Radium and barium removal through blending hydraulic fracturing fluids with acid mine drainage.

Wastewaters generated during hydraulic fracturing of the Marcellus Shale typically contain high concentrations of salts, naturally occurring radioactive material (NORM), and metals, such as barium, that pose environmental and public health risks upon inadequate treatment and disposal. In addition, fresh water scarcity in dry regions or during periods of drought could limit shale gas development. This paper explores the possibility of using alternative water sources and their impact on NORM levels through blending acid mine drainage (AMD) effluent with recycled hydraulic fracturing flowback fluids (HFFFs). We conducted a series of laboratory experiments in which the chemistry and NORM of different mix proportions of AMD and HFFF were examined after reacting for 48 h. The experimental data combined with geochemical modeling and X-ray diffraction analysis suggest that several ions, including sulfate, iron, barium, strontium, and a large portion of radium (60-100%), precipitated into newly formed solids composed mainly of Sr barite within the first ∼ 10 h of mixing. The results imply that blending AMD and HFFF could be an effective management practice for both remediation of the high NORM in the Marcellus HFFF wastewater and beneficial utilization of AMD that is currently contaminating waterways in northeastern U.S.A.

Elucidating the Molecular Composition of Cartilage by Proteomics.

Articular cartilage consists of chondrocytes and two major components, a collagen-rich framework and highly abundant proteoglycans. Most prior studies defining the zonal distribution of cartilage have extracted proteins with guanidine-HCl. However, an unextracted collagen-rich residual is left after extraction. In addition, the high abundance of anionic polysaccharide molecules extracted from cartilage adversely affects the chromatographic separation. In this study, we established a method for removing chondrocytes from cartilage sections with minimal extracellular matrix protein loss. The addition of surfactant to guanidine-HCl extraction buffer improved protein solubility. Ultrafiltration removed interference from polysaccharides and salts. Almost four-times more collagen peptides were extracted by the in situ trypsin digestion method. However, as expected, proteoglycans were more abundant within the guanidine-HCl extraction. These different methods were used to extract cartilage sections from different cartilage layers (superficial, intermediate, and deep), joint types (knee and hip), and disease states (healthy and osteoarthritic), and the extractions were evaluated by quantitative and qualitative proteomic analyses. The results of this study led to the identifications of the potential biomarkers of osteoarthritis (OA), OA progression, and the joint specific biomarkers.

15N NMR relaxation data reveal significant chemical exchange broadening in the alpha-domain of human α-lactalbumin

Human alpha-lactalbumin (alpha-LA), a 123-residue calcium-binding protein, has been studied using (15)N NMR relaxation methods in order to characterize backbone dynamics of the native state at the level of individual residues. Relaxation data were collected at three magnetic field strengths and analyzed using the model-free formalism of Lipari and Szabo. The order parameters derived from this analysis are generally high, indicating a rigid backbone. A total of 46 residues required an exchange contribution to T(2); 43 of these residues are located in the alpha-domain of the protein. The largest exchange contributions are observed in the A-, B-, D-, and C-terminal 3(10)-helices of the alpha-domain; these residues have been shown previously to form a highly stable core in the alpha-LA molten globule. The observed exchange broadening, along with previous hydrogen/deuterium amide exchange data, suggests that this part of the alpha-domain may undergo a local structural transition between the well-ordered native structure and a less-ordered molten-globule-like structure.

Magnetic modelling and magneto-hydro-dynamic simulations of an aluminium production electrolytic cell

A simulation of the motion of molten aluminium inside an electrolytic cell is presented. Since the driving term of the aluminium motion is the Lorentz (j × B) body force acting within the fluid,this problem involves the solution of the magneto-hydro-dynamic equations. Different solver modules for the magnetic field computation and for the fluid motion simulation are coupled together. The interactions of all these are presented and discussed.

Magneto-hydro-dynamic analysis of an electrolysis cell for aluminum production

An electrolytic cell for Aluminum production contains molten metal subject to high currents and magnetic flux density. The interaction between these two fields creates electromagnetic forces within the liquid metal and can generate oscillations of the fluid similar to the waves at the free surface of oceans and rivers. The study of this phenomenon requires the simulation of the current density field, of the magnetic flux density field and the solution of the equations of motion of the liquid mass. An attempt to analyze the dynamical behavior of this problem is made by coupling different codes, based on different numerical techniques, in a single tool. The simulations are presented and discussed.

Three-phase computations of the continuous casting process

In this paper, the continuous casting process for steel slab production is modelled using a mult-physics approach. For this purpose, a Finite Volume (FV) numerical model was constructed in 3D, with the following characteristics: Time dependent, turbulent fluid flow and heat transfer in the molten steel and flux regions, solidification of the skin layer, under prescribed heat loss boundary conditions, particle tracking simulation of argon bubbles injected with the metal into the mould, full coupling between bubbles and liquid through buoyancy and interfacial forces using a novel gas accumulation technique, and a full transient simulation of flux-metal interface behaviour under the influence of gravity and fluid inertial forces and bubble plume buoyancy. The unstructure mesh FV code PHYSICA developed at Greenwich was used for carry out the simulations with physical process data and properties supplied by IRSID SA.

Obtaining data to validate a model of an induction skull melting furnace

A casting route is often the most cost-effective means of producing engineering components. However, certain materials, particularly those based on Ti, TiAl and Zr alloy systems, are very reactive in the molten condition and must be melted in special furnaces. Induction Skull Melting (ISM) is the most widely-used process for melting these alloys prior to casting components such as turbine blades, engine valves, turbocharger rotors and medical prostheses. A major research project is underway with the specific target of developing robust techniques for casting TiAl components. The aims include increasing the superheat in the molten metal to allow thin section components to be cast, improving the quality of the cast components and increasing the energy efficiency of the process. As part of this, the University of Greenwich (UK) is developing a computer model of the ISM process in close collaboration with the University of Birmingham (UK) where extensive melting trials are being undertaken. This paper describes the experimental measurements to obtain data to feed into and to validate the model. These include measurements of the true RMS current applied to the induction coil, the heat transfer from the molten metal to the crucible cooling water, and the shape of the column of semi-levitated molten metal. Data are presented for Al, Ni and TiAl.

Modelling the performance of lead-Free solder interconnects for copper bumped flip-chip devices

Traditionally, before flip chips can be assembled the dies have to be attached with solder bumps. This process involves the deposition of metal layers on the Al pads on the dies and this is called the under bump metallurgy (UBM). In an alternative process, however, Copper (Cu) columns can be used to replace solder bumps and the UBM process may be omitted altogether. After the bumping process, the bumped dies can be assembled on to the printed circuit board (PCB) by using either solder or conductive adhesives. In this work, the reliability issues of flip chips with Cu column bumped dies have been studied. The flip chip lifetime associated with the solder fatigue failure has been modeled for a range of geometric parameters. The relative importance of these parameters is given and solder volume has been identified as the most important design parameter for long-term reliability. Another important problem that has been studied in this work is the dissolution of protection metals on the pad and Cu column in the reflow process. For small solder joints the amount of Cu which dissolves into the molten solder after the protection layers have worn out may significantly affect solder joint properties.

Modelling the metal arc weldpool

Traditionally, before flip chips can be assembled the dies have to be attached with solder bumps. This process involves the deposition of metal layers on the Al pads on the dies and this is called the under bump metallurgy (UBM). In an alternative process, however, Copper (Cu) columns can be used to replace solder bumps and the UBM process may be omitted altogether. After the bumping process, the bumped dies can be assembled on to the printed circuit board (PCB) by using either solder or conductive adhesives. In this work, the reliability issues of flip chips with Cu column bumped dies have been studied. The flip chip lifetime associated with the solder fatigue failure has been modeled for a range of geometric parameters. The relative importance of these parameters is given and solder volume has been identified as the most important design parameter for long-term reliability. Another important problem that has been studied in this work is the dissolution of protection metals on the pad and Cu column in the reflow process. For small solder joints the amount of Cu which dissolves into the molten solder after the protection layers have worn out may significantly affect solder joint properties.

Cold crucible melting of reactive metals using combined DC and AC magnetic fields

Cold crucible furnace is widely used for melting reactive metals for high quality castings. Although the water cooled copper crucible avoids contamination, it produces a low superheat of the melt. Experimental and theoretical investigations of the process showed that the increase of the supplied power to the furnace leads to a saturation in the temperature rise of the melt, and no significant increase of the melt superheat can be obtained. The computer model of theprocess has been developed to simulate the time dependent turbulent flow, heat transfer with phase change, and AC and DC magnetohydrodynamics in a time varying liquid metal envelope. The model predicts that the supermimposition of a strong DC field on top of the normal AC field reduces the level of turbulience and stirring in the liquid metal, thereby reducing the heat loss through the base of the crucible and increasing the superheat. The direct measurements of the temperature in the commercial size cold crucbile has confirmed the computer redictions and showed that the addition of a DC field increased the superheat in molten TiAl from ~45C (AC field only) to ~81C (DC+AC fields). The present paper reports further predictions of the effect of a dDC field on top of the AC field and compares these with experimental data.

High electric current density-induced interfacial reactions in micro ball grid array (μBGA) solder joints

The effect of a high electric current density on the interfacial reactions of micro ball grid array solder joints was studied at room temperature and at 150 °C. Four types of phenomena were reported. Along with electromigration-induced interfacial intermetallic compound (IMC) formation, dissolution at the Cu under bump metallization (UBM)/bond pad was also noticed. With a detailed investigation, it was found that the narrow and thin metallization at the component side produced “Joule heating” due to its higher resistance, which in turn was responsible for the rapid dissolution of the Cu UBM/bond pad near to the Cu trace. During an “electromigration test” of a solder joint, the heat generation due to Joule heating and the heat dissipation from the package should be considered carefully. When the heat dissipation fails to compete with the Joule heating, the solder joint melts and molten solder accelerates the interfacial reactions in the solder joint. The presence of a liquid phase was demonstrated from microstructural evidence of solder joints after different current stressing (ranging from 0.3 to 2 A) as well as an in situ observation. Electromigration-induced liquid state diffusion of Cu was found to be responsible for the higher growth rate of the IMC on the anode side.

Effect of 0.5 wt % Cu addition in Sn–3.5% Ag solder on the dissolution rate of Cu metallization

The dissolution of thin film under-bump-metallization (UBM) by molten solder has been one of the most serious processing problems in electronic packaging technology. Due to a higher melting temperature and a greater Sn content, a molten lead-free solder such as eutectic SnAg has a faster dissolution rate of thin film UBM than the eutectic SnPb. The work presented in this paper focuses on the role of 0.5 wt % Cu in the base Sn–3.5%Ag solder to reduce the dissolution of the Cu bond pad in ball grid array applications. We found that after 0.5 wt % Cu addition, the rate of dissolution of Cu in the molten Sn–3.5%Ag solder slows down dramatically. Systematic experimental work was carried out to understand the dissolution behavior of Cu by the molten Sn–3.5%Ag and Sn–3.5%Ag–0.5%Cu solders at 230–250 °C, for different time periods ranging from 1 to 10 min. From the curves of consumed Cu thickness, it was concluded that 0.5 wt % Cu addition actually reduces the concentration gradient at the Cu metallization/molten solder interface which reduces the driving force of dissolution. During the dissolution, excess Cu was found to precipitate out due to heterogeneous nucleation and growth of Cu6Sn5 at the solder melt/oxide interface. In turn, more Cu can be dissolved again. This process continues with time and leads to more dissolution of Cu from the bond pad than the amount expected from the solubility limit, but it occurs at a slower rate for the molten Sn–3.5%Ag–0.5%Cu solder. © 2003 American Institute of Physics.

Modeling the diffusion of solid copper into liquid solder alloys

During the soldering process, the copper atoms diffuse into liquid solders. The diffusion process determines integrity and the reworking possibility of a solder joint. In order to capture the diffusion scenarios of solid copper into liquid Sn–Pb and Sn–Cu solders, a computer modeling has been performed for 10 s. An analytical model has also been proposed for calculating the diffusion coefficient of copper into liquid solders. It is found that the diffusion coefficient for Sn–Pb solder is 2.74 × 10− 10 m2/s and for Sn–Cu solder is 6.44 × 10−9 m2/s. The modeling results reveal that the diffusion coefficient is one of the major factors that govern the rate at which solid Cu dissolve in the molten solder. The predicted dissolved amounts of copper into solders have been validated with the help of scanning electron microscopic analysis.

The influence of alkali metal chlorides on the loss of water from glass-ionomer dental cements

The water loss behaviour of a clinical glass-ionomer dental cement has been studied with and without the addition of alkali metal chlorides. Dehydrating conditions were provided by placing specimens in a desiccator over concentrated sulphuric acid. Cements were prepared using either pure water or an aqueous solution of metal chloride (LiCl, NaCl, KCl) at 1.0 mol/dm(3). In addition, NaCl at 0.5 mol/dm(3) was also used to fabricate cements. Disc-shaped specimens of size 6 mm diameter x 2 mm thickness were made, six performulation, and cured at 37 degrees C for 1 hour They were then exposed to desiccating conditions, and the mass measured at regular intervals. All formulations were found to lose water in a diffusion process that equilibrated after approximately 3 weeks. Diffusion coefficients ranged from 2.27 (0.13) x 10(9) with no additive to 1.85 (0.07) x 10(9) m(2)/s with 1.0 mol/dm(3) KCl. For the salts, diffusion coefficients decreased in the order LiCl > NaCl > KCl. There was no statistically significant difference between the diffusion coefficients for 1.0 and 0.5 mol/dm(3) NaCl. For all salts at 1.0 mol/dm(3) and also additive-free cements, equilibrium losses were, with statistical limits, the same, ranging from 6.23 to 6.34%. On the other hand, 0.5 mol/dm(3) NaCl lost significantly more water 7.05%.

Characterisation of products of tricalcium silicate hydration in the presence of heavy metals

The hydration of tricalcium silicate (C(3)S) in the presence of heavy metal is very important to cement-based solidification/stabilisation (s/s) of waste. In this work, tricalcium silicate pastes and aqueous suspensions doped with nitrate salts of Zn(2+), Pb(2+), Cu(2+) and Cr(3+) were examined at different ages by X-ray powder diffraction (XRD), thermal analysis (DTA/TG) and (29)Si solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). It was found that heavy metal doping accelerated C(3)S hydration, even though Zn(2+) doping exhibited a severe retardation effect at an early period of time of C(3)S hydration. Heavy metals retarded the precipitation of portlandite due to the reduction of pH resulted from the hydrolysis of heavy metal ions during C(3)S hydration. The contents of portlandite in the control, Cr(3+)-doped, Cu(2+)-doped, Pb(2+)-doped and Zn(2+)-doped C(3)S pastes aged 28 days were 16.7, 5.5, 5.5, 5.5, and <0.7%, respectively. Heavy metals co-precipitated with calcium as double hydroxides such as (Ca(2)Cr(OH)(7).3H(2)O, Ca(2)(OH)(4)4Cu(OH)(2).2H(2)O and CaZn(2)(OH)(6).2H(2)O). These compounds were identified as crystalline phases in heavy metal doping C(3)S suspensions and amorphous phases in heavy metal doping C(3)S pastes. (29)Si NMR data confirmed that heavy metals promoted the polymerisation of C-S-H gel in 1-year-old of C(3)S pastes. The average numbers of Si in C-S-H gel for the Zn(2+)-doped, Cu(2+)-doped, Cr(3+)-doped, control, and Pb(2+)-doped C(3)S pastes were 5.86, 5.11, 3.66, 3.62, and 3.52. And the corresponding Ca/Si ratios were 1.36, 1.41, 1.56, 1.57 and 1.56, respectively. This study also revealed that the presence of heavy metal facilitated the formation of calcium carbonate during C(3)S hydration process in the presence of carbon dioxide.