On the use of crack-tip-opening displacement to predict the fracture strength of notched graphite/epoxy laminates

The fracture strength and crack-opening displacement of notched graphite/epoxy laminates were measured experimentally using the center-cracked tension-specimen geometry. Four replicate tests were conducted for a variety of laminate stacking sequences, thicknesses, and notch lengths. Most laminates exhibited extensive notch-tip damage prior to fracture. Values of crack-tip-opening displacement (CTOD) at fracture were estimated from values of crack-opening displacement measured at the crack center line. CTOD was independent of specimen crack length for the [0/±45/90] _s , [0/±45/90]_15s , [0/±45] _s , [0/±45/]_15s , and [0/90]_24s laminates. In addition, notched laminate strength was accurately predicted using a Dugdale-type model along with the estimated CTOD.Paper was presented at V International Congress on Experimental Mechanics held in Montreal, Quebec, Canada on June 10–15, 1984.     

On infinitesimal stability and instability of pendulum type oscillations

For the pendulum type of oscillations governed by the equation ? + φ(x) = 0, with φ(x) an odd function, it is shown that according to the linearized disturbance equation, stability is predicted if and only if dTd_x = 0. where T is the period and α is the amplitude of the non-linear steady-state oscillations. From this it follows that for a given non-linear function φ(x). infinitesimal stability can at most be predicted only for certain discrete values of α. It is shown analytically that for a simple pendulum, a power-law spring and a cubic hard or soft spring, the oscillations are infinitesimally unstable for all α. It is further shown, however, that particular cases of non-linear restoring forces do exist for which infinitesimal stability is predicted for certain α's, in contrast to the actual Liapunov instability in these cases.     

Work Hardening Effects in Gellan Gum Gels1

Abstract

Gellan gum is a bacterial polysaccharide that is marketed as a broad spectrum gelling agent. The shear and Young's moduli, and the fracture strength of gellan gels increase with increasing ionic strength, pass through maxima and then decrease to zero at higher ionic strength. The position of the maxima depend on the valency of added counterions and are virtually independent of polymer concentration. At low ionic strength the measured rheological parameters show small variability but these values become increasingly variable with increasing ionic strength. Stress relaxation experiments were carried out in order to examine the mechanical behaviour of gellan gels and to explain these effects. At low ionic strength the gels approximate to elastic solids whereas at high ionic strength the increased stress relaxation is colloid-like in behaviour. However, unlike colloidal dispersions, the magnitude of the stress relaxation decreases on successive applications of stress and the relaxation modulus increases. The gels work harden. Such behaviour is attributed to a heterogeneous structure within the gel.     

Solvent Vapor Annealing of Block Copolymers in Confined Topographies: Commensurability Considerations for Nanolithography

The directed self‐assembly of block copolymer (BCP) materials in topographically patterned substrates (i.e., graphoepitaxy) is a potential methodology for the continued scaling of nanoelectronic device technologies. In this Communication, an unusual feature size variation in BCP nanodomains under confinement with graphoepitaxially aligned cylinder‐forming poly(styrene)‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) BCP is reported. Graphoepitaxy of PS‐b‐P4VP BCP line patterns (C_II) is accomplished via topo­graphy in hydrogen silsequioxane (HSQ) modified substrates and solvent vapor annealing (SVA). Interestingly, reduced domain sizes in features close to the HSQ guiding features are observed. The feature size reduction is evident after inclusion of alumina into the P4VP domains followed by pattern transfer to the silicon substrate. It is suggested that this nano­domain size perturbation is due to solvent swelling effects during SVA. It is proposed that using a commensurability value close to the solvent vapor annealed periodicity will alleviate this issue leading to uniform nanofins.

     

Label‐Free Nanoimaging of Neuromelanin in the Brain by Soft X‐ray Spectromicroscopy

A hallmark of Parkinson's disease is the death of neuromelanin‐pigmented neurons, but the role of neuromelanin is unclear. The in situ characterization of neuromelanin remains dependent on detectable pigmentation, rather than direct quantification of neuromelanin. We show that direct, label‐free nanoscale visualization of neuromelanin and associated metal ions in human brain tissue can be achieved using synchrotron scanning transmission x‐ray microscopy (STXM), through a characteristic feature in the neuromelanin x‐ray absorption spectrum at 287.4 eV that is also present in iron‐free and iron‐laden synthetic neuromelanin. This is confirmed in consecutive brain sections by correlating STXM neuromelanin imaging with silver nitrate‐stained neuromelanin. Analysis suggests that the 1s–σ* (C?S) transition in benzothiazine groups accounts for this feature. This method illustrates the wider potential of STXM as a label‐free spectromicroscopy technique applicable to both organic and inorganic materials.     

Label-Free Nanoimaging of Neuromelanin in the Brain by Soft X-ray Spectromicroscopy

A hallmark of Parkinson's disease is the death of neuromelanin-pigmented neurons, but the role of neuromelanin is unclear. The in situ characterization of neuromelanin remains dependent on detectable pigmentation, rather than direct quantification of neuromelanin. We show that direct, label-free nanoscale visualization of neuromelanin and associated metal ions in human brain tissue can be achieved using synchrotron scanning transmission x-ray microscopy (STXM), through a characteristic feature in the neuromelanin x-ray absorption spectrum at 287.4 eV that is also present in iron-free and iron-laden synthetic neuromelanin. This is confirmed in consecutive brain sections by correlating STXM neuromelanin imaging with silver nitrate-stained neuromelanin. Analysis suggests that the 1s–σ* (C−S) transition in benzothiazine groups accounts for this feature. This method illustrates the wider potential of STXM as a label-free spectromicroscopy technique applicable to both organic and inorganic materials.     

Soft-graphoepitaxy using nanoimprinted polyhedral oligomeric silsesquioxane substrates for the directed self-assembly of PS-b-PDMS

We report here the fabrication of periodic sub-25 nm diameter size cylinder structures using block copolymer (BCP) directed self-assembly on nanoimprinted topographically patterned substrates. Tailored polyhedral oligomeric silsesquioxanes (POSSs) films were spin coated onto silicon substrates and were patterned by nanoimprint lithography to produce topographies commensurable with the BCP domain spacing. The chemistry of the POSS was tuned to control the alignment and orientation of the BCP films. The substrates were used to direct the microphase separation (following toluene solvent annealing) of a hexagonal structure forming polystyrene-block-polydimethylsiloxane (PS-b-PDMS) having a domain spacing of 42.6 nm and PDMS cylinder widths of 23.7 nm. On more hydrophilic POSS substrates the cylinders were obtained parallel to the substrate plane and aligned with the topography. In contrast, in more hydrophobic POSS patterns, the cylinders align perpendicular to the substrate plane. The use of these methods for the nanofabrication of vias, nanofluidic devices or interconnect structures of sub-25 nm feature size is discussed.     

Some Reactions of α-Allenic Boronates

α-Allenic boronates, readily available in high yield from gem-borazirconcene alkanes, react with iodine to give diiodo adducts that when treated with sodium acetate provide 2-iodo-1,3-butadienes. Alternatively, hydrozirconation of the α-allenic boronates followed by treatment with D₂O occurs regioselectively to place deuterium in the allylic position.     

Methodological advances for measuring low-level radium isotopes in seawater

A new approach for quantifying radium isotopes in seawater was developed in advance of the international GEOTRACES program, which has the goal of identifying processes and quantifying fluxes that control the distribution of trace elements and isotopes (TEIs) in the ocean. High-resolution water column samples were collected via a commercially available in situ pump modified to accept multiple filter media including a manganese-oxide (MnO₂) impregnated acrylic cartridge for extracting dissolved radionuclides from seawater. The modifications mitigated prefilter clogging and allowed for up to 1,800 L filtrations in 4 h of pumping. Different MnO₂ cartridge preparation methods were investigated to achieve maximum radium (Ra) extraction efficiency under high sample flow rates. Full-ocean depth profiles were measured for short-lived radium isotopes (²²³Ra and ²²⁴Ra) in shipboard laboratories using a delayed coincidence alpha scintillation counter (RaDeCC). Samples were reanalyzed 4 weeks and 2 months after collection for ²²⁸Th and ²²⁷Ac to correct for supported ²²⁴Ra and ²²³Ra, respectively. Finally, the cartridges were measured on a gamma-ray spectrometer for the long-lived radium isotopes (²²⁶Ra and ²²⁸Ra). Parallel 20 L samples at each pumping depth were collected from Niskin bottles and analyzed via alpha scintillation for ²²⁶Ra to determine radium extraction efficiencies for the cartridges. These modified methods will allow for increased sample throughput, and hence higher spatial resolution for radium isotopes in the ocean. Such resolution will greatly improve the determination of oceanic vertical and horizontal mixing rates over small and large scales, which in turn can be used to calculate fluxes of TEIs into the ocean.     

Total Chemical Synthesis and Biological Activities of Glycosylated and Non‐Glycosylated Forms of the Chemokines CCL1 and Ser‐CCL1

CCL1 is a naturally glycosylated chemokine protein that is secreted by activated T‐cells and acts as a chemoattractant for monocytes. 1 Originally, CCL1 was identified as a 73 amino acid protein having one N‐glycosylation site, 1 and a variant 74 residue non‐glycosylated form, Ser‐CCL1, has also been described. 2 There are no systematic studies of the effect of glycosylation on the biological activities of either CCL1 or Ser‐CCL1. Here we report the total chemical syntheses of both N‐glycosylated and non‐glycosylated forms of (Ser‐)CCL1, by convergent native chemical ligation. We used an N‐glycan isolated from hen egg yolk together with the Nbz linker for Fmoc chemistry solid phase synthesis of the glycopeptide‐^αthioester building block. 3 Chemotaxis assays of these glycoproteins and the corresponding non‐glycosylated proteins were carried out. The results were correlated with the chemical structures of the (glyco)protein molecules. To the best of our knowledge, these are the first investigations of the effect of glycosylation on the chemotactic activity of the chemokine (Ser‐)CCL1 using homogeneous N‐glycosylated protein molecules of defined covalent structure.