An investigation of the factor-analytic approach to the determination of abilities involved in psychomotor learning

This research began with an attempt to solve a practical problem, namely, the prediction of the rate at which an operator will learn a task. From a review of the literature, communications with researchers in this area and the study of psychomotor learning in factories it was concluded that a more fundamental approach was required which included the development of a task taxonomy. This latter objective had been researched for over twenty years by E. A. Fleishman and his approach was adopted. Three studies were carried out to develop and extend Fleishman's approach to the industrial area. However, the results of these studies were not in accord with FIeishman's conclusions and suggested that a critical re-assessment was required of the arguments, methods and procedures used by Fleishman and his co-workers. It was concluded that Fleishman's findings were to some extent an artifact of the approximate methods and procedures which he used in the original factor analyses and that using the more modern computerised factor analytic methods a reliable ability taxonomy could be developed to describe the abilities involved in the learning of psychomotor tasks. The implications for a changing-task or changing-subject model were drawn and it was concluded that a changing task and subject model needs to be developed.

Use of ultrasonic agitation in iron group alloy electrodepositions

The effects of ultrasonic agitation on deposition from two iron group alloy plating solutions, nickel-cobalt and bright nickel-iron, have been studied. Comparison has been made with deposits plated from the same solutions using controlled air agitation. The ultrasonic equipment employed had a fixed frequency of 13 KHz but the power output from each transducer was variable up to a maximum of 350 watts. The effects of air and ultrasonic agitation on hardness, ductility, tensile strength, composition, structure, surface topography, limiting current density, cathode current efficiency and macro-throwing power were determined. Transmission and scanning electron microscopy, electron-probe microanalysis and atomic absorption spectrophotometry have been employed to study the nickel alloy deposits produced. The results obtained show that the use of Ultrasonics increased significantly the hardness of both alloy deposits and altered their composition by decreasing the cobalt and iron contents from nickel-cobalt and nickeliron solutions respectively. The ductility of coatings improved but the tensile strength did not change very much. Ultrasonic agitation gave larger grained deposits than air and they seemed to have a lower stress. Dull cobalt-nickel deposits had a similar pyramidal surface topography regardless of the type of agitation but the bright appearance of the nickel-iron was destroyed by ultrasonic agitation; an unusual ribbed pattern was produced. The use of ultrasonic agitation permitted approximately a twofold increase in the plating current density at which sound deposits could be achieved but there was only a slight increase in cathode current efficiency. Macro-throwing power of the solutions was increased slightly by the use of ultrasonic agitation. ultrasonic agitation is an expensive means of agitating plating Solutions and would be worthwhile only if significant improvements in properties could be achieved. The simultaneous improvement in hardness and ductility is a novel feature that should have useful engineering applications.

Efficacy of memantine for agitation in Alzheimer's dementia:a randomised double-blind placebo controlled trial

Background - Agitation in Alzheimer’s disease (AD) is common and associated with poor patient life-quality and carer distress. The best evidence-based pharmacological treatments are antipsychotics which have limited benefits with increased morbidity and mortality. There are no memantine trials in clinically significant agitation but post-hoc analyses in other populations found reduced agitation. We tested the primary hypothesis, memantine is superior to placebo for clinically significant agitation, in patients with moderate-to-severe AD. Methods and Findings - We recruited 153 participants with AD and clinically significant agitation from care-homes or hospitals for a double-blind randomised-controlled trial and 149 people started the trial of memantine versus placebo. The primary outcome was 6 weeks mixed model autoregressive analysis of Cohen-Mansfield Agitation Inventory (CMAI). Secondary outcomes were: 12 weeks CMAI; 6 and 12 weeks Neuropsychiatric symptoms (NPI), Clinical Global Impression Change (CGI-C), Standardised Mini Mental State Examination, Severe Impairment Battery. Using a mixed effects model we found no significant differences in the primary outcome, 6 weeks CMAI, between memantine and placebo (memantine lower -3.0; -8.3 to 2.2, p = 0.26); or 12 weeks CMAI; or CGI-C or adverse events at 6 or 12 weeks. NPI mean difference favoured memantine at weeks 6 (-6.9; -12.2 to -1.6; p = 0.012) and 12 (-9.6; -15.0 to -4.3 p = 0.0005). Memantine was significantly better than placebo for cognition. The main study limitation is that it still remains to be determined whether memantine has a role in milder agitation in AD. Conclusions - Memantine did not improve significant agitation in people with in moderate-to-severe AD. Future studies are urgently needed to test other pharmacological candidates in this group and memantine for neuropsychiatric symptoms.

Agitation conditions for the culture and detachment of hMSCs from microcarriers in multiple bioreactor platforms

In our recent work in different bioreactors up to 2.5L in scale, we have successfully cultured hMSCs using the minimum agitator speed required for complete microcarrier suspension, N JS. In addition, we also reported a scaleable protocol for the detachment from microcarriers in spinner flasks of hMSCs from two donors. The essence of the protocol is the use of a short period of intense agitation in the presence of enzymes such that the cells are detached; but once detachment is achieved, the cells are smaller than the Kolmogorov scale of turbulence and hence not damaged. Here, the same approach has been effective for culture at N JS and detachment in-situ in 15mL ambr™ bioreactors, 100mL spinner flasks and 250mL Dasgip bioreactors. In these experiments, cells from four different donors were used along with two types of microcarrier with and without surface coatings (two types), four different enzymes and three different growth media (with and without serum), a total of 22 different combinations. In all cases after detachment, the cells were shown to retain their desired quality attributes and were able to proliferate. This agitation strategy with respect to culture and harvest therefore offers a sound basis for a wide range of scales of operation.

Liposomes:Formulation and characterisation as contrast agents and as vaccine delivery systems

Liposome systems are well reported for their activity as vaccine adjuvants; however novel lipid-based microbubbles have also been reported to enhance the targeting of antigens into dendritic cells (DCs) in cancer immunotherapy (Suzuki et al 2009). This research initially focused on the formulation of gas-filled lipid coated microbubbles and their potential activation of macrophages using in vitro models. Further studies in the thesis concentrated on aqueous-filled liposomes as vaccine delivery systems. Initial work involved formulating and characterising four different methods of producing lipid-coated microbubbles (sometimes referred to as gas-filled liposomes), by homogenisation, sonication, a gas-releasing chemical reaction and agitation/pressurisation in terms of stability and physico-chemical characteristics. Two of the preparations were tested as pressure probes in MRI studies. The first preparation composed of a standard phospholipid (DSPC) filled with air or nitrogen (N2), whilst in the second method the microbubbles were composed of a fluorinated phospholipid (F-GPC) filled with a fluorocarbon saturated gas. The studies showed that whilst maintaining high sensitivity, a novel contrast agent which allows stable MRI measurements of fluid pressure over time, could be produced using lipid-coated microbubbles. The F-GPC microbubbles were found to withstand pressures up to 2.6 bar with minimal damage as opposed to the DSPC microbubbles, which were damaged at above 1.3 bar. However, it was also found that DSPC-filled with N2 microbubbles were also extremely robust to pressure and their performance was similar to that of F-GPC based microbubbles. Following on from the MRI studies, the DSPC-air and N2 filled lipid-based microbubbles were assessed for their potential activation of macrophages using in vitro models and compared to equivalent aqueous-filled liposomes. The microbubble formulations did not stimulate macrophage uptake, so studies thereafter focused on aqueous-filled liposomes. Further studies concentrated on formulating and characterising, both physico-chemically and immunologically, cationic liposomes based on the potent adjuvant dimethyldioctadecylammonium (DDA) and immunomodulatory trehalose dibehenate (TDB) with the addition of polyethylene glycol (PEG). One of the proposed hypotheses for the mechanism behind the immunostimulatory effect obtained with DDA:TDB is the ‘depot effect’ in which the liposomal carrier helps to retain the antigen at the injection site thereby increasing the time of vaccine exposure to the immune cells. The depot effect has been suggested to be primarily due to their cationic nature. Results reported within this thesis demonstrate that higher levels of PEG i.e. 25 % were able to significantly inhibit the formation of a liposome depot at the injection site and also severely limit the retention of antigen at the site. This therefore resulted in a faster drainage of the liposomes from the site of injection. The versatility of cationic liposomes based on DDA:TDB in combination with different immunostimulatory ligands including, polyinosinic-polycytidylic acid (poly (I:C), TLR 3 ligand), and CpG (TLR 9 ligand) either entrapped within the vesicles or adsorbed onto the liposome surface was investigated for immunogenic capacity as vaccine adjuvants. Small unilamellar (SUV) DDA:TDB vesicles (20-100 nm native size) with protein antigen adsorbed to the vesicle surface were the most potent in inducing both T cell (7-fold increase) and antibody (up to 2 log increase) antigen specific responses. The addition of TLR agonists poly(I:C) and CpG to SUV liposomes had small or no effect on their adjuvanticity. Finally, threitol ceramide (ThrCer), a new mmunostimulatory agent, was incorporated into the bilayers of liposomes composed of DDA or DSPC to investigate the uptake of ThrCer, by dendritic cells (DCs), and presentation on CD1d molecules to invariant natural killer T cells. These systems were prepared both as multilamellar vesicles (MLV) and Small unilamellar (SUV). It was demonstrated that the IFN-g secretion was higher for DDA SUV liposome formulation (p<0.05), suggesting that ThrCer encapsulation in this liposome formulation resulted in a higher uptake by DCs.

Mass transfer characteristics of two-aqueous-phase liquid-liquid mixtures

Mass transfer rates were studied using the falling drop method. Cibacron Blue 3 GA dye was the transferring solute from the salt phase to the PEG phase. Measurements were undertaken for several concentrations of the dye and the phase-forming solutes and with a range of different drop sizes, e.g. 2.8, 3.0 and 3.7 mm. The dye was observed to be present in the salt phase as finely dispersed solids but a model confirmed that the mass transfer process could still be described by an equation based upon the Whitman two-film model. The overall mass transfer coefficient increased with increasing concentration of the dye. The apparent mass transfer coefficient ranged from 1 x 10-5 to 2 x 10 -4 m/s. Further experiments suggested that mass transfer was enhanced at high concentration by several mechanisms. The dye was found to change the equilibrium composition of the two phases, leading to transfer of salt between the drop and continuous phases. It also lowered the interfacial tension (i.e. from 1.43 x 10-4 N/m for 0.01% w/w dye concentration to 1.07 x 10-4 N/m for 0.2% w/w dye concentration) between the two phases, which could have caused interfacial instabilities (Marangoni effects). The largest drops were deformable, which resulted in a significant increase in the mass transfer rate. Drop size distribution and Sauter mean drop diameter were studied on-line in a 1 litre agitated vessel using a laser diffraction technique. The effects of phase concentration, dispersed phase hold-up and impeller speed were investigated for the salt-PEG system. An increase in agitation speed in the range 300 rpm to 1000 rpm caused a decrease in mean drop diameter, e.g. from 50 m to 15 m. A characteristic bimodal drop size distribution was established within a very short time. An increase in agitation rate caused a shift of the larger drop size peak to a smaller size.

NMR spectroscopy in the presence of ultrasound and other perturbations

The work described in this thesis has been concerned with exploring the potential uses of ultrasound in Nuclear Magnetic Resonance (NMR) spectroscopy, The NMR spectra of liquids provide detailed structural information that may be deduced from the chemical shifts and spin-spin coupling, that are evident in the narrow resonances, arising from some of the nuclear broadening interactions being reduced to zero. In the solid state, all of the nuclear broadening interactions are present and broad lines in the NMR spectrum are observed. Current techniques employed to reduce the line widths in solids are based on coherent averaging techniques such as MAS NMR1,2 which can remove first order interactions. Recently DOR3 and DAS4 have become available to remove higher order interactions. SINNMR (Sonically Induced Narrowing of the NMR spectra of solids) has been reported by Homer et al5 and developed by Homer and Howard6 to reduce the line widths of solids. The basis of their work is the proposal that a colloidal suspension of solid particles can be made to move like large molecules by using ultrasonic agitation. The advantage of the technique is that the particles move incoherently removing all of the nuclear interactions responsible for broad lines. This thesis describes work on the extension of SINNMR by showing that the line width of 27AI and 11B for the glass Na20/B203/AI203 can be reduced by placing solid particles in a colloidal suspension. Further line width reduction is possible by applying ultrasound, at 2 MHz, of sufficient intensity. It is proposed that a cavitation field is responsible for imparting sufficient rotational motion to the solid particles to partially average the nuclear interactions responsible for broad lines. Rapid stirring of the colloidal suspension generates turbulent flow, however, the motion is insufficient to narrow the line widths for 27AI in the glass. Investigations of sonochemical reactions for in situ rate measurements by NMR have been made. 8y using the Weissler reaction7, it has been shown that ultrasonic cavitation is possible up to 10MHz. Preliminary studies have been carried out into the rate of ultrasonic polymerisation of methylmethacrylate by NMR. Long range order in liquid crystals can imposed when they are aligned in the presence a magnetic field. The degree of alignment can be monitored by NMR using, for example a deuterated solute added to the liquid crystal8. Ultrasonic streaming can then be employed to deflect the directors of the liquid crystal from their equilibrium position, resulting in a change In the NMR spectrum. The angle of deflection has been found for the thermotropic liquid crystal (I35) to be ca, 35° and for the lyotropic (ZLI-1167) to be ca, 20°, Mechanical stirring can used to re- orientate the liquid crystal but was found to give a smaller deflection, In a separate study, that did not use ultrasound, it has been found that the signal to noise ratio of 13C NMR signals can be enhanced by rapidly stirring a Iiquid. Accelerating the diffusion of nuclei out of the coil region enables M0 to be re-established more rapidly than the normal relaxation process. This allows the pulse repetition rate to be reduced without saturating the spin system. The influence of varying the relaxation delay, acquisition time and inter-pulse delay have been studied and parameters optimised. By studying cholesterol the technique was found to be most effective for nuclei with long relaxation times, such as quaternary carbon sites. Key Worde: NMR, Ulf.rasciund, 1,.lqi.fi!:l cryllltalt!h SCll1C1otlemlstryl I!r1hano~d algnflllf

Fermentation methods for dextransucrase production

Several fermentation methods for the production of the enzyme dextransucrase have been employed. The theoretical aspects of these fermentation techniques have been given in the early chapters of this thesis together with a brief overview of enzyme biotechnology. A literature survey on cell recycle fermentation has been carried out followed by a survey report on dextransucrase production, purification and the reaction mechanism of dextran biosynthesis. The various experimental apparatus as employed in this research are described in detail. In particular, emphasis has been given to the development of continuous cell recycle fermenters. On the laboratory scale, fed-batch fermentations under anaerobic low agitation conditions resulted in dextransucrase activities of about 450 DSU/cm3 which are much higher than the yields reported in the literature and obtained under aerobic conditions. In conventional continuous culture the dilution rate was varied in the range between 0.375 h-1 to 0.55 h-1. The general pattern observed from the data obtained was that the enzyme activity decreased with increase in dilution rate. In these experiments the maximum value of enzyme activity was ∼74 DSU/cm3. Sparging the fermentation broth with CO2 in continuous culture appears to result in a decrease in enzyme activity. In continuous total cell recycle fermentations high steady state biomass levels were achieved but the enzyme activity was low, in the range 4 - 27 DSU/cm3. This fermentation environment affected the physiology of the microorganism. The behaviour of the cell recycle system employed in this work together with its performance and the factors that affected it are discussed in the relevant chapters. By retaining the whole broth leaving a continuous fermenter for between 1.5 - 4 h under controlled conditions, the enzyme activity was enhanced with a certain treatment from 86 DSU/cm3 to 180 DSU/cm3 which represents a 106% increase over the enzyme activity achieved by a steady-state conventional chemostat. A novel process for dextran production has been proposed based on the findings of this latter part of the experimental work.

BTX extraction by sulfolane in a mixer-settler cascade

The literature relating to the extraction of the aromatics, benzene, toluene and xylene (BTX) using different commercial solvents, and to mixer-settler design and performance, has been reviewed. Liquid-liquid equilibria of the ternary systems: hexane-benzene-sulfolane, n-heptane-toluene-sulfolane, and octane-xylene-sulfolane were determined experimentally at temperatures of 30oC, 35oC, and 40oC. The work was then extended to a multicomponent system. The data were correlated by using Hand's method and were found to be in a good agreement with theoretical predictions using the UNIFAC method. A study was made of the performance of a 10-stage laboratory mixer-settler cascade for the extraction of BTX from a synthetic reformate utilizing sulfolane as a solvent. Murphree stage efficiency decreased with stage number but 99% extraction was achievable within 4 stages. The effects of temperature, phase ratio, and agitator speed were investigated. The efficiency increased with agitator speed but > 1050 rpm resulted in secondary haze formation. An optimum temperature of 30oC was selected from the phase equilibria; the optimum solvent: feed ratio was 3:1 for 4 stages. The experimental overall mass transfer coefficients were compared with those predicted from single drop correlations and were in all cases greater, by a factor of 1.5 to 3, due to the surface renewal associated with drop break-up and coalescence promoted by agitation. A similar investigation was performed using real reformate from the Kuwait Oil Company. The phase ratios were in the range 0.5 to 1 to 3.25 to 1, the agitator speed 1050 rpm, and the operating temperature 30oC. A maximum recovery of 99% aromatics was achieved in 4 stages at a phase ratio of 3.25 to 1. A backflow model was extended to simulate conditions in the mixer-settler cascade with this multicomponent system. Overall mass transfer coefficients were estimated by obtaining the best fit between experimental and predicted concentration profiles. They were up to 10% greater than those with the synthetic feed but close agreement was not possible because the distribution coefficient and phase ratio varied with stage number. Sulfolane was demonstrated to be an excellent solvent for BTX recovery and a mixer-settler cascade was concluded to be a technically viable alternative to agitated columns for this process.

The production of the enzyme dextransucrase by batch and continuous fermentation techniques

A review of the literature of work carried out on dextransucrase production, purification, immobilization and reactions has been carried out. A brief review has also been made of the literature concerning general enzyme biotechnology and fermentation technology. Fed-batch fermentation of the bacteria Leuconostoc mesenteroides NRRL B512 (F) to produce dextransucrase has formed the major part of this research. Aerobic and anaerobic fermentations have been studied using a 16 litre New Brunswick fermenter which has a 3-12 litre working volume. The initial volume of broth used in the studies was 6 litres. The results of the fed-batch fermentations showed for the first time that yields of dextransucrase are much higher under the anaerobic conditions than during the aerobic fermentations. Dextransucrase containing 300-350 DSU/cm3 of enzyme activity has been obtained during the aerobic fermentations, while in the anaerobic fermentations, enzyme yields containing 450-500 DSU/cm3 have been obtained routinely. The type of yeast extract used in the fermentation medium has been found to have significant effects on enzyme yield. Of the different types studied, the Gistex Standard was found to be the type that favoured the highest enzyme production. Studies have also been carried out on the effect of agitation rate and antifoam on the enzyme production during the anaerobic experiments. Agitation rates of up to 600 rpm were found not to affect the enzyme yield, however, the presence of antifoam in the medium led to a significant reduction in enzyme activity (less than 300 DSU/cm3). Scale-up of the anaerobic fermentations has been performed at up to the 1000 litre level with enzyme yields containing more than 400 DSU/cm3 of activity being produced. Some of the enzyme produced at this scale was used for the first time to produce dextran on an industrial scale via the enzyme route, with up to 99% conversion of sucrose to dextran being obtained. An attempt has been made at continuous dextransucrase production. Cell washout was observed to occur at dilution rates of greater than 0.4 h-1. Dextransucrase containing up to 25 DSU/cm3/h has been produced continuously.

Inhibition of microbial colonization of shipboard fuel systems

The aim of the investigation was to study the problem of colonization of shipboard fuel systems and to examine the effect of a number of environmental factors on microbial growth and survival in order to find potential preservative treatments. A variety of microbial species were isolated from samples taken from fuel storage tanks. Bacteria were more numerous than yeasts or fungi and most microorganisms were found at the fuel/water interface. 1he salinity, pH and phosphate concentration of some water bottoms were characteristic of sea water. Others were brackish, acidic and varied in phosphate content. Microorganisms were cultured under a number of environmental conditions. After prolonged incubation, the inoculum size had no effect on the final biomass of Cladosporium resinae but the time required to achieve the final mass decreased with increasing spore number. Undecane supported better growth of the fungus than diesel fuel and of four types of diesel fuel, two allowed more profuse growth. With sea water as the aqueous phase, a number of isolates were inhibited but the addition of nutrients allowed the development of many of the organisms. Agitation increased the growth of C. resinae on glucose but inhibited it on hydrocarbons. The optimum temperature fgr growth of C. resinae on surface culture lay between 25º C and 30º C and growth was evident at 5º C but not at 45º C. In aqueous suspension, 90% of spores were inactivated in around 60 hours at 45ºC and the same proportion of spores of C. resinae and Penicillium corylophilum were destroyed after about 30 seconds at 65ºC. The majority of bacteria and all yeasts in a water bottom sample were killed within 10 seconds at this temperature. An increase in the concentration of an organo-boron compound caused more rapid inactivation of C. resinae spores and raising the temperature from 25ºC to 45°C significantly enhanced the potency of the biocide.

The postantibiotic effect of the carbapenem antibiotics on gram-negative bacteria

Postantibiotic effect (PAE) describes the suppression of microbial growth occurring after a short exposure to an antimicrobial agent. PAE appears to be a property of the majority of antimicrobial agents and is demonstrated by a wide variety of microorganisms. At present, carbapenems and penems are the only members of the -lactam group of antimicrobial agents that exhibit a significant PAE on Gram-negative bacilli. A standardised method was developed to evaluate the in vitro PAE of three carbapenems; imipenem, meropenem and biapenem on Gram-negative bacteria under reproducible laboratory conditions that partially mimicked those occurring in vivo. The effects on carbapenem PAE of the method of antimicrobial removal, concentration, exposure duration, inoculum size, inoculum growth phase, multiple exposures and pooled human serum were determined. Additionally, the reproducibility, susceptibility prior to and after PAE determination and inter-strain variation of carbapenem PAE were evaluated. The method developed determined PAE by utilising viable counts and demonstrated carbapenem PAE to be reproducible, constant over successive exposures, dependent on genera, concentration, duration of exposure, inoculum size and growth phase. In addition, carbapenem PAE was not significantly effected either by agitation, the antimicrobial removal method or the viable count diluent. At present, the mechanism underlying PAE is undetermined. It is thought to be due to either the prolonged persistence of the antimicrobial at the cellular site of action or the true recovery period from non-lethal damage. Increasing the L-lysine concentration and salinity at recovery decreased and increased the carbapenem and imipenem PAE of Pseudomonas aeruginosa, respectively. In addition, no apparent change was observed in the production of virulence factors by P.aeruginosa in PAE phase. However, alterations in cell morphology were observed throughout PAE phase, and the reappearance of normal cell morphology corresponded to the duration of PAE determined by viable count. Thus, the recovery of the penicillin binding protein target enzymes appears to be the mechanism behind carbapenem PAE in P. aeruginosa.

The use of anticholinergic agents to treat excessive oropharyngeal and tracheal secretions in palliative care

Palliative care involves a multi-professional team approach to the provision of active, holistic care for patients and their families when the patient's disease is no longer responsive to curative treatment. Patient care encompasses medical and pharmacological intervention for symptom control, together with psychological, spiritual and social support for patients and families. Care is provided by teams in hospice, hospital or community environments. Although traditionally associated with providing care for cancer patients, palliative care services are increasingly providing for patients with non-malignant disease. Symptoms commonly associated with terminal phase of disease include pain, nausea, agitation, respiratory symptoms and general fatigue. During the last few days of life, patients may become weak, resulting in difficulty taking oral medication and have periods of unconsciousness. Some patients may require drug administration via subcutaneous infusion. A proportion of patients may develop difficulty clearing respiratory secretions causing a characteristic ‘death rattle’, which although not generally considered to be distressing for the patient, is often treated with a variety of anticholinergic drugs in an attempt to reduce the ‘noisy breathing’ for the benefit of relatives and others who may be closely associated with the patient.This study examined treatment of death rattle in two Hospices focusing on objective and subjective outcome measures in order to determine the efficacy of anticholinergic regimens in current use. Qualitative methods were employed to elicit attitudes of professionals and carers working closely with the patient. The number of patients recruited and monitored were small, many confounding factors were identified which questioned firstly the clinical rationale for administering anticholinergic drugs routinely to treat death rattle and secondly, the ethics of administering drug regimens to patients to treat death rattle with the primary aim of relieving distress for others. Ethnical issues, including those of consent are discussed in relation to their impact on the methodology of end of life studies in medicines management in palliative care.

Electrodeposition of corrosion resistant zinc alloy coatings

With the increase use of de-icing salts on roads for safety, the need for improved corrosion resistance of the traditional galvanized automobile bodies has never been greater. In the present work, Zn alloy coatings (Zn-Ni and Zn-Co) were studied as an alternative to pure Zn coatings. The production of these deposits involved formulation of various acidic (pH of about 5.5) chloride based solutions. These showed anomalous deposition, that is, alloys were deposited much more easily than expected from the noble behaviour of Ni and Co metals. Coating compositions ranging from 0 to about 37% Ni and 20% Co were obtained. The chemical composition of the coatings depended very much on the electrolytes nature and operating conditions. The Ni content of deposits increased with increase in Ni bath concentration, temperature, pH and solution agitation but decreased considerably with increase in current density. The throwing power of the Zn-Ni solution deteriorated as Ni metal bath concentration increased. The Co content of deposits also increased with increase in Co bath concentration and temperature, and decreased with increase in current density. However, the addition of commercial organic additives to Zn-Co plating solutions suppressed considerably the amount of Co in the coatings. The Co content of deposits plated from Zincrolyte solution was found to be more sensitive to variation in current density than in the case of deposits plated from the alkaline Canning solution. The chromating procedures were carried out using laboratory formulated solution and commercially available ones. The deposit surface state was of great significance in influencing the formulation of conversion coatings. Bright and smooth deposits acquired an iridescent colour when treated with the laboratory formulated solution. However, the dull deposits acquired a brownish appearance. The correlation between the electrochemical test results and the neutral salt spray in marine environment was good. Non-chromated Zn-Ni coatings containing about 11-14% Ni increased in corrosion resistance compared to pure Zn. Non-chromated Zn-Co deposits of composition 4-8% were required to show a significant improvement in corrosion resistance Corrosion resistance was improved considerably by conversion coating. However, the type of conversion coating was very important. Samples treated in a laboratory solution performed badly compared to those treated in commercial solutions. Zn alloy coatings were superior to pure Zn, the Schloetter sample (13.8% Ni) had the lowest corrosion rate, followed by the Canning sample (1.0% Co) and then Zincrolyte (0.3% Co).Neither the chromium content of the conversion films nor the chromium state was found to have an effect on corrosion performance of the coatings.

Autocatalytic deposition of composite coatings

The deposition and properties of electroless nickel composite coatings containing graphite, PTFE and chromium were investigated. Solutions were developed for the codeposition of graphite and chromium with electroless nickel. Solutions for the deposition of graphite contained heavy metal ions for stability, with non-ionic and anionic surfactants to provide wetting and dispersion of the particles. Stability for the codeposition of chromium particles was achieved by oxidation of the chromium. Thin oxide layers of 200 nm thick prevented initiation of the electroless reaction onto the chromium. A mechanism for the formation of electroless composite coatings was considered based on the physical adsorption of particles and as a function of the adsorption of charged surfactants and metal cations from solution. The influence of variables such as particle concentration in solution, particle size, temperature, pH, and agitation on the volume percentage of particles codeposited was studied. The volume percentage of graphite codeposited was found to increase with concentration in solution and playing rate. An increase in particle size and agitation reduced the volume percentage codeposited. The hardness of nickel-graphite deposits was found to decrease with graphite content in the as-deposited and heat treated condition. The frictional and wear properties of electroless nickel-graphite were studied and compared to those of electroless nickel-PTFE. The self-lubricating nature of both coatings was found to be dependent on the ratio of coated area to uncoated area, the size and content of lubricating material in the deposit, and the load between contacting surfaces. The mechanism of self-lubrication was considered, concluding that graphite only produced an initial lubricating surface due to the orientation of flakes, unlike PTFE, which produced true self-lubrication throughout the coating life. Heat treatment of electroless nickel chromium deposits at 850oC for 8 and 16 hours produced nickel-iron-chromium alloy deposits with a phosphorus rich surface of high hardness. Coefficients of friction and wear rates were intially moderate for the phosphorus rich layer but increased for the nickel-iron-chromium region of the coating.