Vibration thresholds for fretting corrosion in electrical connectors

Single frequency vibration tests were used to induce fretting corrosion in tin alloy plated contacts. The samples used in this study were connectors consisting of 25 pairs of mated pin and socket contacts. Experimental results for a variety of vibration levels, frequencies, and wiring tie-off lengths are presented. The experiments consisted of running a series of vibration tests at each frequency where the excitation level was stepped through a range of g-levels. During each test run contact resistance was monitored as a performance characteristic. The results exhibit threshold behavior at each frequency for the onset of fretting degradation. Typically a plateau region was observed where similar g-levels produced similar fretting rates. It was also found that outside the plateau region the g-levels varied according to the dynamic behavior of the mechanical system. In addition, a transfer matrix model was used to analyze these results. An empirical fit of the data correlated well with the model when damping was used. This analysis revealed the importance of the bending moment induced at the contact interface as a result of excitation levels and tie-off configurations. Consequently, it is concluded that dynamic response of the mechanical system under various g-levels and tie off configurations can greatly impact the performance of a connector system subjected to vibration stresses.     

Highly organized spherical hosts that bind organic guests in aqueous solution with micromolar affinity: microcalorimetry studies

Two novel closed-shell hemicarcerand-like hosts with spherical cavities of 11 A diameter that are soluble in aqueous solution were constructed. The binding of xylenes, aryl ethers, polyaromatic compounds, ferrocene derivatives, and bicyclic aliphatic compounds were examined by NMR spectroscopy and microcalorimetry. NMR binding studies indicated that binding depended upon guest hydrophobicity and shape. No binding was detected for guests in which a charge must be desolvated as part of inclusion or for guests that can not fit within the cavity of the host. Three complexes 2.naphthalene, 2.p-xylene, and 2.ferrocene were isolated and found to be indefinitely stable in the solid phase and in aqueous solution. The binding constants for these complexes are estimated to be greater than 10(8) M-1. Thirteen guests were examined by microcalorimetry with binding constants ranging between 10(7) and 10(3) M-1. A comparison of results obtained here with those from previous work with beta-cyclodextrin and cyclophane hosts, along with analysis of the entropy-enthalpy compensation data, indicate that there is a higher degree of guest desolvation with this host structure than with open-shell hosts. This accounts at least partially for the increase in affinity observed with these closed-shell hosts. Replacing a hydroxy group in the host portal with a hydrogen atom does not affect the binding constant, a finding consistent with the guest residing deeply buried within the host cavity. It was observed that aromatic guests are bound with higher affinity than aliphatic ones in agreement with results that point to the importance of London dispersion forces in the association of aromatic components in face-to-edge orientations. The correlation of changes in NMR chemical shift with microcalorimetry data supports a model in which increased CH-pi interactions strengthen association between host and guest due to the dominant role of van der Waals dispersion forces. Remarkably, the binding constant for the 1,4 isomer of dimethoxybenzene is 32 times higher than for the 1,2 isomer, and even greater discrimination is observed between the xylene guests since the binding constant for p-xylene is 80 times greater than that for o-xylene. This discrimination between isomeric guests by a rigid host indicates that changes in specific hydrophobic interactions have substantial effects upon binding affinity.     

Kinetic Spectroelectrochemical Assay for Uric Acid in Human Urine

A spectroelectrochemical (SEC) assay for uric acid in human urine has been developed that is essentially reagent-free and involves relatively short analysis times of ∼12 min per specimen using a single-point standard addition approach. The SEC method was demonstrated to be selective for uric acid in human urine, avoiding interference through both the usual control parameters (electrolysis potential and measurement wavelength) and the relatively slow kinetics of a post-electrolysis reaction involving the oxidation product. Results from the SEC analysis of a split set of human urine specimens were well correlated to those obtained using a standard high-performance liquid chromatography method, suggesting the feasibility of clinical applications.     

Mechanistic study of beta-substituent effects on the mechanism of ketone reduction by SmI(2)

The rate constants for the reduction of 2-butanone, methylacetoacetate, N, N-dimethylacetoacetamide, and a series of 4'- and 2'-substituted acetophenone derivatives by SmI(2) were determined in dry THF using stopped-flow absorption decay experiments. Activation parameters for the electron-transfer processes in each series of compounds were determined by a temperature-dependence study over a range of 30 to 50 degrees C. Two types of reaction pathways are possible for these electron-transfer processes. One proceeds through coordination (Scheme 1) while the other involves chelation (Scheme 2). The results described herein unequivocally show that both coordination and chelation provide highly ordered transition states for the electron-transfer process but the presence of a chelation pathway dramatically increases the rate of the reduction of these substrates by SmI(2). The ability of various functional groups to promote a chelated reaction pathway plays a crucial role in determining the rate of the reaction. Among the 2'-substituted acetophenone series, the presence of a fluoro, amino, or methoxy substituent enhances the rate of reduction compared to the 4'-analogues. In particular, the presence of a 2'-fluoro substituent on acetophenone provides a highly ordered transition state and considerably enhances the rate of ketone reduction.     

A Facile synthesis of 3-alkylthio-(or arylthio-)pyridines and 3,5-bis(alkylthio)pyridines

3-Alkylthio- (or 3-arylthio-)pyridines and 3,5-bis(alkylthio)pyridine can be conveniently prepared by the reaction of 3-thiocyanato- or 3,5-bis(thiocyanato)pyridines with tri-n-butylphosphine in the presence of alcohol.     

Influence of Molecular Conformation on the Constitutive Response of Polyethylene: A Comparison of HDPE, UHMWPE, and PEX

The current work presents the characterization and comparison of the mechanical response of three different industrial forms of polyethylene. Specifically, high-density polyethylene (HDPE), ultra high molecular weight polyethylene (UHMWPE), and cross-linked polyethylene (PEX) were tested in compression as a function of temperature (−75 to 100°C) and strain-rate (10⁻⁴ to 2,600 s⁻¹). The responses of UHMWPE and PEX are very similar, whereas HDPE exhibits some differences. The HDPE samples display a significantly higher yield stress followed by a flat flow behavior. Conversely UHMWPE and PEX both exhibit significant strain hardening after yield. The temperature and strain-rate dependence are captured by simple linear and logarithmic fits over the full range of conditions investigated. The yield behavior is presented in terms of an empirical mapping function that is extended to analytically solve for the mapping constant. The power-law dependence on strain-rate observed in some polymers is explained using this mapping function.