The pore system and engineering properties of hardened cement paste

The work described in this thesis is an attempt to elucidate the relationships between the pore system and a number of engineering properties of hardened cement paste, particularly tensile strength and resistances to carbonation and ionic penetration. By examining aspects such as the rate of carbonisation, the pore size distribution, the concentration of ions in the pore solution and the phase composition of cement pastes, relationships between the pore system (pores and pore solution) and the resistance to carbonation were investigated. The study was carried out in two parts. First, cement pastes with different pore systems were compared, whilst secondly comparisons were made between the pore systems of cement pastes with different degrees of carbonation. Relationships between the pore structure and ionic penetration were studied by comparing kinetic data relating to the diffusion of various ions in cement pastes with different pore systems. Diffusion coefficients and activation energies for the diffusion process of Cl- and Na+ ions in carbonated and non-carbonated cement pastes were determined by a quasi-steady state technique. The effect of the geometry of pores on ionic diffusion was studied by comparing the mechanisms of ionic diffusion for ions with different radii. In order to investigate the possible relationship between tensile strength and macroporosity, cement paste specimens with cross sectional areas less than 1mm2 were produced so that the chance of a macropore existing within them was low. The tensile strengths of such specimens were then compared with those of larger specimens.

The structural permeability of concrete at cryogenic temperatures

The thesis describes a programme of research designed to identify concretes for application at cryogenic temperature, in particular for storage of Liquefield Natural Gas which is maintained at a temperature of -165oC. The programme was undertaken in two stages. Stage 1 involved screening tests on seventeen concrete mixes to investigate the effects of strength grade (and water/cement ratio), air entrainment, aggregate type and cement type. Four mixes were selected on the basis of low temperature strength, residual strength after thermal cycling and permeability at ambient temperature. In Stage 2 the selected mixes were subjected to a comprehensive range of tests to measure those properties which determine the leak tightness of a concrete tank at temperatures down to -165oC. These included gas permeability; tensile strength, strain capacity, thermal expansion coefficient and elastic modulus, which in combination provide a measure of resistance to cracking; and bond to reinforcement, which is one of the determining factors regarding crack size and spacing. The results demonstrated that the properties of concrete were generally enhanced at cryogenic temperature, with reduced permeability, reduced crack proneness and, by virtue of increased bond to reinforcement, better control of cracking should it occur. Of the concretes tested, a lightweight mix containing sintered PFA aggregate exhibited the best performance at ambient and cryogenic temperature, having appreciably lower permeability and higher crack resistance than normal weight concretes of the same strength grade. The lightweight mix was most sensitive to thermal cycling, but there was limited evidence that this behaviour would not be significant if the concrete was prestressed. Relationships between various properties have been identified, the most significant being the reduction in gas permeability with increasing strain capacity. The structural implications of the changing properties of the concrete have also been considered.

The spalling of concrete in fires

The occurrence of spalling is a major factor in determining the fire resistance of concrete constructions. The apparently random occurrence of spalling has limited the development and application of fire resistance modelling for concrete structures. This Thesis describes an experimental investigation into the spalling of concrete on exposure to elevated temperatures. It has been shown that spalling may be categorised into four distinct types, aggregate spalling, corner spalling, surface spalling and explosive spalling. Aggregate spalling has been found to be a form of shear failure of aggregates local to the heated surface. The susceptibility of any particular concrete to aggregate spalling can be quantified from parameters which include the coefficients of thermal expansion of both the aggregate and the surrounding mortar, the size and thermal diffusivity of the aggregate and the rate of heating. Corner spalling, which is particularly significant for the fire resistance of concrete columns, is a result of concrete losing its tensile strength at elevated temperatures. Surface spalling is the result of excessive pore pressures within heated concrete. An empirical model has been developed to allow quantification of the pore pressures and a material failure model proposed. The dominant parameters are rate of heating, pore saturation and concrete permeability. Surface spalling may be alleviated by limiting pore pressure development and a number of methods to this end have been evaluated. Explosive spalling involves the catastrophic failure of a concrete element and may be caused by either of two distinct mechanisms. In the first instance, excessive pore pressures can cause explosive spalling, although the effect is limited principally to unloaded or relatively small specimens. A second cause of explosive spalling is where the superimposition of thermally induced stresses on applied load stresses exceed the concrete's strength.

The use of lubricants in iron powder metallurgy

This investigation has been concerned with the behaviour of solid internal lubricant during mixing, compaction, ejection, dewaxing and sintering of iron powder compacts. Zinc stearate (0.01%-4.0%) was added to irregular iron powder by admixing or precipitation from solution. Pressure/density relationships, determined by continuous compaction, and loose packed densities were used to show that small additions of zinc stearate reduced interparticle friction during loose packing and at low compaction pressures. Large additions decreased particle/die-wall friction during compaction and ejection but also caused compaction inhibition. Transverse rupture strengths were determined on compacts containing various stearate based lubricants and it was found that green strength was reduced by the interposition of a thin lubricant layer within inter~particle contacts. Only materials much finer than the iron powder respectively) were able to form such layers. Investigations were undertaken to determine the effect of the decomposition of these lubricants on the development of mechanical properties in dewaxed or sintered compacts. Physical and chemical influences on tensile strength were observed. Decomposition of lubricants was associated with reductions of strength caused by the physical effects of pressure increases and removal of lubricant from interparticle contacts. There were also chemical effects associated with the influence of gaseous decomposition products and solid residues on sintering mechanisms. Thermogravimetry was used to study the decomposition behaviour of various lubricants as free compounds and within compacts. The influence of process variables such as atmosphere type, flow-rate and compact density were investigated. In a reducing atmosphere the decomposition of these lubricants was characterised by two stages. The first involved the rapid decomposition of the hydrocarbon radical. The second, higher temperature, reactions depended on lubricant type and involved solid residues. The removal of lubricant could also markedly affect dimensional change.

Electrodeposition on aluminium and its alloys

Aluminium alloys S1C, NS4, HE9, LM25 and the 'difficult' zinc containing U.S. specification alloy used for automobile bumpers (X-7046), have been successfully electroplated using pretreatments which utilized either conventional immersion, elevated temperature or electrolytic modified alloy zincate (M.A.Z.) deposits. Satisfactory adhesion in excess of 7•5 KN m -I was only achieved on X-7046 using an electrolytic M.A.Z. pretreatment. The limitations of simple zincate solutions were demonstrated. Growth of deposits ~as monitored using a weight loss technique and the morphology of the various deposits studied using scanning electron microscopy. The characteristics of a specific alloy and processing sequence selected had a significant influence on the growth and morphology of the N.A.Z. deposi t. These all affected subsequent adhesion of electrodeposited nickel. The advantages of double-dip sequences were confirmed. Superior adhesion was associated with a uniform, thin, fine grained M.A.Z. deposit which exhibited rapid and complete surface coverage of the aluminium alloy. The presence of this preferred type deposit did not guarantee adhesion because a certain degree of etching was essential. For a satisfactory combination of alloy and M.A.Z. pretreatment, there was a specific optimum film weight per unit area which resulted in maximum adhesion. An ideal film weight of 0•06 :!: 0•01 mg cm-2was determined for S1C. Different film weights were required for the other alloys due to variations in surface topography caused by pretreatment. S1C was the easiest alloy on which to achieve high bond strength. Peel adhesion was not directly related to tensile strength of the alloy. The highest adhesion value was obtained on S1C which had the lowest strength of the alloys studied. The characteristics of the failure surfaces after peeling depended on alloy type, adhesion level and pretreatment employed. Plated aluminium alloys exhibited excellent corrosion resistance when appropriately pretreated. The M.A.Z. layer was not preferentially attacked. There was a threshold value of adhesion below which corrosion performance ~a8 poor. Alloy type, pretreatment and coating system influenced corrosion performance. Microporous chromium gave better corrosion protection than decorative chromium.

The mechanical properties and formability of dual-phase steel

In recent years dual phase steels comprising of 5-20% martensite in a ferrite matrix have come into the limelight of high strength cold formable steels because of their potential for vehicle weight saving. They show the following features: no yield point; relatively low initial flow stress; high initial workhardening rate; well sustained work hardening. As a consequence of these characteristics, dual phase steels exhibit a better combination of strength and elongation than other HSLA steels. In this thesis, a broad view of the factors which influence their properties is presented. Mechanical properties and forming ability of a commercially available dual phase steel and an AL-Si killed steel processed to dual phase form are investigated to ascertain the effect of their microstructure on their properties. It is found that the yield phenomena are masked by the transformation induced stresses present during processing and so yield point could be recovered under suitable ageing treatment; that apart from giving the above properties dual phasing gives rise to very low strain-rate sensitivity and a low R value ~ 1; that the mechanical response under rolling conditions is not different from those under tension; that there is a danger of damage to tooling during forming operations of these steels if fracture should precede instability as a result of grain size dependent strength found for these steels. It is also found that very little deformation of the martensite islands took place during deformation except at high strains. The work-hardening and the strength levels can be controlled by either decreasing the grain size or increasing the martensite volume fraction, but it is found that increasing martensite has a detrimental effect on ductility and the ductility and fracture strength can be controlled better by refining the grain size. A remarkable effect found in the dual phase steel tested is that the compressive strength is higher than the tensile strength. The reason for this observation is not yet clear but it is suggested that it might be due to the introduction of emissary type dislocations into the ferrite lattice as a result of twins formed in the martensite during transformation from austenite. The twins are envisaged to be {111} <112> in character.

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.

Damping in zinc-based alloys

The damping behaviour of the cold chamber pressure-die-casting alloy: M3, ZA8, ZA27, ZM11, Cosmal, Supercosmal and newly developed ZA27H1 and ZA27H2 was investigated at room temperature and elevated temperatures of up to 90 degrees C. The damping properties of the alloys were established at all temperatures. Formulas were established to predict damping properties of each alloy at any given temperature. The prediction formulae were found to be very accurate. All of the experimental alloys were heterogenous with varying microstructure and grain size; this was the major contribution and dominated the damping properties of the alloys. Super cosmal and ZA27 possessed the highest tensile strength but ZA27H1, ZA27H2 and ZM11 showed the highest damping properties. The relationship between microstructure and damping capacity of all alloys was also examined using back-scattered electron on the SEM. Further more detailed examinations of the microstructures of alloys ZM11, Cosmal and Supercosmal were carried out on the transmission electron microscope in order to establish the phases present in all alloys. These helped to obtain the mechanism of damping in the experimental alloys. The main damping mechanism in most of the experimental alloys was due to grain-boundary-sliding. Micro structural examinations also revealed the absence of -phase in the Cosmal and Supercosmal. This was thought to be due to a change in solid solubility of the alloys, which could have been caused by the addition of Si.

The mechanical and wear behaviour of B(SiC) fibre-reinforced composite materials

The mechanical properties and wear behaviour of B(SiC) fibre-reinforced metal matrix composites (MMCs) and aluminium alloy (2014) produced by metal infiltration technique were determined. Tensile tests were peliormed at different conditions on both the alloy matrix and its composite, and the tensile fracture surfaces were also examined by Scanning Electron Microscopy (SEM). Dry wear of the composite materials sliding on hardened steel was studied using a pin-on-disc type machine. The effect of fibre orientation on wear rate was studied to provide wear resistance engineering data on the MMCs. Tests were carried out with the wear surface sliding direction set normal, parallel and anti-parallel to the fibre axis. Experiments were perfonned for sliding speeds of 0.6, 1.0 and 1.6 m/s for a load range from 12 N to 60 N. A number of sensitive techniques were used to examine worn surface and debris, i.e: Scanning Electron Microscopy (SEM), Backscattered Electron Microscopy (BSEM) and X-ray Photoelectron Spectroscopy (XPS). Finally, the effect of fibre orientation on the wear rate of the Borsic-reinforced plastic matrix composites (PMCs) produced by hot pressing technique was also investigated under identical test conditions. It was found that the composite had a markedly increased tensile strength compared with the matrix. The wear results also showed that the composite exhibited extremely low wear rates compared to the matrix material and the wear rate increased with increasing sliding speed and normal load. The effect of fibre orientation was marked, the lowest wear rates were obtained by arranging the fibre perpendicular to the sliding surface, while the highest wear was obtained for the parallel orientation. The coefficient of friction was found to be lowest in the parallel orientation than the others. Wear of PMCs were influenced to the greatest extent by these test parameters although similar findings were obtained for both composites. Based on the results of analyses using SEM, BSED and XPS, possible wear mechanisms are suggested to explain the wear of these materials.

Quality control of pharmaceutical ingredients:developing a caking test for industry

Objectives - Powdered and granulated particulate materials make up most of the ingredients of pharmaceuticals and are often at risk of undergoing unwanted agglomeration, or caking, during transport or storage. This is particularly acute when bulk powders are exposed to extreme swings in temperature and relative humidity, which is now common as drugs are produced and administered in increasingly hostile climates and are stored for longer periods of time prior to use. This study explores the possibility of using a uniaxial unconfined compression test to compare the strength of caked agglomerates exposed to different temperatures and relative humidities. This is part of a longer-term study to construct a protocol to predict the caking tendency of a new bulk material from individual particle properties. The main challenge is to develop techniques that provide repeatable results yet are presented simply enough to be useful to a wide range of industries. Methods - Powdered sucrose, a major pharmaceutical ingredient, was poured into a split die and exposed to high and low relative humidity cycles at room temperature. The typical ranges were 20–30% for the lower value and 70–80% for the higher value. The outer die casing was then removed and the resultant agglomerate was subjected to an unconfined compression test using a plunger fitted to a Zwick compression tester. The force against displacement was logged so that the dynamics of failure as well as the failure load of the sample could be recorded. The experimental matrix included varying the number of cycles, the amount between the maximum and minimum relative humidity, the height and diameters of the samples, the number of cycles and the particle size. Results - Trends showed that the tensile strength of the agglomerates increased with the number of cycles and also with the more extreme swings in relative humidity. This agrees with previous work on alternative methods of measuring the tensile strength of sugar agglomerates formed from humidity cycling (Leaper et al 2003). Conclusions - The results show that at the very least the uniaxial tester is a good comparative tester to examine the caking tendency of powdered materials, with a simple arrangement and operation that are compatible with the requirements of industry. However, further work is required to continue to optimize the height/ diameter ratio during tests.

A systematic and mechanistic evaluation of aspartic acid as filler for directly compressed tablets containing trimethoprim and trimethoprim aspartate

The generally accepted paradigm of 'inert' and 'mono functional' excipient in dosage form has been recently challenged with the development of individual excipients capable of exhibiting multiple functions (e.g. binder-disintegrants, surfactant which affect P-gp function). The proposed study has been designed within the realm of multifunctionality and is the first and novel investigation towards evaluation of aspartic acid as a filler and disintegration enhancing agent for the delivery of biopharmaceutical class IV model drug trimethoprim. The study investigated powder characteristics using angle of repose, laser diffractometry and scanning electron microscopy (SEM). The prepared tablets were characterised using Heckel analysis, disintegration time and tensile strength measurements. Although Heckel analysis revealed that both TMP and TMP aspartate salt have high elasticity, the salt form produced a stronger compact which was attributed to the formation of agglomerates. Aspartic acid was found to have high plasticity, but its incorporation into the formulations was found to have a negative impact on the compaction properties of TMP and its salt. Surface morphology investigations showed that mechanical interlocking plays a vital role in binding TMP crystals together during compaction, while the small particle size of TMP aspartate agglomerates was found to have significant impact on the tensile strength of the tablets. The study concluded that aspartic acid can be employed as filler and disintegrant and that compactability within tablets was independent of the surface charge of the excipients.

Application of transglutaminases in the modification of wool textiles

The use of the protein-crosslinking enzymes transglutaminases (EC 2.3.2.13), as biocatalysts in the processing of wool textiles offers a variety of exciting and realistic possibilities, which include reducing the propensity of wool fabric to shrink and maintaining or increasing fabric strength. Guinea pig liver (GPL) transglutaminase or the microbial transglutaminase isolated from Streptoverticilium mobaraense, when applied to wool either alone or following a protease treatment, resulted in an increase in wool yarn and fabric strength (up to a 25% increase compared to a control). This indicates that transglutaminases can remediate the negative effects of proteolytic treatments in terms of loss in fibre strength. Incubation of samples pretreated with different oxidative and reducing agents with both sources of transglutaminases led to significant increases in tensile strength for all samples tested, suggesting that yarn strength lost following chemical treatments can also be recovered. The two different transglutaminases (TGases) could also impart a significant reduction in fabric shrinkage. The incorporation of primary amine transglutaminase substrates into wool fibres, with a view to altering wool functionality, was demonstrated using the incorporation of the fluorescent primary amine fluorescein cadaverine (FC). Incubation of wool with this fluorescent amine and transglutaminase led to high levels of incorporation into the fibres. The treatment of wool textiles with transglutaminases indicates that a number of novel and radically different finishes for wool textiles can be developed.

High stress monitoring of prestressing tendons in nuclear concrete vessels using fibre-optic sensors

Maintaining the structural health of prestressed concrete nuclear containments is a key element in ensuring nuclear reactors are capable of meeting their safety requirements. This paper discusses the attachment, fabrication and characterisation of optical fibre strain sensors suitable for the prestress monitoring of irradiated steel prestressing tendons. The all-metal fabrication and welding process allowed the instrumented strand to simultaneously monitor and apply stresses up to 1300 MPa (80% of steel's ultimate tensile strength). There were no adverse effects to the strand's mechanical properties or integrity. After sensor relaxation through cyclic stress treatment, strain transfer between the optical fibre sensors and the strand remained at 69%. The fibre strain sensors could also withstand the non-axial forces induced as the strand was deflected around a 4.5 m bend radius. Further development of this technology has the potential to augment current prestress monitoring practices, allowing distributed measurements of short- and long-term prestress losses in nuclear prestressed-concrete vessels. © 2014 Elsevier B.V.

Characterisation of electrospun polystyrene scaffolds for three-dimensional in vitro biological studies

The purpose of this study was to produce a well-characterised electrospun polystyrene scaffold which could be used routinely for three-dimensional (3D) cell culture experimentation. A linear relationship (p<0.01p<0.01) between three principal process variables (applied voltage, working distance and polymer concentration) and fibre diameter was reliably established enabling a mathematical model to be developed to standardise the electrospinning process. Surface chemistry and bulk architecture were manipulated to increase wetting and handling characteristics, respectively. X-ray photoelectron spectroscopy (XPS) confirmed the presence of oxygen-containing groups after argon plasma treatment, resulting in a similar surface chemistry to treated tissue culture plastic. The bulk architecture of the scaffolds was characterised by scanning electron microscopy (SEM) to assess the alignment of both random and aligned electrospun fibres, which were calculated to be 0.15 and 0.66, respectively. This compared to 0.51 for collagen fibres associated with native tissue. Tensile strength and strain of approximately of 0.15 MPa and 2.5%, respectively, allowed the scaffolds to be routinely handled for tissue culture purposes. The efficiency of attachment of smooth muscle cells to electrospun scaffolds was assessed using a modified 3-[4,5-dimethyl(thiazol-2yl)-3,5-diphery] tetrazolium bromide assay and cell morphology was assessed by phalloidin-FITC staining of F-actin. Argon plasma treatment of electrospun polystyrene scaffold resulted in significantly increased cell attachment (p<0.05p<0.05). The alignment factors of the actin filaments were 0.19 and 0.74 for the random and aligned scaffold respectively, compared to 0.51 for the native tissue. The data suggests that electrospinning of polystyrene generates 3D scaffolds which complement polystyrene used in 2D cell culture systems.

A methodological evaluation and predictive in silico investigation into the multi-functionality of arginine in directly compressed tablets

The acceleration of solid dosage form product development can be facilitated by the inclusion of excipients that exhibit poly-/multi-functionality with reduction of the time invested in multiple excipient optimisations. Because active pharmaceutical ingredients (APIs) and tablet excipients present diverse densification behaviours upon compaction, the involvement of these different powders during compaction makes the compaction process very complicated. The aim of this study was to assess the macrometric characteristics and distribution of surface charges of two powders: indomethacin (IND) and arginine (ARG); and evaluate their impact on the densification properties of the two powders. Response surface modelling (RSM) was employed to predict the effect of two independent variables; Compression pressure (F) and ARG percentage (R) in binary mixtures on the properties of resultant tablets. The study looked at three responses namely; porosity (P), tensile strength (S) and disintegration time (T). Micrometric studies showed that IND had a higher charge density (net charge to mass ratio) when compared to ARG; nonetheless, ARG demonstrated good compaction properties with high plasticity (Y=28.01MPa). Therefore, ARG as filler to IND tablets was associated with better mechanical properties of the tablets (tablet tensile strength (σ) increased from 0.2±0.05N/mm2 to 2.85±0.36N/mm2 upon adding ARG at molar ratio of 8:1 to IND). Moreover, tablets' disintegration time was shortened to reach few seconds in some of the formulations. RSM revealed tablet porosity to be affected by both compression pressure and ARG ratio for IND/ARG physical mixtures (PMs). Conversely, the tensile strength (σ) and disintegration time (T) for the PMs were influenced by the compression pressure, ARG ratio and their interactive term (FR); and a strong correlation was observed between the experimental results and the predicted data for tablet porosity. This work provides clear evidence of the multi-functionality of ARG as filler, binder and disintegrant for directly compressed tablets.