Hot isostatic pressed pyrochlore glass-ceramics: Revealing structure insides at the reaction interface

As potential waste forms for immobilizing actinide-rich radioactive wastes, Eu₂Ti₂O₇ (Eu as a surrogate for minor actinides) pyrochlore glass-ceramics were fabricated via hot isostatic pressing (HIPing) at 1200°C. The structure and microstructure at the reaction interface between the glass-ceramic waste form and the stainless steel (SS) canister under HIPing conditions were carefully investigated with scanning electron microscopy (SEM), transmission electron microscopy (TEM), and synchrotron single crystal X-ray diffraction (SC-XRD). The interactions at the reaction interface led to the formations of a ~10-µm-thick Cr₂O₃ layer as the oxidation front of the SS and a layer of a mixed oxide phase (Eu_1.25SiCr_0.8Ti_1.2O_7.5) on the glass-ceramic side of the reaction interface. The crystal structure of such a unique mixed oxide phase was revealed indubitably with a combination of synchrotron SC-XRD and TEM assisted with a focused ion beam (FIB) SEM system. The improved structural understanding of the reaction interface will help to support the utilization of HIPing as a versatile hot consolidation process for the treatment of radioactive wastes.     

Role of MoS2 morphology on wear and friction under spectrum loading conditions

One of the ways by which grease is evaluated is by using a four‐ball wear test using ASTM D2266. However, actual applications may require bearings to be subjected to spectrum loading conditions. This study focuses on using ball milling to mitigate the wear from sharp edges in the MoS₂ particles. Two different blends of greases were formulated using MoS₂ in the as‐received state (unmilled) and milled MoS₂; they were tested under spectrum loading conditions where the load and frequency of the tests were treated as variables. It was found that ball milling of the MoS₂ significantly reduces the wear under spectrum loading condition both for ramp‐up and ramp‐down conditions. It was also shown that shortening the time step for both the ramp‐up and ramp‐down cycles resulted in larger wear for unmilled MoS₂ particles in comparison with milled MoS₂ particles in grease. The milling process did not play a significant role when frequency of the test was either ramped up or down. Copyright © 2015 John Wiley & Sons, Ltd.     

Wavelet domain analysis for identification of vehicle axles from bridge measurements

Bridge weigh-in-motion (B-WIM) is a process by which the axle and gross vehicle weights of vehicles travelling at highway speeds can be determined from instrumented bridges. The traditional method of attaching strain transducers to the soffit of the bridge and placing axle detectors on the road surface has been replaced here by using additional transducers underneath the bridge for axle detection and nothing-on-the-road (NOR). This paper presents a wavelet based analysis of strain signals and shows the efficacy of using wavelets in pattern recognition of these signals. The transformed signals are used to identify axle passage and hence the vehicle velocity and the axle spacing. In addition to numerically generated strains, signals acquired from such a NOR instrumentation of a bridge in Slovenia have been analysed by the method of wavelet transformation to extract axle position information that was not readily detectable using existing methods.     

Interaction between borosilicate melt and Inconel

Understanding the mode of interaction between borosilicate melt and Inconel is important for long time usage of melter pot in vitrification plant. The present study shows that significant elemental exchanges take place across the borosilicate melt/Inconel interface resulting in the development of (Fe, Ni)CrO₄ needle and (Fe, Ni)Cr₂O₄ cubic phases. This results in significant depletion of Cr within Inconel near the interface. Beside these, CrB precipitates formed along the Inconel grain boundaries.     

Processing, physical and thermal properties of BlackglasTM matrix composites reinforced with NextelTM fabric

The cure and pyrolysis behavior of a BlackglasTM resin and NextelTM 440 impregnated with BlackglasTM resin were studied. Cure of the BlackglasTM resin is an exothermic process and DSC studies indicate that with an increase of catalyst content from 0.1 to 1.0%, the onset and peak temperature of cure are decreased coupled with an increase in the enthalpy of cure indicating a greater extent of cross linking. However, pyrolysis char yield of the pyrolyzate is relatively insensitive to cure conditions.Cure pressure and pyrolysis environment are variables in the processing of BlackglasTM matrix composite reinforced with NextelTM 440 Plain weave fabric. Variations in cure pressure from 30 to 80 psi had no discernible effect on the chemistry of the pryrolyzate. However, the higher cure pressure resulted in top and bottom ply damage. Pyrolysis in an Ar environment resulted in incorporationj of up to 12 wt % C of which 8 wt % as graphitic in nature in the ceramic matrix. Pyrolysis in NH3 resulted in 3.9 wt % nitrogen and 1.5 wt % carbon in the matrix, with all the nitrogen and carbon bonded to Si. The cured panels have to be pyrolyzed/densified between 6–7 times to achieve required density and porosity content. Oxidation behavior of the composites at 1000°C indicate that the argon pyrolyzed CMC's lose more weight due to decomposition of the pyrolytic carbon, whereas, NH3 pyrolyzed CMC's are stable as both the N and C are bonded to Si in the matrix. Dielectric constants K and K measured at 1 GHz in the as-processed condition are high in the argon pyrolyzed CMC, (K = 11–28) due to the presence of pyrolytic carbon. On the other hand NH3 pyrolyzed CMC exhibit low dielectric constant (K = 4). On oxidation, the dielectric constant in both the Ar and NH3 pyrolyzed panels is approximately 4.0.     

Studies on Hg(II) ion retention properties of cross-linked graft copolymer of acrylic acid and its analytical application

The effects of different parameters such as time, concentration, pH and temperature, on metal ion retention properties of the polymer have been investigated. Metal ion adsorption kinetics, isotherms and thermodynamics have been studied. A plausible mechanism for mercury ion retention has been suggested. Mercuric ion has been isolated quantitatively from various synthetic mixture containing metal ions (Ni²⁺, Cd²⁺, Pb²⁺ and Zn²⁺).     

Synthesis of Fluorinated ZDDP Compounds

Volatile degradation products of zinc dialkyl dithio phosphate (ZDDP) composed of phosphorus and sulfur compounds reduce the efficiency of catalytic converters resulting in harmful emissions. A unique way of reducing ZDDP level while maintaining good antiwear performance has been achieved by reacting a novel additive FeF₃ with ZDDP. The objective of this research is to examine the chemical interactions between ZDDP and FeF₃ that yield the new chemical species responsible for the improved wear performance. The approach adopted involves studies of thermal degradation products of ZDDP that are formed in presence and absence of FeF₃. These intermediate products are responsible for the formation of protective tribofilms on the surface. Nuclear Magnetic Resonance Spectroscopy (³¹P and ¹⁹F) has been principally used to identify these products. Results have indicated the formation of new fluorinated phosphorus compounds formed as ‘early intermediate’ products in the reaction between ZDDP and FeF₃. The chemical differences observed were used to justify the improved tribological behavior of the new fluorinated ZDDP compounds in comparison to ZDDP. Paper was presented at the STLE/ASME International Joint Tribology Conference, October 23–25, 2006, San Antonio, TX. Paper Number IJTC2006-12053.     

Synthesis of cross-linked graft copolymer from [2-(methacryloyloxy)ethyl] trimethylammonium chloride and poly(vinyl alcohol) for removing chromium(VI) from aqueous solution

A novel graft copolymer of [2-(methacryloyloxy)ethyl] trimethylammonium chloride onto poly(vinyl alcohol) has been synthesized and it is cross-linked by glutaraldehyde for the investigation of its efficiency in removing Cr(VI) from aqueous solution. The chemical nature of the ion-exchange resin has been elucidated with the help of chemical test, Fourier transform infrared, thermo gravimetric analysis and DTA. Particle size, surface area, ion-exchange capacity, optimum pH, reaction time and temperature for Cr(VI) extraction were determined. Chromium(VI) adsorption kinetics, isotherm and thermodynamics have been studied. A plausible mechanism for chromium ion-exchange has been suggested.     

Impression creep of monolithic and composite lead free solders

Even though several EMS (Electronic manufacturing services) companies are currently producing “lead free” products, a general notion of apprehension still exists in the industry, primarily due to the lack of sufficient mechanical reliability data supporting the use of lead free alloys. The current study was an effort to generate an understanding of the mechanisms of creep deformation in monolithic and composite (Ag and Cu reinforced) Sn–3.5Ag and Sn–3.0Ag–0.5Cu lead free alloys in the high stress high temperature regime. Small volume solder samples were reflowed using a custom built computer controlled resistance furnace. Impression creep testing was employed to determine the activation energy and stress exponent. A careful analysis of the collected data revealed the underlying creep mechanisms and the following conclusions could be made. Both Sn–3.5Ag and Sn–3.0Ag–0.5Cu exhibited higher creep resistance as compared to the eutectic tin–lead solder under all tested conditions, with the ternary lead free alloy marginally outperforming the binary lead free alloy. Composite solders performed better as compared to monolithic solders. Furthermore, Cu reinforced solders demonstrated higher creep resistance as compared to Ag reinforced solders.     

XANES analysis of calcium and sodium phosphates and silicates and hydroxyapatite–Bioglass®45S5 co-sintered bioceramics

Bioglass®45S5 was co-sintered with hydroxyapatite at 1200 °C. When small amounts (< 5 wt.%) of Bioglass®45S5 was added it behaved as a sintering aid and also enhanced the decomposition of hydroxyapatite to β-tricalcium phosphate. However when 10 wt.% and 25 wt.% Bioglass®45S5 was used it resulted in the formation of Ca₅(PO₄)₂SiO₄ and Na₃Ca₆(PO₄)₅ in an amorphous silicate matrix respectively. These chemistries show improved bioactivity compared to hydroxyapatite and are the subject of this study. The structure of several crystalline calcium and sodium phosphates and silicates as well as the co-sintered hydroxyapatite–Bioglass®45S5 bioceramics were examined using XANES spectroscopy. The nature of the crystalline and amorphous phases were studied using silicon (Si) and phosphorus (P) K- and L_2,3-edge and calcium (Ca) K-edge XANES.Si L_2,3-edge spectra of sintered bioceramic compositions indicates that the primary silicates present in these compositions are sodium silicates in the amorphous state. From Si K-edge spectra, it is shown that the silicates are in a similar structural environment in all the sintered bioceramic compositions with 4-fold coordination.Using P L_2,3-edge it is clearly shown that there is no evidence of sodium phosphate present in the sintered bioceramic compositions. In the P K-edge spectra, the post-edge shoulder peak at around 2155 eV indicates that this shoulder to be more defined for calcium phosphate compounds with decreasing solubility and increasing thermodynamic stability. This shoulder peak is more noticeable in hydroxyapatite and β-TCP indicating greater stability of the phosphate phase. The only spectra that does not show a noticeable peak is the composition with Na₃Ca₆(PO₄)₅ in a silicate matrix indicating that it is more soluble compared to the other compositions.