl, RbCl, and CsCl, and the dependence of step speed on citrate concentration for a range of COM supersaturations. We find that varying the background electrolyte results in significant differences in the measured step speeds and in step morphology, with KCl clearly producing the smallest impact and NaCl the largest. The kinetic coefficient for the former is nearly three times larger than for the latter, while the steps change from smooth to highly serrated when KCl is changed to NaCl. The results on the dependence of step speed on citrate concentration show that citrate produces a dead zone whose width increases with citrate concentration as well as a continual reduction in kinetic coefficient with increasing citrate level. We relate these results to a molecular-scale view of inhibition that invokes a combination of kink blocking and step pinning. Furthermore, we demonstrate that the classic step-pinning model of Cabrera and Vermilyea (C–V model) does an excellent job of predicting the effect of citrate on COM step kinetics provided the model is reformulated to more realistically account for impurity adsorption, include an expression for the Gibbs–Thomson effect that is correct for all supersaturations, and take into account a reduction in kinetic coefficient through kink blocking. The detailed derivation of this reformulated C–V model is presented and the underlying materials parameters that control its impact are examined. Despite the fact that the basic C–V model was proposed nearly 50 years ago and has seen extensive theoretical treatment, this study represents the first quantitative and molecular scale experimental confirmation for any crystal system.

Many transition metal complexes exhibit infrared or visible optical absorption arising from d-d transitions that are the key to functionality in technological applications and biological processes. The observed spectral characteristics of the absorption spectra depend on several underlying physical parameters whose relative contributions are still not fully understood. Although conventional arguments based on ligand-field theory can be invoked to rationalize the peak absorption energy, they cannot describe the detailed features of the observed spectral profile such as the spectral width and shape, or unexpected correlations between the oscillator strength and absorption peak position. Here, we combine experimental observations with first-principles simulations to investigate origins of the absorption spectral profile in model systems of aqueous Cu(2+) ions with Cl(-), Br(-), NO2(-) and CH3CO2(-) ligands. The ligand identity and concentration, fine structure in the electronic d-orbitals of Cu(2+), complex geometry, and solvation environment are all found to play key roles in determining the spectral profile. Moreover, similar physiochemical origins of these factors lead to interesting and unexpected correlations in spectral features. The results provide important insights into the underlying mechanisms of the observed spectral features and offer a framework for advancing the ability of theoretical models to predict and interpret the behavior of such systems.

Fe-doped lithium sodium silicate glasses codoped with Sn and C to promote the Fe²⁺ redox state are investigated under simultaneous excitation at the first and third harmonics of a nanosecond Nd:YAG laser. The aim is to evaluate critical parameters associated with the potential use of this material as an optical filter that transmits the third harmonic but blocks the fundamental frequency. Estimations of the excited-state absorption coefficient and photobleaching (reduction of absorption at the fundamental) are provided. The results provide insight on the design and expected operational parameters of this type of Fe-doped materials.

Calcium oxalate monohydrate (COM) is the primary constituent of the majority of renal stones. Osteopontin (OPN), an aspartic acid-rich urinary protein, and citrate, a much smaller molecule, are potent inhibitors of COM crystallization at levels present in normal urine. Current concepts of the role of site-specific interactions in crystallization derived from studies of biomineralization are reviewed to provide a context for understanding modulation of COM growth at a molecular level. Results from in situ atomic force microscopy (AFM) analyses of the effects of citrate and OPN on growth verified the critical role of site-specific interactions between these growth modulators and individual steps on COM crystal surfaces. Molecular modeling investigations of interactions of citrate with steps and faces on COM crystal surfaces provided links between the stereochemistry of interaction and the binding energy levels that underlie mechanisms of growth modification and changes in overall crystal morphology. The combination of in situ AFM and molecular modeling provides new knowledge that will aid rationale design of therapeutic agents for inhibition of stone formation.

The classic theory of Cabrera and Vermilyea (C-V) postulates that inhibition of crystallization by impurities is the result of pinning of step motion. Although generally accepted, the predictions of the C-V model have not been previously linked to studies of impurity adsorption in macroscopic crystallization systems. Since calcium oxalate monohydrate (COM) is the primary constituent of most human kidney stones, effects of impurities on COM crystallization are biologically relevant. Recent in situ atomic force microscopy (AFM) studies suggest that citrate molecules adsorb to COM step edges on the (−101) face, thereby pinning step motion and decreasing the velocity of the steps. We have now investigated the crystallization kinetics of COM in the presence of citrate at 37 °C and I = 0.15 mol L-1 using the constant composition (CC) method. The dependence of growth rate on both supersaturation and citrate concentration were measured, and the behavior of the COM−citrate system was found to be in reasonable agre...

The design of effective crystallization inhibitors of calcium oxalate monohydrate (COM), the primary constituent of kidney stones, is a significant goal. Inhibitory molecules identified in urine include a small organic anion, citrate, and osteopontin (OPN), an aspartic acid-rich protein. The results of molecular-scale analyses combining force microscopy with molecular modeling raised the possibility that inhibition of COM crystallization might be increased by the additive effects of citrate and OPN because they act on different crystal faces. Constant composition (CC) kinetics studies of COM crystal growth now confirm that additive effects are, indeed, achieved in vitro when both citrate and OPN are present. These results suggest that a strategy employing combinations of inhibitors may provide a useful therapeutic approach to urinary stone disease.

We investigate defects forming in Ce³⁺-doped fused silica samples following exposure to nanosecond ultraviolet laser pulses and their relaxation as a function of time and exposure to low intensity light at different wavelengths. A subset of these defects are responsible for inducing absorption in the visible and near infrared spectral range, which is of critical importance for the use of this material as ultraviolet light absorbing filter in high power laser systems. The dependence of the induced absorption as a function of laser fluence and methods to most efficiently mitigate this effect are presented. Experiments simulating the operation of the material as a UV protection filter for high power laser systems were performed in order to determine limitations and practical operational conditions.

The response of a potential candidate protective capping layer (SiO2 or Al2O3) to laser exposure of 1ω (1053 nm) to high-reflector silica-hafnia multilayer coatings in the presence of variously shaped Ti particles is investigated by combining laser damage testing and numerical modeling. Each sample is exposed to a single oblique angle (45 deg) laser shot (p-polarization, ∼10 J/cm2, 14 ns) in the presence of spherically or irregularly shaped Ti particles on the surface. The two capping layers show markedly different responses. For the spherical particles, the Al2O3 cap layer exhibits severe damage, with the capping layer becoming completely delaminated at the particle locations. The SiO2 capping layer is only mildly modified by a shallow depression, likely due to plasma erosion. The different response of the capping layer is attributed to the large difference in the thermal expansion coefficient of the materials, with that of the Al2O3 about 15 times greater than that of the SiO2 layer. For the irregular particles, the Al2O3 capping layer displays minimal to no damage while the SiO2 capping layer is significantly damaged. The difference is due to the disparity in mechanical strength with Al2O3 possessing approximately 10 times higher fracture toughness.

Growing laser damage sites on multilayer high-reflector coatings can limit mirror performance. One of the strategies to improve laser damage resistance is to replace the growing damage sites with predesigned benign mitigation structures. By mitigating the weakest site on the optic, the large-aperture mirror will have a laser resistance comparable to the intrinsic value of the multilayer coating. To determine the optimal mitigation geometry, the finite-difference time-domain method was used to quantify the electric-field intensification within the multilayer, at the presence of different conical pits. We find that the field intensification induced by the mitigation pit is strongly dependent on the polarization and the angle of incidence (AOI) of the incoming wave. Therefore, the optimal mitigation conical pit geometry is application specific. Furthermore, our simulation also illustrates an alternative means to achieve an optimal mitigation structure by matching the cone angle of the structure with the AOI of the incoming wave, except for the p-polarized wave at a range of incident angles between 30° and 45°.

Femtosecond laser machining is used to create mitigation pits to stabilize nanosecond laser-induced damage in multilayer dielectric mirror coatings on BK7 substrates. In this paper, we characterize features and the artifacts associated with mitigation pits and further investigate the impact of pulse energy and pulse duration on pit quality and damage resistance. Our results show that these mitigation features can double the fluence-handling capability of large-aperture optical multilayer mirror coatings and further demonstrate that femtosecond laser macromachining is a promising means for fabricating mitigation geometry in multilayer coatings to increase mirror performance under high-power laser irradiation.

Substrate scratches can limit the laser resistance of multilayer mirror coatings on high-peak-power laser systems. To date, the mechanism by which substrate surface defects affect the performance of coating layers under high power laser irradiation is not well defined. In this study, we combine experimental approaches with theoretical simulations to delineate the correlation between laser damage resistance of coating layers and the physical properties of the substrate surface defects including scratches. A focused ion beam technique is used to reveal the morphological evolution of coating layers on surface scratches. Preliminary results show that coating layers initially follow the trench morphology on the substrate surface, and as the thickness increases, gradually overcoat voids and planarize the surface. Simulations of the electrical-field distribution of the defective layers using the finite-difference time-domain (FDTD) method show that field intensification exists mostly near the top surface region of the coating near convex focusing structures. The light intensification could be responsible for the reduced damage threshold. Damage testing under 1064 nm, 3 ns laser irradiation over coating layers on substrates with designed scratches show that damage probability and threshold of the multilayer depend on substrate scratch density and width. Our preliminary results show that damage occurs on the region of the coating where substrate scratches reside and etching of the substrate before coating does not seem to improve the laser damage resistance.

Computer simulations using finite difference time domain of conical pits show that electric field intensification within multilayer high reflector coatings is minimized when the incident and cone angle are matched.

Femtosecond laser machining is optimized to stabilize nanosecond induced-laser damage and to double the power handling capability of multilayer mirror coatings. Higher per-pulse energy of the machining laser degrades the feature edge quality.

Removal of laser-induced damage sites provides a possible mitigation pathway to improve damage resistance of coated multilayer dielectric mirrors. In an effort to determine the optimal mitigation geometry which will not generate secondary damage precursors, the electric field distribution within the coating layers for a variety of mitigation shapes under different irradiation angles has been estimated using the finite difference time domain (FDTD) method. The coating consists of twenty-four alternating layers of hafnia and silica with a quarter-wave reflector design. A conical geometrical shape with different cone angles is investigated in the present study. Beam incident angles range from 0° to 60° at 5° increments. We find that light intensification (square of electric field, |E|2) within the multilayers depends strongly on the beam incident direction and the cone angle. By comparing the field intensification for each cone angle under all angles of incidence, we find that a 30° conical pit generates the least field intensification within the multilayer film. Our results suggest that conical pits with shallow cone angles (≤ 30°) can be used as potential optimal mitigation structures.

The growth of calcium oxalate monohydrate in the presence of Tamm-Horsfall protein (THP), osteopontin, and the 27-residue synthetic peptides (DDDS)6DDD and (DDDG)6DDD (D = aspartic acid, S = serine, and G = glycine) was investigated via in situ atomic force microscopy. The results show that these four growth modulators create extensive deposits on the crystal faces. Depending on the modulator and crystal face, these deposits can occur as discrete aggregates, filamentary structures, or uniform coatings. These proteinaceous films can lead to either the inhibition of or an increase in the step speeds (with respect to the impurity-free system), depending on a range of factors that include peptide or protein concentration, supersaturation, and ionic strength. While THP and the linear peptides act, respectively, to exclusively increase and inhibit growth on the \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ \left( {\bar{1}01} \right) $$\end{document} face, both exhibit dual functionality on the (010) face, inhibiting growth at low supersaturation or high modulator concentration and accelerating growth at high supersaturation or low modulator concentration. Based on analyses of growth morphologies and dependencies of step speeds on supersaturation and protein or peptide concentration, we propose a picture of growth modulation that accounts for the observations in terms of the strength of binding to the surfaces and steps and the interplay of electrostatic and solvent-induced forces at the crystal surface.

Fe-doped lithium sodium silicate glasses codoped with Sn and C to promote the Fe2+ redox state are investigated under simultaneous excitation at the first and third harmonics of a nanosecond Nd:YAG laser. The aim is to evaluate critical parameters associated with the potential use of this material as an optical filter that transmits the third harmonic but blocks the fundamental frequency. Estimations of the excited-state absorption coefficient and photobleaching (reduction of absorption at the fundamental) are provided. The results provide insight on the design and expected operational parameters of this type of Fe-doped materials.

Calcium oxalate monohydrate (COM) kidney stone formation is prevented in most humans by urinary crystallization inhibitors. Urinary osteopontin (OPN) is a prototype of the aspartic acid-rich proteins (AARP) that modulate biomineralization. Synthetic poly(aspartic acids) that resemble functional domains of AARPs provide surrogate molecules for exploring the role of AARPs in biomineralization. Effects of linear aspartic acid-rich peptides on COM growth kinetics and morphology were evaluated by the combination of constant composition (CC) analysis and atomic force microscopy (AFM). A spacer amino acid (either glycine or serine) was incorporated during synthesis after each group of 3 aspartic acids (DDD) in the 27-mer peptide sequences. Kinetic CC studies revealed that the DDD peptide with serine spacers (DDDS) was more than 30 times more effective in inhibiting COM crystal growth than the DDD peptide with glycine spacers (DDDG). AFM revealed changes in morphology on (010) and (-101) COM faces that were generally similar to those previously described for OPN and citrate, respectively. At comparable peptide levels, the effects of step pinning and reduced growth rate caused by DDDS were remarkably greater. In CC nucleation studies, DDDS caused a greater prolongation of induction periods than DDDG. Thus, nucleation studies link changes in interfacial energy caused by peptide adsorption to COM to the CC growth and AFM results. These studies indicate that, in addition to the number of acidic residues, the contributions of other amino acids to the conformation of DDD peptides are also important determinants of the inhibition of COM nucleation and growth.

The majority of human kidney stones are composed primarily of calcium oxalate monohydrate (COM) crystals. Thus, determining the molecular modulation of COM crystallization by urinary constituents is crucial for understanding and controlling renal stone disease. A comprehensive molecular-scale view of COM shape modification by citrate, obtained through a combination of in situ atomic force microscopy and molecular modeling, is presented here. We find that while the most important factors determining binding strength are coordination between COO- groups on citrate and Ca ions in the lattice, as well as H-bonds formed between the OH group of citrate and an oxalate group, the nonplanar geometry of the steps provides the most favorable environment due to the ability of the step-edge to accommodate all Ca-COO- coordinations with minimal strain. However, binding to all steps and terraces on the (010) face is much less favorable than on the (101) face due to electrostatic repulsion between oxalate and COO- groups. For example, the maximum binding energy, -166.5 kJ mol(-1), occurs for the [101] step on the (101) face, while the value for the [021] step on the (010) face is only -56.9 kJ mol(-1). This high selectivity leads to preferential binding to steps on the (101) face that pins step motion. Yet anisotropy in interaction strength on this face drives anisotropic changes in step kinetics that are responsible for shape modification of macroscopic COM crystals. Thus, the molecular scale growth kinetics and the bulk crystal habit are fully consistent with the simulations.

We investigate defects forming in Ce3+-doped fused silica samples following exposure to nanosecond ultraviolet laser pulses and their relaxation as a function of time and exposure to low intensity light at different wavelengths. A subset of these defects are responsible for inducing absorption in the visible and near infrared spectral range, which is of critical importance for the use of this material as ultraviolet light absorbing filter in high power laser systems. The dependence of the induced absorption as a function of laser fluence and methods to most efficiently mitigate this effect are presented. Experiments simulating the operation of the material as a UV protection filter for high power laser systems were performed in order to determine limitations and practical operational conditions.