Filament Growth and Related Instabilities during Adsorbate Suppressed Electrodeposition.

Anisotropic growth of a single filament on a microelectrode is demonstrated by galvanostatic electrodeposition in a bistable passive-active critical system. Specifically, a Cu filament is formed by disruption of a passivating polyether-halide bilayer triggered by metal deposition with positive feedback guiding highly localized deposition. For macroscale electrodes, complex passive-active Turing patterns develop, while for micrometer-sized electrodes, bifurcation is frustrated and a single active zone develops, which is reinforced by hemispherical transport. As deposition proceeds, hemispherical symmetry is broken with lateral propagation of a single filament while an increasing fraction of the applied current supports expansion of the passive sidewall area that eventually leads to termination of anisotropic growth. Different polyether suppressors alter the dynamic range between passive and active growth that determines the shape and extent of filament formation. The impact of electrode area, geometry, and applied current on morphological evolution was also briefly examined. The results highlight the utility of appropriately scaled microelectrodes in the study of growth instabilities during breakdown of additive suppressed layers in critical electrodeposition systems.

Selected Area Electron Beam Induced Deposition of Pt and W for EBSD Backgrounds.

Applying high-resolution electron backscatter diffraction (HR-EBSD) to materials without regions that are amenable to the acquisition of backgrounds for static flat fielding (background subtraction) can cause analysis problems. To address this difficulty, the efficacy of electron beam induced deposition (EBID) of material as a source for an amorphous background signal is assessed and found to be practical. Using EBID material for EBSD backgrounds allows single crystal and large-grained samples to be analyzed using HR-EBSD for strain and small angle rotation measurement.

Detecting Carbon in Carbon: Exploiting Differential Charging to Obtain Information on the Chemical Identity and Spatial Location of Carbon Nanotube Aggregates in Composites by Imaging X-ray Photoelectron Spectroscopy.

To better assess risks associated with nano-enabled products including multiwalled carbon nanotubes (MWCNT) within polymer matrices, it is important to understand how MWCNT are dispersed throughout the composite. The current study presents a method which employs imaging X-ray photoelectron spectroscopy (XPS) to chemically detect spatially segregated MWCNT rich regions at an epoxy composites surface by exploiting differential charging. MWCNT do not charge due to high conductivity and have previously been shown to energetically separate from their insulating surroundings when characterized by XPS. XPS in imaging mode revealed that these conductive regions were spatially separated due to micrometer-scale MWCNT aggregation and poor dispersion during the formation of the composite. Three MWCNT concentrations were studied; (1, 4 and 5) % by mass MWCNT within an epoxy matrix. Images acquired in periodic energy intervals were processed using custom algorithms designed to efficiently extract spectra from regions of interest. As a result, chemical and electrical information on aggregate and non-aggregate portions of the composite was extracted. Raman imaging and scanning electron microscopy were employed as orthogonal techniques for validating this XPS-based methodology. Results demonstrate that XPS imaging of differentially charging MWCNT composite samples is an effective means for assessing dispersion quality.

Accurate flexural spring constant calibration of colloid probe cantilevers using scanning laser Doppler vibrometry.

Calibration of the flexural spring constant for atomic force microscope (AFM) colloid probe cantilevers provides significant challenges. The presence of a large attached spherical added mass complicates many of the more common calibration techniques such as reference cantilever, Sader, and added mass. Even the most promising option, AFM thermal calibration, can encounter difficulties during the optical lever sensitivity measurement due to strong adhesion and friction between the sphere and a surface. This may cause buckling of the end of the cantilever and hysteresis in the approach-retract curves resulting in increased uncertainty in the calibration. Most recently, a laser Doppler vibrometry thermal method has been used to accurately calibrate the normal spring constant of a wide variety of tipped and tipless commercial cantilevers. This paper describes a variant of the technique, scanning laser Doppler vibrometry, optimized for colloid probe cantilevers and capable of spring constant calibration uncertainties near ±1%.

Smart Electronic Laboratory Notebooks for the NIST Research Environment.

Laboratory notebooks have been a staple of scientific research for centuries for organizing and documenting ideas and experiments. Modern laboratories are increasingly reliant on electronic data collection and analysis, so it seems inevitable that the digital revolution should come to the ordinary laboratory notebook. The most important aspect of this transition is to make the shift as comfortable and intuitive as possible, so that the creative process that is the hallmark of scientific investigation and engineering achievement is maintained, and ideally enhanced. The smart electronic laboratory notebooks described in this paper represent a paradigm shift from the old pen and paper style notebooks and provide a host of powerful operational and documentation capabilities in an intuitive format that is available anywhere at any time.

Experimental determination of mode correction factors for thermal method spring constant calibration of AFM cantilevers using laser Doppler vibrometry.

Mode correction factors (MCFs) represent a significant adjustment to the spring constant values measured using the thermal cantilever calibration method. Usually, the ideal factor of 0.971 for a tipless rectangular cantilever is used, which adjusts the value by 3% for the first flexural mode. An experimental method for determining MCFs has been developed that relies on measuring the areas under the first few resonance peaks for the flexural mode type. Using this method, it has been shown that MCFs for the first flexural mode of commercially available atomic force microscope cantilevers actually vary from 0.95 to 1.0, depending on the shape and end mass of the cantilever. Triangular shaped cantilevers tend to lower MCFs with tipless versions providing the lowest values. Added masses (including tips) tend to increase the first flexural mode's MCF to higher values with large colloid probes at the high extreme. Using this understanding and applying it to the recently developed laser Doppler vibrometry thermal calibration method it is now possible to achieve very accurate and precise cantilever spring constant calibrations (uncertainties close to ±1%) with commonly available commercial cantilevers such as tipped rectangular and triangular cantilevers, and colloid probes.

Growth and Decomposition of Pt Surface Oxides.

The formation and thermal stability of Pt surface oxides on a Pt thin film were studied in situ using ambient-pressure X-ray photoelectron spectroscopy. At an oxygen pressure of 73 Pa (550 mTorr), the surface Pt oxide was gradually formed, evidenced by the O 1s peak at 529.5 eV as the Pt film was heated. The Pt oxide peak reached a maximum between 217 and 317 °C and then decreased as the sample temperature was further increased. A similar response was seen on cooling from 480 to 23 °C; the intensity of the Pt oxide peak first increased and then decreased. The remaining Pt surface oxides partially decomposed during ultra-high-vacuum (UHV) pumping and completely decomposed during heating in UHV, which highlights the challenge of characterizing these surfaces with UHV instruments. These results have important implications for the understanding of the surface states of platinum films in different environments and the roles of different catalytic mechanisms.

Visualizing shed skin cells in fingerprint residue using dark-field microscopy.

This proof-of-concept study shows that dark-field microscopy provides sufficient contrast for cell visualization in fingerprints with high sebum content. Although the application is limited to smooth surfaces that do not scatter light, such as polyethylene terephthalate (PET), it was able to measure the number of cells deposited within a fingerprint residue and the reduction in cell transfer with repeated skin contact. On a PET surface, at roughly 5 N of contact force, a typical finger transfers several hundred cells onto the surface. Over subsequent finger contacts onto a clean PET surface, this number decreased exponentially until a steady state was reached, which is characterized by the transfer of (78 ± 36) cells or (0.46 ± 0.21) cells/mm2 when normalized for fingerprint area. High uncertainty in cell transfer was due to: the highly variable nature of a human finger (where the number of loose cells varies from person to person and from day to day depending on what they touch) and difficulties in controlling the contact force and finger movement such as twisting during deposition (where twisting of the finger can expose a new patch of skin to the substrate, increasing the number of cell transfer). Plasma etching was also explored as an effective way to validate dark-field microscopy for cell counting. Although limited to inorganic substrates due to etching effects, exposing the fingerprint for less than 10 min can remove a majority of the sebum while keeping the cells intact for a before-and-after comparison using light microscopy.

The long-term hydriding and dehydriding stability of the nanoscale LiNH2+LiH hydrogen storage system.

The long-term cyclic durability of nano-engineered solid-state hydrogen storage systems is investigated using LiNH2+LiH as a model system. Through 60 hydriding and dehydriding cycles over the course of more than 200 h, a small decrease in the kinetics of the dehydrogenation reaction leads to a 10% reduction in the amount of hydrogen liberated during a 2.5 h desorption. Although a 75% loss in the specific surface area is encountered within the first 10 cycles, the crystallite size remains relatively stable near 20 nm while enduring 72% of the average melting temperature of the phases. The lack of microstructural growth is attributed to low packing efficiency of the ball milled powder in combination with the mixture of multiple phases present and repeated nucleation of fine grains during hydriding and dehydriding reactions.

Cutting Procedures, Tensile Testing, and Ageing of Flexible Unidirectional Composite Laminates.

Many body armor designs incorporate unidirectional (UD) laminates. UD laminates are constructed of thin (<0.05 mm) layers of high-performance yarns, where the yarns in each layer are oriented parallel to each other and held in place using binder resins and thin polymer films. The armor is constructed by stacking the unidirectional layers in different orientations. To date, only very preliminary work has been performed to characterize the ageing of the binder resins used in unidirectional laminates and the effects on their performance. For example, during the development of the conditioning protocol used in the National Institute of Justice Standard-0101.06, UD laminates showed visual signs of delamination and reductions in V50, which is the velocity at which half of the projectiles are expected to perforate the armor, after ageing. A better understanding of the material property changes in UD laminates is necessary to comprehend the long-term performance of armors constructed from these materials. There are no current standards recommended for mechanically interrogating unidirectional (UD) laminate materials. This study explores methods and best practices for accurately testing the mechanical properties of these materials and proposes a new test methodology for these materials. Best practices for ageing these materials are also described.

pQCT bone geometry and strength: population epidemiology and concordance in Australian children aged 11-12 years and their parents.

OBJECTIVES: To describe the epidemiology and concordance of bone health in a population-based sample of Australian parent-child dyads at child age 11-12 years. DESIGN: Population-based cross-sectional study (the Child Health CheckPoint) nested between waves 6 and 7 of the Longitudinal Study of Australian Children (LSAC). SETTING: Assessment centres in seven cities around Australia, February 2015-March 2016. PARTICIPANTS: of all participating CheckPoint families (n=1874), bone data were available for 1222 dyads (1271 children, 50% girls; 1250 parents, 86% mothers). OUTCOME MEASURES: Peripheral quantitative CT (pQCT) of the non-dominant leg scanned at the 4% (distal) and 66% (mid-calf) tibial sites. Stratec XCT 2000 software generated estimates of bone density, geometry and polar stress-strain index.Parent-child concordance were assessed using Pearson's correlation coefficients and multivariable linear regression models. Percentiles were determined using survey weights. Survey weights and methods accounted for LSAC's complex sampling, stratification and clustering within postcodes. RESULTS: Concordances were greater for the geometric pQCT parameters (periosteal circumference 0.38, 95% CI 0.33 to 0.43; endosteal circumference 0.42, 95% CI 0.37 to 0.47; total cross-sectional area 0.37, 95% CI 0.32 to 0.42) than density (cortical density 0.25, 95% CI 0.19 to 0.30). Mother-child and father-child values were similar. Relationships attenuated only slightly on adjustment for age, sex and body mass index. Percentiles and concordance are presented for the whole sample and by sex. CONCLUSIONS: There is strong parent-child concordance in bone geometry and, to a lesser extent, density even before the period of peak adolescent bone deposition. This geometrical concordance suggests that future intergenerational bone studies could consider using pQCT rather than the more commonly used dual X-ray absorptiometry (DXA).

Strain measurement of 3D structured nanodevices by EBSD.

We present a new methodology to accurately measure strain magnitudes from 3D nanodevices using Electron Backscatter Diffraction (EBSD). Because the dimensions of features on these devices are smaller than the interaction volume for backscattered electrons, EBSD patterns from 3D nanodevices will frequently be the superposition of patterns from multiple material regions simultaneously. The effect of this superposition on EBSD strain measurement is demonstrated, along with an approach to separate EBSD patterns from these devices via subtraction. The subtraction procedure is applied to 33 nm wide SiGe lines, and it provides accurate strain magnitudes where the traditional EBSD strain analysis method undervalues the strain magnitude by an order of magnitude. The approach provides a strain measurement technique for nanoscale 3D structures that is high spatial resolution, nondestructive, and accurate.

In-situ elastic strain mapping during micromechanical testing using EBSD.

Compared to more commonly used strain measurement techniques, electron backscatter diffraction (EBSD) offers improved spatial resolution and measurement sensitivity. Additionally, EBSD can provide the full deformation tensor, whereas other techniques, such as digital image correlation (DIC), are limited to only in-plane strains and rotations. In this work, EBSD was used to measure strains and rotations in-situ during testing of a single-crystal silicon micromechanical test specimen. The theta-like specimen geometry was chosen due to the complex and spatially-varying strain states that exist in the circular frame of the sample during testing, as well as the nominally uniform strains in the central web. Full-field strain maps were generated for each strain and rotation component and compared to those from finite element analyses (FEA), showing strong agreement in all cases. Additionally, potential sources of error and their impact on both measurement accuracy and uncertainty are discussed.

Bone health, activity and sedentariness at age 11-12 years: Cross-sectional Australian population-derived study.

AIM: To examine cross-sectional associations of children's bone health (size, density, strength) with moderate-vigorous physical activity (MVPA) and sedentary behaviour by considering: (1) duration of activity, (2) fragmentation, and (3) duration/fragmentation combined. METHODS: Design: Population-based cross-sectional study. PARTICIPANTS: 11-12 year-olds in the Longitudinal Study of Australian Children's Child Health CheckPoint. Exposures: MVPA and sedentary behaviour (7-day accelerometry), yielding (1) daily average durations (min/day) and (2) fragmentations (the parameter alpha, representing the relationship between activity bout frequency and bout length). OUTCOMES: Tibial peripheral quantitative computed tomography (bone density, geometry, strength). ANALYSIS: Multivariable regression models including activity durations and fragmentations separately and combined. RESULTS: Of 1357 children attending the CheckPoint, 864 (64%) provided both bone and accelerometry data (mean age 11.4 years (standard deviation (SD) 0.5); 49% male). Mean daily MVPA and sedentary behaviour durations were 34.4 min/day (SD 28.3) and 667.9 min/day (SD 71.9) respectively for boys and girls combined. Each additional daily hour of MVPA was associated with small bone health benefits comprising greater periosteal and endosteal circumference (standardised effect sizes 0.25, 95% CI 0.10 to 0.40 and 0.21, 95% CI 0.03 to 0.39, respectively) and bone strength (0.26, 95% CI 0.14 to 0.38). Sedentary duration and fragmentation of either MVPA or sedentary behaviour showed little association with bone health. CONCLUSIONS: In early adolescence, MVPA duration showed associations with better bone health that, while modest, could be of population-level importance. MVPA fragmentation and sedentary behaviour duration and fragmentation seemed less important.

Multi-environment Nanocalorimeter with Electrical Contacts for Use in the Scanning Electron Microscope.

We have developed a versatile nanocalorimeter sensor which allows imaging and electrical measurements of samples under different gaseous environments using the scanning electron microscope (SEM) and can simultaneously measure the sample temperature and associated heat of reaction. This new sensor consists of four independent heating/sensing elements for nanocalorimetry and eight electrodes for electrical measurements, all mounted on a 50 nm thick, 250 µm × 250 µm suspended silicon nitride membrane. This membrane is highly electron transparent and mechanically robust enabling in situ SEM observation under realistic temperatures, environmental conditions and pressures up to one atmosphere. To demonstrate this new capability, we report here on 1) in situ SEM-nanocalorimetry study of melting and solidification of polyethylene oxide, 2) the temperature dependence of conductivity of a nanowire; 3) the electron beam induced current measurements (EBID) of a nanowire in vacuum and air. Furthermore, the sensor is easily adaptable to operate in liquid environment and is compatible with most existing SEM. This versatile platform couples nanocalorimetry with in situ SEM imaging under various gaseous and liquid environments and is applicable to materials research, nanotechnology, energy, catalysis and biomedical applications.

Stability of lithium hydride in argon and air.

The oxidation behaviors of LiH under a high purity argon atmosphere, an argon atmosphere with some O2 and H2O impurities, and ambient air at both room and high temperatures, are investigated using a variety of analytical instruments including X-ray diffractometry, thermogravimetry, mass spectrometry, scanning electron microscopy, and specific surface area analysis. The oxidation behaviors of the ball-milled LiH under different atmospheres are also studied and compared with those without ball milling. It is shown that no oxidation of LiH occurs under a high-purity argon atmosphere. However, oxidation of LiH takes place when the argon atmosphere contains some H2O and O2 impurities. At temperatures higher than approximately 55 degrees C, oxidation of LiH proceeds via the reaction of LiH + 1/4 O2 = 1/2 Li2O + 1/2 H2, whereas at room temperature oxidation of LiH is likely caused by the simultaneous reactions of LiH + H2O = LiOH + H2 and LiH + 1/2 O2 = LiOH. The oxidation behavior of LiH in ambient air with a 27% relative humidity can be well described by the Johnson-Mehl-Avrami equation. Furthermore, the ball-milled LiH oxidizes faster than the unmilled one, which is due to the finer particle size and larger surface area of the ball-milled powder.

Assessing strain mapping by electron backscatter diffraction and confocal Raman microscopy using wedge-indented Si.

The accuracy of electron backscatter diffraction (EBSD) and confocal Raman microscopy (CRM) for small-scale strain mapping are assessed using the multi-axial strain field surrounding a wedge indentation in Si as a test vehicle. The strain field is modeled using finite element analysis (FEA) that is adapted to the near-indentation surface profile measured by atomic force microscopy (AFM). The assessment consists of (1) direct experimental comparisons of strain and deformation and (2) comparisons in which the modeled strain field is used as an intermediate step. Direct experimental methods (1) consist of comparisons of surface elevation and gradient measured by AFM and EBSD and of Raman shifts measured and predicted by CRM and EBSD, respectively. Comparisons that utilize the combined FEA-AFM model (2) consist of predictions of distortion, strain, and rotation for comparison with EBSD measurements and predictions of Raman shift for comparison with CRM measurements. For both EBSD and CRM, convolution of measurements in depth-varying strain fields is considered. The interconnected comparisons suggest that EBSD was able to provide an accurate assessment of the wedge indentation deformation field to within the precision of the measurements, approximately 2×10(-4) in strain. CRM was similarly precise, but was limited in accuracy to several times this value.

Patients with non-specific neck disorders commonly report upper limb disability.

Patients with neck disorders can report difficulties with functional use of their upper limb because of their neck pain. Yet, there is little information on the frequency and specifically, the nature of these upper limb activities. This study surveyed patients with neck pain disorders (n = 103) presenting for management at private physiotherapy clinics in a large metropolitan area to investigate the frequency and nature of reduced upper limb function. Participants were asked to complete four questionnaires, the Disabilities of the Arm, Shoulder and Hand (DASH) questionnaire, the Neck Disability Index (NDI), Pictorial Fear of Activity Scale-Cervical (PFActS-C) and Patient Specific Functional Scale (PSFS). Approximately 80% of patients spontaneously reported that upper limb activities aggravated their neck pain (PSFS). Most frequently, these activities involved loading of the upper limb such as lifting. Eight activity items on the DASH were scored positive by ≥50% of participants. Participants had mild to moderately severe neck pain (NDI: range 2-68%). The DASH and NDI were moderately-highly correlated (ρ = 0.669; p < 0.001), indicating the higher the neck pain severity the greater the upper limb functional restrictions. There was a low correlation between the NDI and PFActS-C (ρ = 0.319; p = 0.001). These findings provide evidence that upper limb function is often impaired in association with neck pain disorders and suggest clinicians should routinely question patients regarding upper limb function. The DASH could be used as a suitable outcome measure in its current or possibly a modified form.

Surface mediated assembly of small, metastable gold nanoclusters.

The unique properties of metallic nanoclusters are attractive for numerous commercial and industrial applications but are generally less stable than nanocrystals. Thus, developing methodologies for stabilizing nanoclusters and retaining their enhanced functionality is of great interest. We report the assembly of PPh3-protected Au9 clusters from a heterogeneous mixture into films consisting of sub 3 nm nanocluster assemblies. The depositing nanoclusters are metastable in solution, but the resulting nanocluster assemblies are stabilized indefinitely in air or fresh solvent. The films exhibit distinct structure from Au nanoparticles observed by X-ray diffraction, and film dissolution data support the preservation of small nanoclusters. UV-Vis spectroscopy, electrospray ionization mass spectrometry, X-ray photoelectron spectroscopy and electron microscopy are used to elucidate information regarding the nanocluster formation and assembly mechanism. Preferential deposition of nanocluster assemblies can be achieved on multiple substrates, including polymer, Cr, Si, SiO2, SiNx, and metal-organic frameworks (MOFs). Unlike other vapor phase coating processes, nanocluster assembly on the MIL-68(In) MOF crystal is capable of preferentially coating the external surface and stabilizing the crystal structure in hydrothermal conditions, which should enhance their storage, separation and delivery capabilities.