Tin whisker mitigation by means of a post-electroplating electrochemical oxidation treatment

There are very few studies that have investigated directly the effect of an oxide film on tin whisker growth, since the ‘cracked oxide theory’ was proposed by Tu in 1994 [K.-N. Tu: Phys. Rev., 1994, 49, (3), 2030–2034]. The current study has investigated the effect of an electrochemically produced oxide on tin whisker growth, for both Sn–Cu electrodeposits on Cu and pure Sn electrodeposits on brass. X-ray photoelectron spectroscopy (XPS) has been used to investigate the effect of the applied electrochemical oxidation potential on the oxide film thickness. Focused ion beam has been used to prepare cross sections from electrodeposited samples to investigate the influence of the electrochemically formed oxide film on deposit microstructure during long-term room temperature storage. The XPS studies show that the thickness of electrochemically formed oxide film is directly influenced by the applied potential and the total charge passed. Whisker growth studies show that the electrochemical oxidation treatment mitigates whisker growth for both Sn–Cu electrodeposits on Cu and pure Sn electrodeposits on brass. For Sn electrodeposits on brass, the electrochemically formed oxide greatly reduces both the formation of zinc oxide at the surface and the formation of intermetallic compounds, which results in the mitigation of tin whisker growth. For Sn–Cu electrodeposits on Cu, the electrochemically formed oxide has no apparent effect on intermetallic compound formation and acts simply as a physical barrier to hinder tin whisker growth.     

An Electrochemical Evaluation of Possible Non-Chromate Conversion Coating Treatments for Electrodeposited Zinc-Nickel Alloys

A number of possible non-chromate conversion coating formulations have been studied to examine their efficacy as replacements for chromate-based coating treatments on electrodeposited zinc-nickel alloys. Data have been collected from both electrochemical and conventional salt fog corrosion tests. In the latter tests all the alternative non-chromate systems studied delayed the onset of the corrosion of the zinc-nickel coating itself but only the simple molybdate and the permanganatelmolybdate dual treatment brought about improvements in times to red rusting of the steel substrate. The electrochemical evaluations suggested that simple molybdate-treated surfaces act as only moderate barriers to the chloride environments. Of the two dual treatments, permanganatel molybdate behaved similarly to the simple molybdate treated surfaces in the electrochemical tests, but the molybdatel permanganate was more protective, although this was not exhibited in the salt fog corrosion tests.     

Replacing Chromates for the Passivation of Zinc Surfaces

The search for low toxicity alternatives to Chromate for the formation of conversion coatings (passivation treatments) for zinc-based surfaces, has been a long one. For many years no real candidate was found to be completely suitable, a variety of possibilities being examined. More recently trivalent chromium-based treatments have been suggested as possibly the answer. This paper examines the past literature and data, and examines these new low toxicity systems.     

Effects of surface heterogeneity on the adsorption of CO₂ in microporous carbons

Carbon capture combined with utilization and storage has the potential to serve as a near-term option for CO(2) emissions reduction. CO(2) capture by carbon-based sorbents and CO(2) storage in geologic formations such as coal and shale both require a thorough understanding of the CO(2) adsorption properties in microporous carbon-based materials. Complex pore structures for natural organic materials, such as coal and gas shale, in addition to general carbon-based porous materials are modeled as a collection of independent, noninterconnected, functionalized graphitic slit pores with surface heterogeneities. Electronic structure calculations coupled with van der Waals-inclusive corrections have been performed to investigate the electronic properties of functionalized graphitic surfaces. With Bader charge analysis, electronic structure calculations can provide the initial framework comprising both the geometry and corresponding charge information required to carry out statistical modeling. Grand canonical Monte Carlo simulations were carried out to determine the adsorption isotherms for a given adsorbent-adsorbate interaction at temperature/pressure conditions relevant to carbon capture applications to focus on the effect of the surface functionalities. On the basis of the current work, oxygen-containing functional groups were predicted to enhance CO(2) adsorption in microporous carbon materials in the absence of water vapor, and the hydrated graphite was found to hinder CO(2) adsorption.     

Effect of smoke-free policies on the behaviour of social smokers

OBJECTIVE: To test the hypothesis that proposed amendments to the Occupational Safety and Health Act making all enclosed workplaces in Western Australia smoke free would result in a decrease in cigarette consumption by patrons at nightclubs, pubs, and restaurants without adversely affecting attendance. DESIGN: Cross sectional structured interview survey. PARTICIPANTS AND SETTING: Patrons of several inner city pubs and nightclubs in Perth were interviewed while queuing for admission to these venues. OUTCOME MEASURES: Current social habits, smoking habits; and how these might be affected by the proposed regulations. Persons who did not smoke daily were classified as "social smokers." RESULTS: Half (50%) of the 374 patrons interviewed were male, 51% currently did not smoke at all, 34.3% smoked every day, and the remaining 15.7% smoked, but not every day. A clear majority (62.5%) of all 374 respondents anticipated no change to the frequency of their patronage of hospitality venues if smoke-free policies became mandatory. One in five (19.3%) indicated that they would go out more often, and 18.2% said they would go out less often. Half (52%) of daily smokers anticipated no change to their cigarette consumption, while 44.5% of daily smokers anticipated a reduction in consumption. A majority of social smokers (54%) predicted a reduction in their cigarette consumption, with 42% of these anticipating quitting. CONCLUSIONS: One in nine (11.5%) of smokers say that adoption of smoke-free policies would prompt them to quit smoking entirely without a significant decrease in attendance at pubs and nightclubs. There can be few other initiatives as simple, cheap, and popular that would achieve so much for public health.     

Milk production from Holstein half udders after concurrent thirty- and seventy-day dry periods

The objective of this study was to use a within-cow, half-udder model to compare the effect of cessation of milk removal from mammary quarters within respective half udders at either 30 or 70 d before expected calving date (ECD) on the ability of the half udders to subsequently produce milk. Pregnant Holstein cows were assigned to control (n = 14) or treatment (TRT, n = 26) groups. All mammary quarters in the udder of cows in the control group had 70-d (68 ± 9 d) dry periods, whereas in each cow of the TRT group, 1 randomly selected half udder was dried at 70 d before ECD and the other half udder continued to be milked twice daily until dried at 30 d before ECD. From 80 through 70 d before ECD, amounts of milk produced by the left and right half udders of cows in the TRT group were measured at the first-shift milking. No differences were detected in the actual or relative amounts of milk produced by the left (3.46 ± 0.2 kg; 48.8 ± 1.0%) and the right (3.63 ± 0.2 kg; 51.2 ± 1.0%) half udders. Furthermore, the actual and relative amounts of milk produced by the half udders (n = 12 left, 14 right) subsequently dry for 67 ± 7 d (3.56 ± 0.2 kg; 50.2 ± 1.0%) and the half udders (n = 14 left, 12 right) subsequently dry for 27 ± 7 d (3.54 ± 0.2 kg; 49.8 ± 1.0%) did not differ before they were dried. However, from 3 to 100 d of the subsequent lactation, the 30-d dry half udders produced 18.9% less milk than the 70-d dry half udders (16.3 vs. 20.1 ± 1.0 kg/d). In addition, relative amounts of total-udder milk produced by the 30- and 70-d dry half udders in the same cow differed (44.9 vs. 55.1 ± 0.2%, respectively). Cows in the control group produced more milk than cows in the TRT group through 80 DIM (39.5 vs. 35.2 ± 0.6 kg/d), but not from 3 through 150 DIM (39.0 vs. 36.2 ± 1.6 kg/d). Thus, half udders that produced the same actual and relative amounts of milk before being dried did not do so when given a 30-d dry period instead of a 70-d dry period. When compared with the pre-dry value (49.8%), the relative contribution of half udders dry for 30 d to the total milk yield during the first 100 DIM was decreased by 9.8%.     

Charged nucleobases and their potential for RNA catalysis

Catalysis in living cells is carried out by both proteins and RNA. Protein enzymes have been known for over 200 years, but RNA enzymes, or "ribozymes", were discovered only 30 years ago. Developing insight into RNA enzyme mechanisms is invaluable for better understanding both extant biological catalysis as well as the primitive catalysis envisioned in an early RNA-catalyzed life. Natural ribozymes include large RNAs such as the group I and II introns; small RNAs such as the hepatitis delta virus and the hairpin, hammerhead, VS, and glmS ribozymes; and the RNA portion of the ribosome and spliceosome. RNA enzymes use many of the same catalytic strategies as protein enzymes, but do so with much simpler side chains. Among these strategies are metal ion, general acid-base, and electrostatic catalysis. In this Account, we examine evidence for participation of charged nucleobases in RNA catalysis. Our overall approach is to integrate direct measurements on catalytic RNAs with thermodynamic studies on oligonucleotide model systems. The charged amino acids make critical contributions to the mechanisms of nearly all protein enzymes. Ionized nucleobases should be critical for RNA catalysis as well. Indeed, charged nucleobases have been implicated in RNA catalysis as general acid-bases and oxyanion holes. We provide an overview of ribozyme studies involving nucleobase catalysis and the complications involved in developing these mechanisms. We also consider driving forces for perturbation of the pK(a) values of the bases. Mechanisms for pK(a) values shifting toward neutrality involve electrostatic stabilization and the addition of hydrogen bonding. Both mechanisms couple protonation with RNA folding, which we treat with a thermodynamic formalism and conceptual models. Furthermore, ribozyme reaction mechanisms can be multichannel, which demonstrates the versatility of ribozymes but makes analysis of experimental data challenging. We examine advances in measuring and analyzing perturbed pK(a) values in RNA. Raman crystallography and fluorescence spectroscopy have been especially important for pK(a) measurement. These methods reveal pK(a) values for the nucleobases A or C equal to or greater than neutrality, conferring potential histidine- and lysine/arginine-like behavior on them. Structural support for ionization of the nucleobases also exists: an analysis of RNA structures in the databases conducted herein suggests that charging of the bases is neither especially uncommon nor difficult to achieve under cellular conditions. Our major conclusions are that cationic and anionic charge states of the nucleobases occur in RNA enzymes and that these states make important catalytic contributions to ribozyme activity. We conclude by considering outstanding questions and possible experimental and theoretical approaches for further advances.     

Responsive behaviour of galvanic anodes in concrete and the basis for its utilisation

In this study, a unique concrete specimen was used to analyse the response of embedded sacrificial zinc and steel anodes to rainfall and fluctuations in temperature. Current from the zinc and steel anodes increased when the environment was aggressive, showing that the required protection current depends on the present level of corrosion risk. A basis for using the ‘responsive behaviour’ of galvanic anodes is provided by the protective effects of pit re-alkalisation and pH maintenance. By contrast, protection based on achieving adequate polarisation inhibits the use of responsive behaviour and galvanic anodes might only deliver adequate polarisation in aggressive environments.     

The inspection of anisotropic single-crystal components using a 2-D ultrasonic array

Single-crystal metal alloys are used extensively in the manufacture of jet engine components for their excellent mechanical properties at elevated temperatures. The inspection of these components using 2-D ultrasonic arrays potentially allows the detection of subsurface defects in threedimensions from one inspection location. Such methods are not currently suitable for the inspection of single-crystal components because the high elastic anisotropy of single-crystal materials causes directional variation in ultrasonic waves. In this paper, a model of wave propagation in anisotropic material is used to correct an ultrasonic imaging algorithm and is applied to a single-crystal test specimen. For this correctedalgorithm, the orientation of the crystal in a specimen must be known before the inspection. Using the same ultrasonic array to measure the orientation and perform the defect inspection offers the most practical solution. Therefore, potential crystallographic orientation methods using 2-D ultrasonic arrays are also developed and evaluated.     

Reversible back-propagation imaging algorithm for postprocessing of ultrasonic array data

The paper describes a method for processing data from an ultrasonic transducer array. The proposed algorithm is formulated in such a way that it is reversible, i.e., the raw data set can be recovered from the image. This is of practical significance because it allows the raw-data to be spatially filtered using the image to extract, for example, only the raw data associated with a particular scatterer. The method is tested on experimental data obtained from a commercial 64-element, 5.5-MHz array on an aluminum specimen that contains several machined slots and side-drilled holes. The raw transmitter-receiver data corresponding to each scatterer is extracted, and the scattering matrices of different scatterers are reconstructed. This allows the signals from 1-mm-long slot and a 1-mm-diameter hole to be clearly distinguished and the orientation and the size of the slots to be determined.