Effect of metal chlorides on the sintering and densification of hydroxyapatite adsorbent

This work is part of a series of studies dealing with the evaluation of the effects of major elements of solid waste, especially metallic oxides, nitrates, sulfates, and chlorides, on the sintering and the densification of calcium hydroxyapatite (Ca-HAP) adsorbent. The effects of chloride salts of potassium (KCl) and zinc (ZnCl2) on sintering and densification of Ca-HAP were studied using surface area reduction and shrinkage measurements. The addition of KCl (2% w/w) activated the sintering process by bringing a swift reduction in surface area and lowering the densification temperature. However, a low final densification was achieved. Increasing the amount of this additive to 10% w/w further lowered the final densification and lowered the densification temperature of hydroxyapatite by 150 degrees C. On the other hand, the addition of 2 wt % of ZnCl2 deactivated the sintering process by slowing down the densification process and raising the densification temperature. However, the reduction of surface area was comparable to that of Ca-HAP. The densification rate contained two or more rate maxima indicating the additives (salts) bring multiple speeds in the densification process.

The effect of ionic strength variation and anion competition on the development of nitrate accumulations in variable charge subsoils

The leaching of N fertilisers has led to the formation of nitrate (NO3) accumulations in deep subsoils (>5 m depth) of the Johnstone River catchment. This paper outlines the chemical mechanism by which these NO3 accumulations are formed and maintained. This was achieved via a series of column experiments designed to investigate NO3 leaching in relation to the soil charge chemistry and the competition of anions for exchange sites. The presence of variable charge minerals has led to the formation positive surface charge within these profiles. An increase in the soil solution ionic strength accompanying the fertiliser leaching front acts to increase the positive (and negative) charge density, thus providing adsorption sites for NO3. A decrease in the soil solution ionic strength occurs after the fertiliser pulse moves past a point in the profile, due to dilution with incoming rainwater. Nitrate is then released from the exchange back into the soil solution, thus buffering the decrease in the soil solution ionic strength. Since NO3 was adsorbed throughout the profile in this experiment it does not effectively explain the situation occurring in the field. Previous observations of the sulfate (SO4) profile distribution indicated that large SO4 accumulations in the upper profile may influence the NO3 distribution through competition for adsorption sites. A subsequent experiment investigating the effect of SO4 additions on NO3 leaching showed that NO3 adsorption was minimal in the upper profile. Adsorption of NO3 did occur, though only in the region of the profile where SO4 occupancy was low, i.e. in the lower profile. Therefore, the formation of the NO3 accumulations is dependent on the variable charge mineralogy, the variation of charge density with soil solution ionic strength, and the effects of SO4 competition for adsorption sites.

The effect of salinity on plant available water

Salinity acts to inhibit plant access to soil water by increasing the osmotic strength of the soil solution. As the soil dries, the soil solution becomes increasingly concentrated, further limiting plant access to soil water. An experiment was conducted to examine the effect of salt on plant available water in a heavy clay soil, using a relatively salt tolerant species, wheat ‘Kennedy’, and a more salt sensitive species, chickpea ‘Jimbour’. Sodium chloride was applied to Red Ferrosol at 10 rates from 0 to 3 g/kg. Plants were initially maintained at field capacity. After 3 weeks, plants had become established and watering was ceased. The plants then grew using the water stored in the soil. Once permanent wilting point was reached plants were harvested, and soil water content was measured. The results showed that without salt stress, wheat and chickpea extracted approximately the same amount of water. However, as the salt concentration increased, the ability of chickpea to extract water was severely impaired, while wheat’s ability to extract water was not affected over the range of concentrations examined. Growth of both wheat and chickpea was reduced even from low salt concentrations. Possible explanations for this are that the effect on growth is due to Cl- toxicity and that this occurs at lower concentrations than the osmotic effect of salinity, or that the metabolic demands of maintaining plant water balance and extracting soil water under saline conditions result in reduced growth.

Characterization of a volume-sensitive chloride current in rat osteoblast-like (ROS 17/2.8) cells

1. During osmotic swelling, cultured osteoblastic cells (ROS 17/2.8) exhibited activation of large amplitude Cl- currents in the whole-cell configuration of the patch-clamp technique. Effects of hypotonic shock on cell volume and membrane conductance were rapidly reversed on return to isotonic conditions. 2. Voltage command pulses in the range -80 to +50 mV produce instantaneous activation of Cl- currents. At potentials more positive than +50 mV the current exhibited time-dependent inactivation. The instantaneous current-voltage relationship was outwardly rectifying. 3. The anion permeability sequence of the induced current was SCN- (2.2) > I- (1.9) > Br- (1.5) > Cl- (1.0) > F- (0.8) > gluconate- (0.2). This corresponds to Eisenman's sequence I. 4. The volume-sensitive Cl- current was effectively inhibited by the Cl- channel blockers 4,4'-diisothiocyanatostilbene-2,2-disulphonic acid (DIDS) and 5-nitro-2-(3-phenylpropylamino) benzoic acid (NPPB). Outward currents were more effectively suppressed by DIDS than inward currents. The concentrations for 50% inhibition (IC50) of outward and inward currents were 81 and 298 μM, respectively. NPPB was equally effective at inhibiting outward and inward currents (IC50 of 64 μM). The current was relatively insensitive to diphenylamine-2-carboxylate (DPC), 500 μM producing only 22.5 ± 4.0% inhibition. 5. Inhibitors of protein kinase A (H-89, 1 μM) and tyrosine kinase (tyrphostin A25, 200 μM) were without effect upon activation of Cl- currents in response to hypotonic shock. Under isotonic conditions, elevation of intracellular Ca2+ by ionomycin (1 μM) or activation of protein kinase C by 12-O-tetradecanoylphorbol 13-acetate (TPA, 0.1 μM) failed to evoke increases in basal Cl- conductance levels. 6. It is concluded that an outwardly rectifying Cl- conductance is activated upon osmotic swelling and may be involved in cell volume regulation of ROS 17/2.8 cells.

The effect of selected water-soluble excipients on the dissolution of paracetamol and ibuprofen

The purpose of this investigation was to study the dissolution behavior of paracetamol and ibuprofen in the presence of a range of selected potential excipients. First, a pH-solubility profile was generated for both drugs, and the effect of changing hydrodynamic conditions on the intrinsic dissolution rate was investigated. It was established that both drugs dissolved according to the diffusion-layer model. Paracetamol solubility (approximately 20.3 mg mL -1) did not vary from pH 1.2-8.0, corresponding to the in vivo range in the gastrointestinal tract. Ibuprofen had an intrinsic solubility of approximately 0.06 mg mL-1, and pKa was calculated as 4.4. Second, the effects of selected potential excipients (lactose, potassium bicarbonate, sodium bicarbonate, sodium chloride, and tartaric acid) were evaluated by measuring the effect of the inclusion of each additive in the dissolution medium on drug solubility, drug intrinsic dissolution rate, and solution viscosity. The results were evaluated using the diffusion-layer model, and it was determined that for paracetamol, the collected data fitted the model for all the excipients studied. For ibuprofen, it was found that there were differences between the excipients that raised the solution pH above the pK a to those that did not. For the excipients raising the pH above the pKa, the effect on intrinsic dissolution rate was not as high as that expected from the change in drug solubility. It was postulated that this might be due to lack of penetration of the excipient into the drug boundary layer microenvironment. Formulators may calculate the effect of adding an excipient based on solubility increases but may not find the dissolution rate improvement expected. Copyright © 2005 Taylor & Francis Inc.

Effect of osmotic and matrix potential on Saprolegnia diclina and S. ferax

Growth of biomass and sporulation of pathogenic and non-pathogenic Saprolegnia species was markedly decreased at reduced water potentials. Oogonium and zoosporangium formation were more sensitive to reduced osmotic and matrix potentials than growth in biomass. Although little difference was observed between the effects of matrix and osmotic potentials, the Saprolegnia species investigated responded differently to those solutes utilized in control of osmotic potential. Biomas, oogonium and zoosporangium formation were greater in the presence of reduced osmotic potentials mediated by mannitol than equivalent potentials mediated by potassium chloride. Endogenous potassium levels varied little with reduced matrix or osmotic potentials. Conversly, mannitol content of colonies exposed to reduced osmotic potentials mediated by mannitol initailly increased while endogenous amino acid levels were observed to rise in response to moderately reduced water potentials. Sensitivity of Saprolegnia species to reduced potantials and effects on substrate colonization are discussed in the light of these observations.

Effect of the Hofmeister anions upon the swelling of a self-assembled pH-responsive hydrogel

We report the effect of a range of monovalent sodium salts on the molecular equilibrium swelling of a simple synthetic microphase separated poly(methyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate)-block-poly(methyl methacrylate) (PMMA88-b-PDEA223-b-PMMA88) pH-responsive hydrogel. Sodium acetate, sodium chloride, sodium bromide, sodium iodide, sodium nitrate and sodium thiocyanate were selected for study at controlled ionic strength and pH; all salts are taken from the Hofmeister series (HS). The influence of the anions on the expansion of the hydrogel was found to follow the reverse order of the classical HS. The expansion ratio of the gel measured in solutions containing the simple sodium halide salts (NaCl, NaBr, and NaI) was found to be strongly related to parameters which describe the interaction of the ion with water; surface charge density, viscosity coefficient, and entropy of hydration. A global study which also included nonspherical ions (NaAce, NaNO3 and NaSCN) showed the strongest correlation with the viscosity coefficient. Our results are interpreted in terms of the Collins model,(1) where larger ions have more mobile water in the first hydration cage immediately surrounding the gel, therefore making them more adhesive to the surface of the stationary phase of the gel and ultimately reducing the level of expansion.

Dipole moments and Kerr effect of poly(n-vinylcarbazole) and its complexes with trinitrofluorenone

N-vinylcarbazole was polymerised using the free radical catalyst (azo-bisisobutyronitrile) and cationic catalysts (boron-trifluoride etherate and aluminium chloride). The polymers produced were characterised by molecular weight measurements and powder x-ray diffraction. The tacticity of the polymer samples was determined using proton and carbon-13 nuclear magnetic resonance spectroscopy. Measurements of their static dielectric permittivity and electro-optical birefringence (Kerr effect) in solution in 1,4-dioxane were carried out over a range of temperatures. The magnitudes of the dipole moments and Kerr constants were found to vary with changes in the tacticity of poly(N-vinylcarbazole). The results of these measurements support the view that the stereostructure of poly(N-vinylcarbazole) is sensitive to the mechanism of polymerisation. These results, together with proton and carbon-13 N.M.R. data, are discussed in terms of the possible conformations of the polymer chains and the relative orientation of the bulky carbazole side groups. The dielectric and molecular Kerr effect studies have also been carried out on complexes formed between 2,4,7-trinitro-9-fluorenone (TNF) and different stereoregular forms of poly(N-vinylcarbazole) in solution in 1,4-dioxane. The differences in the molar Kerr constants between pure (uncomplexed) and complexed poly(N-vinylcarbazole) samples were attributed to changes in optical anisotropy and dipole moments. A molecular modelling computer program Desktop Molecular Modeller was used to examine the 3/1 helical isotactic and 2/1 helical syndiotactic forms of poly(N-vinylcarbazole). These models were used to calculate the pitch distances of helices and the results were interpreted in terms of van der Waal's radii on TNF. This study indicated that the pitch distance in 3/1 isotactic helices was large enough to accommodate the bulky TNF molecules to form sandwich type charge transfer complexes whereas the pitch distance in syndiotactic poly(N-vinylcarbazole) was smaller and would not allow a similar type of complex formation.

Effect of pulsed current on the electrodeposition of chromium and copper

This research was concerned with the effects of pulsed current on the electrodeposition of chromium and copper. In the case of the latter metal, a novel application has been studied and a theory proposed for the ability to improve throwing power by the joint use of organic additives and pulsed reverse current. During the course of the research, several improvements were made to the pulse plating unit.Chromium. A study was made of the effect of square wave pulsed current on various physical properties of deposits from three hard chromium plating electrolytes. The effect of varying frequency at a duty cycle of 50% on the mean bulk internal stress, visual appearance, hardness, crack characteristics and surface topography of the electrodeposits was determined. X-ray diffraction techniques were used to study the phases present in the deposits. The effect of varying frequency on the cathodic efficiencies of the electrolytes was also determined. It was found that pulsed current reduced the internal stress of deposits from the sulphate catalysed electrolyte. It also reduced or eliminated cracking of deposits and reduced deposit brightness. Under certain conditions, pulsed current was found to induce the co-deposition of hydrides of chromium. Deposit hardness was found to be reduced by the use of pulsed current. Cathodic efficiencies of the high efficiency electrolytes were reduced by use of pulsed current although this effect was minimised at high frequencies. The sulphate catalysed electrolyte showed an increase in efficiency over the frequency range where hydrides were co-deposited.Copper. The polarisation behaviour of acid copper solutions containing polyethers, sulphopropyl sulphides and chloride ions was studied using both direct and pulse reverse current. The effect of these additives on the rest potentials of copper deposits immersed in the electrolyte was also studied. Hole Throwing Power on printed circuit boards was determined using a specially designed test cell. The effect of pulsed reverse current on the hole throwing power of commercially produced printed circuit boards was also studied. Polyethers were found to have an inhibiting effect on the deposition of copper whereas the sulphopropyl sulphides produced a stimulating (i.e. depolarising) effect. Studies of rest potentials made when both additives were present indicated that the sulphopropyl sulphide was preferentially adsorbed. The use of pulsed reverse current in solutions containing both polyether and sulphopropyl sulphide was found to cause desorption of the sulphopropyl sulphide at the cathode surface. Thus, at higher current densities, the inhibiting effect of the polyether produced an increase in the cathodic polarisation potential. At lower current densities, the depolarisation effect of the sulphopropyl sulphide could still occur. On printed circuit boards, this effect was found to produce an increase in the `hole throwing power' due to depolarisation of the holes relative to the surface of the boards. Typically, using direct current, hole/surface thickness ratios of 40% were obtained when plating 0.6 mm holes in a 3.2 mm thick board at a current density of 3 A/dm2 whereas using pulsed reverse current, ratios of 80% could be obtained at an equivalent rate of deposition. This was observed both in laboratory tests and on commercially plated boards.

Electrochemical chloride extraction to halt corrosion of reinforcement

This thesis presents results of experiments designed to study the effect of applying electrochemical chloride extraction (ECE) to a range of different hardened cement pastes. Rectangular prism specimens of hydrated cement paste containing sodium chloride at different concentrations were subjected to electrolysis between the embedded steel cathodes and external anodes of activated titanium mesh. The cathodic current density used was in the range of 1 to 5 A/m2 with treatment periods of 4 to 12 weeks. After treatment, the specimens were cut into sections which were subjected to pore-solution expression and analysis in order to determine changes in the distribution of free and total ionic species. The effect of the ECE treatment on the physical and microstructural properties of the cements was studied by using microhardness and MIP techniques. XRD was employed to look at the possibility of ettringite redistribution as a result of the accumulation of soluble sulphate ions in the cement matrix near the cathode during ECE. Remigration of chloride which remains after the ECE treatment and distribution of other ions were studied by analysing specimens which had been stored for several months, after undergoing ECE treatment. The potentials of the steel cathodes were also monitored over the period to detect any changes in their corrosion state. The main findings of this research were as follows: 1, ECE, as applied in this investigation, was capable of removing both free and bound chloride. The removal process occurred relatively quickly and an equilibrium between free and bound chlorides in the specimens was maintained throughout. At the same time, alkali concentrations in the pore solution near the steel cathode increased. The soluble sulphate ionic concentration near the cathode also increased due to the local increase in the pH of the pore solution. 2, ECE caused some changes in physical and microstructural of the cement matrix. However these changes were minimal and in the case of microhardness, the results were highly scattered. Ettringite in the bulk material well away from the cathode was found not to increase significantly with the increase in charge passed.3, Remigration of chloride and other ionic species occurred slowly after cessation of ECE with a resultant gradual increase in the Cl-/OH- ratio around the steel.4, The removal of chloride from blended cements was slower than that from OPC.

Effect of poor curing conditions and remedies on the durability of steel in concrete

An investigation was undertaken to study the effect of poor curing simulating hot climatic conditions and remedies on the durability of steel in concrete. Three different curing environments were used i.e. (1) Saturated Ca(OH)2 solution at 20°C, (2) Saturated Ca(OH)2 solution at 50°C and (3) Air at 50°C at 30% relative humidity. The third curing condition corresponding to the temperature and relative humidity typical of Middle Eastern Countries. The nature of the hardened cement paste matrix, cured under the above conditions was studied by means of Mercury Intrusion Porosimetry for measuring pore size distribution. The results were represented as total pore volume and initial pore entry diameter. The Scanning Electron Microscope was used to look at morphological changes during hydration, which were compared to the Mercury Intrusion Porosimetry results. X-ray defraction and Differential Thermal Analysis techniques were also employed for looking at any phase transformations. Polymer impregnation was used to reduce the porosity of the hardened cement pastes, especially in the case of the poorly cured samples. Carbonation rates of unimpregnated and impregnated cements were determined. Chloride diffusion studies were also undertaken to establish the effect of polymer impregnation and blending of the cements. Finally the corrosion behaviour of embedded steel bars was determined by the technique of Linear Polarisation. The steel was embedded in both untreated and polymer impregnated hardened cement pastes placed in either a solution containing NaCl or an environmental cabinet which provided carbonation at 40°C and 50% relative humidity.

Aspects of the prevention and repair of chloride-induced corrosion of steel in concrete

Sodium formate, potassium acetate and a mixture of calcium and magnesium acetate (CMA) have all been identified as effective de-icing agents. In this project an attempt has been made to elucidate potentially deleterious effects of these substances on the durability of reinforced concrete. Aspects involving the corrosion behaviour of embedded steel along with the chemical and physical degradation of the cementitious matrix were studied. Ionic diffusion characteristics of deicer/pore solution systems in hardened cement paste were also studied since rates of ingress of deleterious agents into cement paste are commonly diffusion-controlled. It was found that all the compounds tested were generally non-corrosive to embedded steel, however, in a small number of cases potassium acetate did cause corrosion. Potassium acetate was also found to cause cracking in concrete and cement paste samples. CMA appeared to degrade hydrated cement paste although this was apparently less of a problem when commercial grade CMA was used in place of the reagent grade chemical. This was thought to be due to the insoluble material present in the commercial formulation forming a physical barrier between the concrete and the de-icing solution. With the test regimes used sodium formate was not seen to have any deleterious effect on the integrity of reinforced concrete. As a means of restoring the corrosion protective character of chloride-contaminated concrete the process of electrochemical chloride removal has been previously developed. Potential side-effects of this method and the effect of external electrolyte composition on chloride removal efficiency were investigated. It was seen that the composition of the external electrolyte has a significant effect on the amount of chloride removed. It was also found that, due to alterations to the composition of the C3A hydration reaction products, it was possible to remove bound chloride as well as that in the pore solution. The use of an external electrolyte containing lithium ions was also tried as a means of preventing cathodically-induced alkali-silica reaction in concretes containing potentially reactive aggregates. The results obtained were inconclusive and further practical development of this approach is needed.

Protein-protein interactions in ovalbumin solutions studied by small angle scattering: effect of ionic strength, and the chemical nature of cations

The influence of ionic strength and of the chemical nature of cations on the protein-protein interactions in ovalbumin solution was studied using small-angle X-ray and neutron scattering (SAXS/SANS). The globular protein ovalbumin is found in dimeric form in solutions as suggested by SANS/SAXS experiments. Due to the negative charge of the proteins at neutral pH, the protein-protein interactions without any salt addition are dominated by electrostatic repulsion. A structure factor related to screened Coulombic interactions together with an ellipsoid form factor was used to fit the scattering intensity. A monovalent salt (NaCl) and a trivalent salt (YCl3) were used to study the effect of the chemical nature of cations on the interaction in protein solutions. Upon addition of NaCl, with ionic strength below that of physiological conditions (150 mM), the effective interactions are still dominated by the surface charge of the proteins and the scattering data can be understood using the same model. When yttrium chloride was used, a reentrant condensation behavior, i.e., aggregation and subsequent redissolution of proteins with increasing salt concentration, was observed. SAXS measurements reveal a transition from effective repulsion to attraction with increasing salt concentration. The solutions in the reentrant regime become unstable after long times (several days). The results are discussed and compared with those from bovine serum albumin (BSA) in solutions.

Longitudinal dispersion in spiral wound RO modules and its effect on the performance of batch mode RO operations

Operation of reverse osmosis (RO) in cyclic batch mode can in principle provide both high energy efficiency and high recovery. However, one factor that causes the performance to be less than ideal is longitudinal dispersion in the RO module. At the end of the batch pressurisation phase it is necessary to purge and then refill the module. During the purge and refill phases, dispersion causes undesirable mixing of concentrated brine with less concentrated feed water, therefore increasing the salt concentration and energy usage in the subsequent pressurisation phase of the cycle. In this study, we quantify the significance of dispersion through theory and experiment. We provide an analysis that relates the energy efficiency of the batch operation to the amount of dispersion. With the help of a model based on the analysis by Taylor, dispersion is quantified according to flow rate. The model is confirmed by experiments with two types of proprietary spiral wound RO modules, using sodium chloride (NaCl) solutions of concentration 1000 to 20,000 ppm. In practice the typical energy usage increases by 4% to 5.5% compared to the ideal case of zero dispersion.

Effect of calcium source on structure and properties of sol-gel derived bioactive glasses

The aim was to determine the most effective calcium precursor for synthesis of sol-gel hybrids and for improving homogeneity of sol-gel bioactive glasses. Sol-gel derived bioactive calcium silicate glasses are one of the most promising materials for bone regeneration. Inorganic/organic hybrid materials, which are synthesized by incorporating a polymer into the sol-gel process, have also recently been produced to improve toughness. Calcium nitrate is conventionally used as the calcium source, but it has several disadvantages. Calcium nitrate causes inhomogeneity by forming calcium-rich regions, and it requires high temperature treatment (>400 C) for calcium to be incorporated into the silicate network. Nitrates are also toxic and need to be burnt off. Calcium nitrate therefore cannot be used in the synthesis of hybrids as the highest temperature used in the process is typically 40-60 C. Therefore, a different precursor is needed that can incorporate calcium into the silica network and enhance the homogeneity of the glasses at low (room) temperature. In this work, calcium methoxyethoxide (CME) was used to synthesize sol-gel bioactive glasses with a range of final processing temperatures from 60 to 800 C. Comparison is made between the use of CME and calcium chloride and calcium nitrate. Using advanced probe techniques, the temperature at which Ca is incorporated into the network was identified for 70S30C (70 mol % SiO, 30 mol % CaO) for each of the calcium precursors. When CaCl was used, the Ca did not seem to enter the network at any of the temperatures used. In contrast, Ca from CME entered the silica network at room temperature, as confirmed by X-ray diffraction, Si magic angle spinning nuclear magnetic resonance spectroscopy, and dissolution studies. CME should be used in preference to calcium salts for hybrid synthesis and may improve homogeneity of sol-gel glasses.