Deformation microstructures and recrystallization in heavily worked copper

Deformation microstructures in two batches of commercially pure copper (A and B) of allnost similar composition have been studied after rolling reductions from 5% to 95%. X- ray diffraction, optical metallography, scanning electron microscopy in the back-scattered mode, transmission and scanning electron microscopy have been used to examine the deformation microstructure. At low strains (~10 %) the deformation is accommodated by uniform octahedral slip. Microbands that occur as sheet like features usually on the {111} slip planes are formed after 10% reduction. The misorientations between rnicrobonds ond the matrix are usually small (1 - 2° ) and the dislocations within the bands suggest that a single slip system has been operative. The number of microbands increases with strain, they start to cluster and rotate after 60% reduction and, after 90 %, they become almost perfectly aligned with the rolling direction. There were no detectable differences in deformation microstructure between the two materials up to a deformation level of 60% but subsequently, copper B started to develop shear bands which became very profuse by 90% reduction. By contrast, copper A at this stage of deformation developed a smooth laminated structure. This difference in the deformation microstructures has been attributed to traces of unknown impurity in D which inhibit recovery of work hardening. The preferred orientations of both were typical of deformed copper although the presence of shear bands was associated wth a slightly weaker texture. The effects of rolling temperature and grain size on deformation microstructure were also investigated. It was concluded that lowering the rolling temperature or increasing the initial grain size encourages the material to develop shear bands after heavy deformation. Recovery and recrystallization have been studied in both materials during annealing. During recrystallization the growth of new grains showed quite different characteristics in the two cases. Where shear bands were present these acted as nucleation sites and produced a wide spread of recrystallized grain orientations. The resulting annealing textures were very weak. In the absence of shear bands, nucleation occurs by a remarkably long range bulging process which creates the cube orientation and an intensely sharp annealing texture. Cube oriented regions occur in long bands of highly elongated and well recovered cells which contain long range cumulative micorientations. They are transition bands with structural characteristics ideally suited for nucleation of recrystallization. Shear banding inhibits the cube texture both by creating alternative nuclei and by destroying the microstructural features necessary for cube nucleation.

Multifunctional bioactive glass scaffolds coated with layers of poly(d,l-lactide-co-glycolide) and poly(n-isopropylacrylamide-co-acrylic acid) microgels loaded with vancomycin

A new family of multifunctional scaffolds, incorporating selected biopolymer coatings on basic Bioglass® derived foams has been developed. The polymer coatings were investigated as carrier of vancomycin which is a suitable drug to impart antibiotic function to the scaffolds. It has been proved that coating with PLGA (poly(lactic-co-glycolic acid)) with dispersed vancomycin-loaded microgels provides a rapid delivery of drug to give antibacterial effects at the wound site and a further sustained release to aid mid to long-term healing. Furthermore, the microgels also improved the bioactivity of the scaffolds by acting as nucleation sites for the formation of HA crystals in simulated body fluid. © 2013 Elsevier B.V. All rights reserved.

Precipitation studies on alloys from the system copper chromium zirconium

The precipitation reactions occurring in a series of copper-based alloys selected from the system copper-chromium-zirconium have been studied by resistometric and metallographic techniques. A survey of the factors influencing the development of copper-based alloys for high strength, high conductivity applications is followed by a more general review of contemporary materials, and illustrates that the most promising alloys are those containing chromium and zirconium. The few systematic attempts to study alloys from this system have been collated, discussed, and used as a basis for the selection of four alloy compositions viz:- Cu - 0.4% Cr Cu - 0.24. Zr Cu - 0. 3% Cr - 0.1% Zr Cu - 0.2% Cr - 0.2% Zr A description of the experimental techniques used to study the precipitation behaviour of these materials is preceeded by a discussion of the currently accepted theories relating to precipitate nucleation and growth. The experimental results are presented and discussed for each of the alloys independently, and are then treated jointly to obtain an overall assessment of the way in which the precipitation kinetics, metallography and mechanical properties vary with alloy composition and heat treatment. The metastable solid solution of copper-chromium is found to decompose by the rejection of chromium particles which maintain a coherent interface and a Kurdjumov-Sachs type crystallographic orientation relationship with the copper matrix. The addition of 0.1% zirconium to the alloy retards the rate of transformation by a factor of ten and modifies the dispersion characteristics of the precipitate without markedly altering the morphology. Further additions of zirconium lead to the growth of stacking faults during ageing, which provide favourable nucleation sites for the chromium precipitate. The partial dislocations bounding such stacking faults are also found to provide mobile heterogeneous nucleation sources for the precipitation reactions occurring in copper-zirconium.

Comparison of the ageing behaviour of PM 2124 Al alloy and Al-SiCp metal-matrix composite

The ageing response of 2124 Al-SiC particulate metal-matrix composite (MMC) and unreinforced alloy has been examined using hardness measurements and Arrhenius analysis. The formation of phases during precipitation has been studied using differential scanning calorimetry (DSC). The MMC exhibits accelerated ageing compared to unreinforced alloy, due to enhanced S′ formation. The activation energy for diffusion is lower in the MMC than in the unreinforced alloy. DSC scans show Guinier-Preston B (GPB) zone nucleation to occur at a lower temperature in the MMC, whilst the total volume of GPB zones formed is smaller than in the unreinforced alloy. A model has been proposed to explain the GPB zone formation behaviour, in which ease of GPB zone nucleation varies within the MMC, as a function of ageing time and of position within the matrix. S′ formation is enhanced in the MMC because of improved diffusion and a large increase in density of heterogeneous nucleation sites compared to the unreinforced alloy. © 1994 Chapman & Hall.

Photodeposition as a facile route to tunable Pt photocatalysts for hydrogen production:on the role of methanol

Photodeposition of H2PtCl6 in the presence of methanol promotes the formation of highly dispersed, metallic Pt nanoparticles over titania, likely via capture of photogenerated holes by the alcohol to produce an excess of surface electrons for substrate-mediated transfer to Pt complexes, resulting in a high density of surface nucleation sites for Pt reduction. Photocatalytic hydrogen production from water is proportional to the surface density of Pt metal co-catalyst, and hence photodeposition in the presence of high methanol concentrations affords a facile route to optimising photocatalyst design and highlights the importance of tuning co-catalyst properties in photocatalysis.

Pharmaceutical process optimisation of bulk lyophilisates:implications of powder handling

Lyophilisation or freeze drying is the preferred dehydrating method for pharmaceuticals liable to thermal degradation. Most biologics are unstable in aqueous solution and may use freeze drying to prolong their shelf life. Lyophilisation is however expensive and has seen lots of work aimed at reducing cost. This thesis is motivated by the potential cost savings foreseen with the adoption of a cost efficient bulk drying approach for large and small molecules. Initial studies identified ideal formulations that adapted well to bulk drying and further powder handling requirements downstream in production. Low cost techniques were used to disrupt large dried cakes into powder while the effects of carrier agent concentration were investigated for powder flowability using standard pharmacopoeia methods. This revealed superiority of crystalline mannitol over amorphous sucrose matrices and established that the cohesive and very poor flow nature of freeze dried powders were potential barriers to success. Studies from powder characterisation showed increased powder densification was mainly responsible for significant improvements in flow behaviour and an initial bulking agent concentration of 10-15 %w/v was recommended. Further optimisation studies evaluated the effects of freezing rates and thermal treatment on powder flow behaviour. Slow cooling (0.2 °C/min) with a -25°C annealing hold (2hrs) provided adequate mechanical strength and densification at 0.5-1 M mannitol concentrations. Stable bulk powders require powder transfer into either final vials or intermediate storage closures. The targeted dosing of powder formulations using volumetric and gravimetric powder dispensing systems where evaluated using Immunoglobulin G (IgG), Lactate Dehydrogenase (LDH) and Beta Galactosidase models. Final protein content uniformity in dosed vials was assessed using activity and protein recovery assays to draw conclusions from deviations and pharmacopeia acceptance values. A correlation between very poor flowability (p<0.05), solute concentration, dosing time and accuracy was revealed. LDH and IgG lyophilised in 0.5 M and 1 M mannitol passed Pharmacopeia acceptance values criteria with 0.1-4 while formulations with micro collapse showed the best dose accuracy (0.32-0.4% deviation). Bulk mannitol content above 0.5 M provided no additional benefits to dosing accuracy or content uniformity of dosed units. This study identified considerations which included the type of protein, annealing, cake disruption process, physical form of the phases present, humidity control and recommended gravimetric transfer as optimal for dispensing powder. Dosing lyophilised powders from bulk was demonstrated as practical, time efficient, economical and met regulatory requirements in cases. Finally the use of a new non-destructive technique, X-ray microcomputer tomography (MCT), was explored for cake and particle characterisation. Studies demonstrated good correlation with traditional gas porosimetry (R2 = 0.93) and morphology studies using microscopy. Flow characterisation from sample sizes of less than 1 mL was demonstrated using three dimensional X-ray quantitative image analyses. A platinum-mannitol dispersion model used revealed a relationship between freezing rate, ice nucleation sites and variations in homogeneity within the top to bottom segments of a formulation.