Short crack growth behaviour was studied using a method of plastic replication on hour-glass shaped specimens of a medium carbon steel which were subjected to push-pull fatigue testing at ambient temperature. Crack lengths were measured from replicas using an optical microscope from which the growth rate could be calculated. A theory for short crack growth is presented which may be expressed mathematically by the equation:- = (for a < d) da dN where (a) is crack length, (d) is a characteristic dimension between adjacent microstructural obstacles to crack propagation, C1 is a function of stress or strain range and a is a constant. For the medium carbon steel used in this study (d) was equated to the ferrite band length which contained the growing crack. This theory was used to model short crack growth in an Aluminium alloy T6-7075 Al and for the medium carbon steel used in this project. iii By using a second equation to describe "long" crack growth of the form:- da dN = where C2 is a function of the applied strain range and 0 is a constant, it was then possible to describe the complete history of crack growth. By obtaining short crack growth data for different stress levels, quantitative expressions of these two equations were calculated from which fatigue lifetime predictions could be made by integration of the equations for any stress level. Using this method an estimate could also be made of the percentage of fatigue lifetime spent in the initiation and growth of short cracks.

The object of this study was to help clarify some of the fundamental problems occurring in plain and reinforced concrete structural elements suffering from the degradation phenomenon of alkali silica reaction. A laboratory based testing programme was used, so that extreme conditions for generating alkali silica reaction could be used which are not readily achieved in actual structures. Special concrete mixes were also used in which the alkali silica reaction occurs within a period of months rather than years so that observation of the properties of the reacted concrete could be taken throughout the reacti ve process. The laboratory tests undertaken are as follows: fresh and hardened behaviour of alkali silica reactive (ASR) model mixes; mechanical properties and expansion behaviour of ASR concrete; structural behaviour of reinforced ASR concrete beams and columns; bond between reinforcement and ASR concrete in prisms and beams; restraint effect of ASR upon plain and reinforced concrete structural elements. This work shows that, ASR causes an unacceptable level of progressive damage to plain and reinforced concrete. The degradation and expansion in plain ASR concrete is higher than that in reinforced concrete. ASR in concrete reduces the strength and elastic modulus; the stiffness of reinforced beams; the axial load and ultimate bending moment capacity of columns; the ultimate bond between concrete and reinforcement. As a result of expansion in non-symmetrically reinforced structural elements, ASR causes either sagging or hogging displacement. The restraint imposed by reinforcement in ASR concrete elements is however beneficial in terms of inhibiting expansion and crack development, and exerting a small degree of post tensioning which generally improves the strength of members. Preloading of ASR concrete also results in an improvement in the mechanical properties. PhD

Currently in the UK, composite blends of Portland cement (PC) and blastfurnace slag (up to 90%) are commonly used for the encapsulation of low and intermediate level wastes. The high volume replacement of PC is considered necessary in order to to reduce the high heat generation resulting from cement hydration in 500 litre waste packages. While suited to the majority of waste streams, the high pH environment in such systems (usually around 12.5 -13), will cause the corrosion of certain waste metals such as aluminium. Since aluminium is only passive between pH4 - 8.5, the use of an alternative low-pH cement system could serve to reduce/inhibit the corrosion. However, before such cements can be considered, two main research problems must be addressed, as follows: (1) quantitative evaluation of alternative cement systems based on their corrosion performance with aluminium; (2) high heat generation due to the rapid rate of hydration. The research in this thesis was thus divided into two strands, as follows: (1) The design and development of a novel, scientifically robust testing facility for the quantitative monitoring of aluminium corrosion in cement pastes; (2) the development of novel cement composites based on weakly alkaline calcium sulfoaluminate (CSA) cement for the encapsulation of aluminium from nuclear wastes. The output from this research is considered to be of interest to the UK nuclear industry.

Today the use of resources in the industry are not complete to be considered as sustainable from the perspective of nutrient recovery. In the Swedish pulp and paper industry residual streams such as bark, fiber reject and sludge are returned for more sustainable use more frequently. Around 300 000-600 000 tons of sludge is generated every year from different cleaning processes in the pulp and paper industry. About 15 % of that sludge is so called biosludge that is a result from biological water treatment, where large amounts of phosphorus are used. After the cleaning process the total amount of biosludge generated in Sweden each year is estimated to contain approximately 2000 tons of phosphorus (P). The most common way to discard the biosludge today is by incineration, where aspects such as high content of moisture and ash have proven to be problematic. Besides phosphorus, other elements such as sulfur (S), chlorine (Cl) and calcium (Ca) are often found in the biosludge in larger amounts.   This study included co-combustion experiments of current residual streams from the pulp and paper mill SCA Obbola AB where the aim was to investigate how the ash transformation chemistry was affected. The residual streams comprised of bark, fiber reject and biosludge which were combusted together with stem wood in a bench scaled bubbling fluidized bed. To investigate if different ash related operating and technical problems could be reduced and if there was potential of phosphorus recycling from the ashes, produced ash and other samples were examined by SEM/EDS. The fuel mix from SCA Obbola consisted of large amounts of Ca, S and P relative to more ordinary biomass fuels like stem wood. These elements originated from the biosludge and was confirmed by the fuel analysis. Analysis made on collected samples showed that Ca and P together formed phosphates that either stayed in the bed or was collected in the cyclone which indicated that there could be a potential for recovering phosphorus. Although, the Ca/P ratio in the ashes was too high, which probably leads to that phosphates unsuitable for nutrient recovery are formed.   The fiber reject from SCA Obbola contained large amounts of chlorine according to the fuel analysis which was indicated from the results later in the study. During the combustion most of the Cl left the bottom ash via volatilization. It was true for both the fuel blends with and without fiber reject. When larger amounts of biosludge was added to the fuel mix less of the corrosive compound potassium chloride (KCl) was found in depositions and collected fine particulate matter (PM). This was due to that more sulfur was added in the system when the amount of biosludge was increased which lead to that K reacted with SO2 instead of Cl and formed K2SO4. The observed reduction of KCl resulted in; 1) lower amounts of fine particulate matter which means less loaded particulate filters 2) less risk of high temperature corrosion on heat transfer surfaces. The general conclusion that could be drawn from this study was that by increasing the amount of biosludge in the fuel blend at already high mixings of fiber reject, problems such as corrosion and fine particulate matter could be reduced. These advantages must be considered to the amount of lime stone needed to be added for reducing HCl from a cost perspective.

Thesis (MSc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Biofouling in cooling water systems lead to several problems resulting in reduced efficiency and financial losses. Antifouling coatings present an environmental friendly solution to prevent biofouling alternatively to the current use of toxic chemicals in cooling water systems. In this study biofilm growth in a cooling water system was simulated in a modified flow cell system to evaluate industrial antifouling coatings and biocide-enriched coatings as potential antifouling coatings for metal surfaces. The design of a novel antifouling coating was also attempted. Firstly, analytical methods for biofilm monitoring to evaluate selected antifouling coatings and biocides were optimised. Pseudomonas sp. strain CT07 was selected to grow biofilms in the biofilm studies. A metal alloy of stainless steel and mild steel (3CR12) showed no corrosion after a 24 h biofilm growth and was selected as metal surface for the biofilm growth discs. Sonification for 5 min was determined as the optimum biofilm removal method from the growth discs. After biofilm removal the metal growth discs were stained with the LIVE/DEAD® BaclightTM Bacterial Viability kit. Visualisation by confocal laser scanning microscopy and flow cytometry revealed auto fluorescence signals from metal discs that hindered quantitative and qualitative analysis of the metal substrate. The use of Pseudomonas sp. strain CT07::gfp to grow biofilms on the metal growth discs and the exclusion of the stain SYTO9 from the LIVE/DEAD® BaclightTM Bacterial Viability kit reduced auto fluorescence signals from the metal discs. The industrial coatings containing quaternary ammonium salt (QAC), triclosan (TC) and copper oxide (CUO) respectively, showed the highest antimicrobial activity in the disc diffusion test. The minimum inhibition concentrations for silver nitrate (SN) and copper sulphate (CS) were 432 ppm and 160 ppm respectively. A minimum of 6.25 % of furanone solution (FR) was biocidal in the dilution susceptibility test. Secondly, the metal growth discs were coated respectively with the three selected industrial coatings QAC, TC and CUO and the epoxy biocide-enriched coatings SN, CS and FR and chemically characterised before and after exposure to biofilm formation. The antifouling activity of these coatings was also characterized. Growth media inoculated with Pseudomonas sp strain CT07::gfp was circulated through the modified flow cell system via a multichannel peristaltic pump for 48 h before the coated metal discs were removed and washed to perform chemical or antifouling analysis. All the industrial coatings and biocide enriched epoxy coatings complied with the thermal stability requirements of a cooling water system. Scanning electron microscopy (SEM) imaging and Energy dispersive X-ray spectroscopy (EDX) analysis confirmed that the adhesion properties of industrial coatings TC and QAC in aqueous environments were insufficient and that the copper and silver ions leached out of the biocide-enriched epoxy coatings. The qualitative analyses of the attachment of bacteria on the surfaces of both the industrial and biocide enriched epoxy coatings was confirmed by SEM, CLSM. The attached bacteria were removed and analysed quantitatively through plate counts and flow cytometry. None of the industrial coatings or the biocide incorporated epoxy coatings that were used in this study would therefore be efficient for the use on metal surfaces in cooling water systems. Thirdly, several approaches were followed to synthesise a poly(styrene-alt-maleic anhydride) (SMA) coating, chemically bind a furanone derivative, 2,5-dimethyl-4-hydroxy-3-(2H)-furanone, to the polymer back bone of the SMA coating for the application as an antifouling coating for cooling water systems. The synthesis of SMA was confirmed through 1H NMR and SEC and the synthesis of tert-butyl 2-(2-hydroxyethoxy) ethylcarbamate and 4-(2-(2-(tert-butoxycarbonyl)ethoxy)ethoxy)-4- oxobutanoic acid was confirmed through 1H NMR and ES-MS+. The synthesis of the end furanone derivative product could however not be achieved. / AFRIKAANSE OPSOMMING: Bio-aanpaksels in waterverkoelingsisteme veroorsaak talle probleme wat lei tot verminderde doeltreffendheid en finansiële verliese. Antimikrobiese oppervlakbedekkings verskaf ‘n omgewingsvriendelike oplossing om bio-aanpaksels te voorkom en ‘n alternatief vir die huidige gebruik van giftige chemikalieë in waterverkoelingsisteme. Biofilm groei in waterverkoelingsisteme was nageboots in ‘n gewysigde vloeiselsisteem om industriële aanpakwerende en biopsied bevattende antimikrobiese oppervlakbedekkings as potensiële aanpakwerende beskermingslae vir metaaloppervlaktes te evalueer. Die ontwerp van ‘n nuwe aanpakwerende beskermingslaag is ook ondersoek. Eerstens is analitiese moniteringsmetodes vir bio-aanpaksels op geselekteerde aanpakwerende antimikrobiese oppervlakbedekkings en biosiedes geoptimiseer. Pseudomonas sp. stam CT07 was verkies om bio-aanpaksels te simuleer gedurende hierdie studie. ‘n Metaalalooi van vlekvrye staal en sagte staal (3R12) het geen korrosie getoon na 24 uur se groei van bio-aanpaksels nie en is vir hierdie rede gebruik as metaal vir die bio-aanpaksel groeiplate. Dit was vasgestel dat sonifisering die optimale verwyderingsmetode vir groeiplate was. Na verwydering van bio-aanpaksels was die metaal groeiplate bedek met die LIVE/DEAD® BaclightTM bakteriële lewensvatbaarheid-toestel. Visualisering deur middel van konfokale mikroskopie en vloeisitrometrie het outofluoreserende seine vanaf die metaal groeiplate onthul wat kwantitatiewe en kwalitatiewe analise van die metaal substraat verhinder het. Die gebruik van Pseudomonas sp. stam CT07:gfp om bio-aanpaksels te kweek op metal plate en die uitsluiting van SYT09 van die LIVE/DEAD® BaclightTM bakteriële lewensvatbaarheid-toestel, het die outofluoreserende seine van die metaalskywe verminder. Industriële beskerminglae, wat onderskeidelik Kwaternêre ammonium sout (QAC), triclosan (TC) en koperoksied (CUO) bevat, het die hoogste antimikrobiese aktiwiteit in die skyf-diffusie toets getoon. Die minimum inhibisiekonsentrasies vir silwernitraat (SN) en kopersulfaat (CS) was onderskeidelik 432 dpm en 160 dpm. ‘n Minimum konsentrasie van 6.25% van die furanoonoplossing (FO) is geklassifiseer as ‘n biosied in die oplossingstoets.Tweedens was die metaal groei-skywe bedek met drie industriële beskermingslae QAC, TC en CUO en die epoksie-biosied-verrykte lae SN, CS en FR en chemiesgekarakteriseerd voor en na die vorming van bio-aanpaksel. Die karaktereienskappe van die aktiwiteit van die beskermingslae was ook vasgestel. Opgeloste triptiese soja sop vermeng met Pseudomonas sp strain CT07: gfp was gesirkuleer in die gemodifiseerde vloeisel deur ‘n multikanaal peristaltiese pomp vir 48 uur voordat die beskermde metaalskywe verwyder en gewas is om chemiese en aanpakwerende analise uit te voer. Al die industriële beskermingslae en biosied-verrykte epoksie-beskermingslae het aan die vereistes van termiese stabiliteit van ‘n waterverkoelingsisteem voldoen. Skandeer elektronmikroskopie (SEM) en X-straal spektroskopie (EDX) analise het aangetoon dat die aantrekkingseienskappe van industriële beskermingslae TC en QAC in waterige oplossings onvoldoende was en dat die koper- en silwerione uit die biosiedverrykte epoksie-resin beskermingslae diffundeer. Die kwalitatiewe analise van die aanpaksel van bakterieë op die oppervlaktes van beide industriële en biosied -verrykte epoksie-beskermingslae was bevestig deur SEM en CLSM. Die aangepakte bakterieë was verwyder en kwantitatief geanaliseer deur middel van plaattellings en vloeisitrometrie. Nie een van die industriële beskermingslae of die biosied-bevattende epoksie beskermingslae wat in hierdie studie gebruik is, is dus gepas vir gebruik op metaaloppervlaktes in waterverkoelingsisteme nie. Derdens was verskeie pogings aangewend om ‘n poli(stireen-alt-maleic anhidried) (SMA) beskermingslaag chemies te bind tot ‘n furanoon afgeleide 2.5-demitiel-4-hidroksie-3-(2H)- furanoon, tot die polimeer-ruggraat van die SMA beskermingslaag vir aanwending as ‘n aanpakwerende beskermingslaag vir waterverkoelingsisteme. Die sintese van SMA was bevestig deur 1H NMR en SEC en die sintese van tert-butyl 2-(2-hirdoksie-etoksie) etielkarbamaat en 4-(2- (2-(tert-butoksiekarboniel)etoksie)etoksie)-4-oksobutanoiesesuur was bevestig deur 1H NMR en ES-MS+. Die sintese van die uiteindelike afgeleide furanoon kon egter nie behaal word nie.

Coatings are often used as a means of protecting aluminum alloy and steel structures in industry. The assessment of corrosion under these coatings can be challenging. Corrosion sensing coatings can exhibit properties that allow undercoating corrosion to be identified before it can be seen with the naked eye. This would be very advantageous and could potentially result in tremendous savings in time and money when structures undergo routine maintenance. Our work involved the study of corrosion sensing coatings with incorporated fluorescent indicators that can be used to sense the undercoating corrosion on metal substrates. The fluorescent indicator in the coated-aluminum system was a negative indicator, i.e. the indicator in the coating was initially fluorescent and subsequently non-fluorescent due to the reduced pH at the anodic sites of corrosion. The fluorescent indicator in coated-steel system was positive, in the sense that the coating changed from non-fluorescent to fluorescent over the cathodic areas due to increased pH. The corrosion sensing coating was composed of commercial epoxy-polyamide and the indicator: 7-amino-4-methylcoumarin (7-AMC) for the coated-aluminum alloy system and 7-diethylamino-4-methylcoumarin (7-DMC) for the coated-steel system. The feasibility of using 7-AMC for sensing early undercoating corrosion was demonstrated by using fluorescent observations, Electrochemical Impedance Spectroscopy (EIS), Scanning Electron Microscope (SEM) and Energy Dispersive Spectroscopy (EDS) tests. EIS results estimated that with continuous immersion the undercoating corrosion occurred within 24 hours after immersion in the salt solution. When corrosion occurred, the corrosion was invisible under natural light. However, small spots appeared in the fluorescent image, changing from initially fluorescent to non-fluorescent where the anodic sites were identified by SEM and EDS. In other words, the fluorescent indicator could sense the early undercoating corrosion, although blistering can be a competing mechanism associated with corrosion under some conditions. The sensitivity of the 7-AMC corrosion detection system was tested by applying anodic current to the metal and measuring the charge at which fluorescence quenching was detected. The critical charge for a detectable pit under the coating was approximately 2x10⁻⁵ C, which implied a critical radius of a single corrosion spot or set of spots of approximately 10 [mu]m. The fluorescent properties of 7-AMC, its effect on the protectiveness, its sensitivity to pH and its concentration in the coating are explored as well. Fourier transform spectroscopy (FTIR) was used to characterize the structure of the coating with and without 7-AMC. The results suggested that there is no structure change occurring after adding 7-AMC into the coating. Fluorescence behavior, electrochemical behavior, microscopic evidence, and visual observations of coated steel specimens with 7-DMC are compared based on exposure to saltwater conditions. Some of the challenges associated with the use of these types of coatings will be presented. This includes the interference from the increased production of ferrous and ferric ions. All of this information is aimed at the development of corrosion sensing coatings that can reveal undercoating corrosion before it is visible to the naked eye. / text

Reinforced concrete structures deteriorate throughout their lifetime. This is particularly apparent in structures subjected to aggressive environments, which results in corrosion of reinforcing steel. Designers make allowances for accelerated deterioration in these environments in an attempt to ensure the durability of the structure. To combat corrosion, improved concrete characteristics and additional concrete cover are used to increase the protection provided by concrete to reinforcing. In spite of these measures, cracking of structures in service and from natural hazards can limit the effectiveness that these measures provide. Ultimately, this results in structures suffering from corrosion, which affects their strength, stiffness, and ductility. While strength reduction can be associated directly with a reduction in bar area, impacts on stiffness and ductility are associated with more complex mechanisms, one of which is bond deterioration. A key assumption in reinforced concrete design is that there is perfect bonding between steel reinforcing and surrounding concrete to allow for strain compatibility to be assumed. Perfect bond does not exist and diminished bond performance due to corrosion deterioration further violates this assumption, the effects of which are not fully understood. This thesis investigates the effects of bond deterioration due to corrosion on the seismic performance of reinforced concrete structures. 60 monotonic and cyclic pull-out tests were undertaken on corroded reinforced concrete specimens, with corrosion levels ranging from 0% to 25% reinforcing mass loss. Additional tests were also conducted on specimens with variations in the amount of confining steel to simulate losses in confinement associated with corrosion of confining steel. Experimental results were used to develop corrosion and confinement dependent cyclic bond-slip model. The proposed bond-slip model was then used to modelling pull-out of reinforcing bars detailed in accordance with New Zealand design standard NZS3101. Analyses were performed at a range of corrosion levels, levels of confinement, and uncorroded bond strengths. These showed that pull-out of reinforcement occurred at as little as 8% corrosion in low strength, unconfined conditions. Multi-spring modelling of standard reinforced concrete columns, representing a bridge pier to foundation connection, was performed at the full range of deterioration with allowance for bond slippage. These analyses showed significant reductions in stiffness occurring with increased corrosion levels as well as reduced ductility and possible pull-out of reinforcement.

No description available.

No description available.

No description available.