Numerical simulation of vacuum dezincing of lead alloy

Removing zinc by distillation can leave the lead bullion virtually free of zinc and also produces pure zinc crystals. Batch distillation is considered in a hemispherical kettle with water-cooled lid, under high vacuum (50 Pa or less). Sufficient zinc concentration at the evaporating surface is achieved by means of a mechanical stirrer. The numerical model is based on the multiphysics simulation package PHYSICA. The fluid flow module of the code is used to simulate the action of the stirring impeller and to determine the temperature and concentration fields throughout the liquid volume including the evaporating surface. The rate of zinc evaporation and condensation is then modelled using Langmuir’s equations. Diffusion of the zinc vapour through the residual air in the vacuum gap is also taken into account. Computed results show that the mixing is sufficient and the rate-limiting step of the process is the surface evaporation driven by the difference of the equilibrium vapour pressure and the actual partial pressure of zinc vapour. However, at higher zinc concentrations, the heat transfer through the growing zinc crystal crust towards the cold steel lid may become the limiting factor because the crystallization front may reach the melting point. The computational model can be very useful in optimising the process within its safe limits.

Reliability study of the electroless Ni–P layer against solder alloy

Copper (Cu) has been widely used in the under bump metallurgy of chip and substrate metallization for chip packaging. However, due to the rapid formation of Cu–Sn intermetallic compound (IMC) at the tin-based solder/Cu interface during solder reaction, the reliability of this type of solder joint is a serious concern. In this work, electroless nickel–phosphorous (Ni–P) layer was deposited on the Cu pad of the flexible substrate as a diffusion barrier between Cu and the solder materials. The deposition was carried out in a commercial acidic sodium hypophosphite bath at 85 °C for different pH values. It was found that for the same deposition time period, higher pH bath composition (mild acidic) yields thicker Ni–P layer with lower phosphorous content. Solder balls having composition 62%Sn–36%Pb–2%Ag were reflowed at 240 °C for 1 to 180 min on three types of electroless Ni–P layers deposited at the pH value of 4, 4.8 and 6, respectively. Thermal stability of the electroless Ni–P barrier layer against the Sn–36%Pb–2%Ag solder reflowed for different time periods was examined by scanning electron microscopy equipped with energy dispersed X-ray. Solder ball shear test was performed in order to find out the relationship between the mechanical strength of solder joints and the characteristics of the electroless Ni–P layer deposited. The layer deposited in the pH 4 acidic bath showed the weak barrier against reflow soldering whereas layer deposited in pH 6 acidic bath showed better barrier against reflow soldering. Mechanical strength of the joints were deteriorated quickly in the layer deposited at pH 4 acidic bath, which was found to be thin and has a high phosphorous content. From the cross-sectional studies and fracture surface analyses, it was found that the appearance of the dark crystalline phosphorous-rich Ni layer weakened the interface and hence lower solder ball shear strength. Ni–Sn IMC formed at the interfaces was found to be more stable at the low phosphorous content (∼14 at.%) layer. Electroless Ni–P deposited at mild acidic bath resulting phosphorous content of around 14 at.% is suggested as the best barrier layer for Sn–36%Pb–2%Ag solder.

The effects of thermo-electrically induced convection in alloy solidification

The effects of a constant uniform magnetic field on thermoelectric currents during dendritic solidification were investigated using a 2-dimensional enthalpy based numerical model. Using an approximation of the dendrite growing in free space it was found that the resulting Lorentz force generates a circulating flow influencing the solidification pattern. As the magnetic field strength increases it was found that secondary growth on the clockwise side of the primary arm of the dendrite was encouraged, while the anticlockwise side is suppressed due to a reduction in local free energy. The preferred direction of growth rotated in the clockwise sense under an anti-clockwise flow for both the binary alloy and pure material. The tip velociy is significantly increased compared to growth in stagnant flow. This is due to a small recirculation that follows the tip of the dendrite; bringing in colder liquid and lower concentrations of solute. The recirculation being not normally incident on the tip is most likely the cause for the rotation. Grain growth consisting of multiple seeds with the same anisotropy growing in the same plane, gives a competition to release latent heat resulting in stunted growth. The initial growth for each dendrite is very similar to the single seed cases indicating that dendrites must become before the thermoelectric interactions are significant.

Thermoelectric effects on alloy solidification microstructure

Thermoelectric currents in the presence of a magnetic field generate Lorentz forces which can drive fluid flow. In the case of dendritic growth a naturally occurring thermoelectric current exists and in the presence of a high magnetic field micro convections are generated. Experimental evidence has attributed changes in microstructure to this effect. A numerical model has been developed to study the flow field around an unconstricted equiaxed dendrite growing under these conditions. The growth is modeled in 2D and 3D by an enthalpy based method and a complex flow structure has been predicted. Using a pseudo-3D approximation for economy, realistic 2D simulations are obtained where a fully coupled transient scheme reveals significant changes to the dendrite morphology reflecting experimental evidence. There is a rotation of the preferred direction of growth and increased secondary branching.

Modelling the tilt-casting process for the tranquil filling of titanium alloy turbine blades

The tilt-casting method is used to achieve tranquil filling of gamma-TiAl turbine blades. The reactive alloy is melted in a cold crucible using an induction coil and then the complete crucible-mould- running system assembly is rotated through 180degrees to transfer the metal into the mould. The induction current is ramped down gradually as the rotation starts and the mould is preheated to maintain superheat. The liquid metal then enters the mould and the gas within it (argon) escapes through the inlet aperture and through auxiliary vents. Solidification starts as soon the metal enters the mould and it is important to account for this effect to predict and prevent misruns. The rotation rate has to be controlled carefully to allow sufficient time for gas evacuation, but at the same time preserve superheat. This 3-phase system is modelled using the FV method, with a fast implicit numerical scheme used to capture the transient liquid free surface. The enthalpy method is used to model solidification and predict defects such as trapped bubbles, macro-porosity or surface connected porosity. Modeling is used to support an experimental program for the development of a production method for gamma-TiAl blades, with a target length of 40cm. The experiments provide validation for the model and the model in turn optimizes the tilt-casting process. The work is part of the EU project IMPRESS.

Zinc polycarboxylate dental cement for the controlled release of an active organic substance: proof of concept

The potential of employing zinc polycarboxylate dental cement as a controlled release material has been studied. Benzalkonium chloride was used as the active ingredient, and incorporated at concentrations of 1, 2 and 3% by mass within the cement. At these levels, there was no observable effect on the speed of setting. Release was followed using an ion-selective electrode to determine changes in chloride ion concentration with time. This technique showed that the additive was released when the cured cement was placed in water, with release occurring by a diffusion mechanism for the first 3 h, but continuing beyond that for up to 1 week. Diffusion coefficients were in the range 5.62 × 10(−6) cm(2) s(−1) (for 1% concentration) to 10.90 × 10(−6) cm(2) s(−1) (for 3% concentration). Up to 3% of the total loading of benzalkonium chloride was released from the zinc polycarboxylate after a week, which is similar to that found in previous studies with glass-ionomer cement. It is concluded that zinc polycarboxylate cement is capable of acting as a useful material for the controlled release of active organic compounds.

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%.

Review paper: role of aluminum in glass-ionomer dental cements and its biological effects

The role of aluminum in glass-ionomers and resin-modified glass-ionomers for dentistry is reviewed. Aluminum is included in the glass component of these materials in the form of Al(2)O(3) to confer basicity on the glass and enable the glass to take part in the acid-base setting reactions. Results of studies of these reactions by FTIR and magic-angle spinning (MAS)-NMR spectroscopy are reported and the role of aluminum is discussed in detail. Aluminum has been shown to be present in the glasses in predominantly 4-coordination, as well as 5- and 6-coordination, and during setting a proportion of this is converted to 6-coordinate species within the matrix of the cement. Despite this, mature cements may contain detectable amounts of both 4- and 5-coordinate aluminum. Aluminum has been found to be leached from glass-ionomer cements, with greater amounts being released under acidic conditions. It may be associated with fluoride, with which it is known to complex strongly. Aluminum that enters the body via the gastro-intestinal tract is mainly excreted, and only about 1% ingested aluminum crosses the gut wall. Calculation shows that, if a glass-ionomer filling dissolved completely over 5 years, it would add only an extra 0.5% of the recommended maximum intake of aluminum to an adult patient. This leads to the conclusion that the release of aluminum from either type of glass-ionomer cement in the mouth poses a negligible health hazard.

Marginal adaptation and performance of bioactive dental restorative materials in deciduous and young permanent teeth

Objective: The aim of this study was to investigate the adaptation of different types of restorations towards deciduous and young permanent teeth. Materials and Methods: Class V cavities were prepared in deciduous and young permanent teeth and filled with different materials (a conventional glass-ionomer, a resin-modified glass-ionomer, a poly-acid-modified composite resin and a conventional composite resin). Specimens were aged in artificial saliva for 1, 6, 12 and 18 months, then examined by SEM. Results: The composite resin and the polyacid-modified composite had better marginal adaptation than the glass-ionomers,though microcracks developed in the enamel of the tooth. The glass-ionomers showed inferior marginal quality and durability, but no microcracking of the enamel. The margins of the resin-modified glass-ionomer were slightly superior to the conventional glass-ionomer. Conditioning improved the adaptation of the composite resin, but the type of tooth made little or no difference to the performance of the restorative material. All materials were associated with the formation of crystals in the gaps between the filling and the tooth; the quantity and shape of these crystals varied with the material. Conclusions: Resin-based materials are generally better at forming sound, durable margins in deciduous and young permanent teeth than cements, but are associated with microcracks in the enamel. All fluoride-releasing materials give rise to crystalline deposits.

The kinetics of water loss from zinc phosphate and zinc polycarboxylate dental cements

The water desorption behaviour of three different zinc oxide dental cements (two polycarboxylates, one phosphate) has been studied in detail. Disc-shaped specimens of each material were prepared and allowed to lose water by being subjected to a low humidity desiccating atmosphere over concentrated sulfuric acid. In all three cements, water loss was found to follow Fick's second law for at least 6 h (until M(t)/M(infinity) values were around 0.5), with diffusion coefficients ranging from 6.03 x 10(-8 )cm(2 )s(-1) (for the zinc phosphate) to 2.056 x 10(-7 )cm(2 )s(-1) (for one of the zinc polycarboxylates, Poly F Plus). Equilibration times for desorption were of the order of 8 weeks, and equilibrium water losses ranged from 7.1% for zinc phosphate to 16.9% and 17.4% for the two zinc polycarboxylates.

The interaction of zinc oxide-based dental cements with aqueous solutions of potassium fluoride

The ability of zinc oxide-based dental cements (zinc phosphate and zinc polycarboxylate) to take up fluoride from aqueous solution has been studied. Only zinc phosphate cement was found to take up any measurable fluoride after 5 h exposure to the solutions. The zinc oxide filler of the zinc phosphate also failed to take up fluoride from solution. The key interaction for this uptake was thus shown to involve the phosphate groups of the set cement. However, whether this took the form of phosphate/fluoride exchange, or the formation of oxyfluoro-phosphate groups was not clear. Fluoride uptake followed radicaltime kinetics for about 2 h in some cases, but was generally better modelled by the Elovich equation, dq(t)/dt = alpha exp(-beta q(t)). Values for alpha varied from 3.80 to 2.48 x 10(4), and for beta from 7.19 x 10(-3) to 0.1946, though only beta showed any sort of trend, becoming smaller with increasing fluoride concentration. Fluoride was released from the zinc phosphate cements in processes that were diffusion based up to M(t)/M(infinity) of about 0.4. No further release occurred when specimens were placed in fresh volumes of deionised water. Only a fraction of the fluoride taken up was re-released, demonstrating that most of the fluoride taken up becomes irreversibly bound within the cement.

Water transport in resin-modified glass-ionomer dental cement

Water uptake and water loss have been studied in a commercial resin-modified glass-ionomer cement, Fuji II LC, under a variety of conditions. Uptake was generally non-Fickian, but affected by temperature. At room temperature, the equilibrium water uptake values varied from 2.47 to 2.78% whereas at low temperature (12 degrees C), it varied from 0.85 to 1.18%. Cure time affected uptake values significantly. Water uptake was much lower than in conventional glass-ionomer restorative cements exposed to water vapor. Loss of water under desiccating conditions was found to be Fickian for the first 5 h loss at both 22 and 12 degrees C. Diffusion coefficients were between 0.45 and 0.76 x 10( -7) cm(2)/s, with low temperature diffusion coefficients slightly greater than those at room temperature. Plotting water loss as percentage versus s(-(1/2)) allowed activation energies to be determined from the Arrhenius equation and these were found to be 65.6, 79.8, and 7.7 kJ/mol respectively for 30, 20, and 10 s cure times. The overall conclusion is that the main advantage of incorporating HEMA into resin-modified-glass-ionomers is to alter water loss behavior. Rate of water loss and total amount lost are both reduced. Hence, resin-modified glass-ionomers are less sensitive to water loss than conventional glass-ionomers.

Fluoridation for dental public health

This article reviews the means by which fluoride is supplied to populations. Many public health authorities provide fluoridated drinking water, with typical concentrations of fluoride of between 0.5 and 1.0 ppm. This has been found to be safe and effective, though differences in caries incidence between fluoridated and non-fluoridated regions are less than they were 50 years ago, because of the wider availability of fluoridated products to the whole population. Concerns about the effect of fluoride on bone density and associated conditions are reviewed and the general conclusion from considering the literature on fluoride is that there is almost no cause for concern. Alternatives to water as a means of delivering fluoride to the general public that are being used in a number of countries are salt and milk. These alternatives are also reviewed and have been shown to give satisfactory levels of protection against caries, though milk is shown to be less satisfactory than water as a vehicle for fluoride delivery. Milk is also less effective in providing fluoride to individuals in the population, and is less likely to be consumed by people in lower socio-economic groups, precisely those who suffer most from dental caries. This study concludes that mass water fluoridation remains an important contribution to good oral health throughout the community.