The transient behaviour of plain concrete at elevated temperatures

This thesis describes an investigation of the effect of elevated temperatures upon the properties of plain concrete containing a siliceous aggregate. A complete stress-strain relationship and creep behaviour are studied. Transient effects (non-steady state) are also examined in order to simulate more realistic conditions. A temperature range of 20-700ºC is used. corresponding to the temperatures generally attained during an actual fire. In order to carry out the requisite tests, a stiff compression testing machine has been designed and built. The overall control of the test rig is provided by a logger/computer system by developing appropriate software, thus enabling the load to be held constant for any period of tlme. Before outlining any details of the development of the testing apparatus which includes an electric furnace and the.associated instrumentation, previous work on properties of both concrete and. steel at elevated temperatures is reviewed. The test programme comprises four series of tests:stress-strain tests (with and without pre-load), transient tests (heating to failure under constant stress) and creep tests (constant stress and constant temperature). Where 3 stress levels are examined: 0.2, 0.4 & 0.6 fc. The experimental results show that the properties of concrete are significantly affected by temperature and the magnitude of the load. The slope of the descending portion branch of the stress-strain curves (strain softening) is found to be temperature dependent. After normalizing the data, the stress-strain curves for different temperatures are represented by a single curve. The creep results are analysed using an approach involving the activation energy which is found to be constant. The analysis shows that the time-dependent deformation is sensibly linear with the applied stress. The total strain concept is shown to hold for the test data within limits.

The role of oxidation in the protection of sliding metal surfaces

This study is concerned with the mechanisms of growth and wear of protective oxide films formed under various tribological conditions. In the study three different tribological systems are examined in each of which oxidational wear is the dominant equilibrium mode. These are an unlubricated steel on steel system sliding at low and elevated temperatures, a boundary lubricated aluminium bronze on steel system and an unlubricated reciprocating sliding 9% Cr steel system operated at elevated temperature, in an atmosphere of carbon dioxide. The results of mechanical measurements of wear and friction are presented for a range of conditions of load, speed and temper.ature for the systems, together with the results of extensive examinations of the surfaces and sub­ surfaces by various physical methods of analysis. The major part of the thesis, however, is devoted to the development and application of surface models and theoretical quantative expressions in order to explain the observed oxidational wear phenomena. In this work, the mechanisms of formation of load bearing ox ide plateaux are described and are found to be dependent on system geometry and environment. The relative importance of ''in contact" and "out of contact" oxidation is identified together with growth rate constants appropriate to the two situations. Hypotheses are presented to explain the mechanisms of removal of plateaux to form wear debris. The latter hypotheses include the effects of cyclic stressing and dislocation accumulation, together with effects associated with the kinetics of growth and physical properties of the various oxides. The proposed surf ace mode1s have led to the develop­ ment of quantitative expressions for contact temperature, unlubricated wear rates, boundary lubricated wear rates and the wear of rna ter ial during the transition from severe to mild wear. In general theoretical predictions from these expressions are in very good agreement with experimental values.

Creep and fatigue of a single crystal nickel base superalloy

The introduction of single crystal casting techniques has led to the development of existing nickel-base superalloys to produce materials with optimum mechanical properties in the single crystal condition. As single crystals are known to be anisotropic, a study is needed to determine the general mechanical properties of these materials, and determine the effects of crystal orientation upon them. A study has been carried out to identify the effect of orientation and temperature on the creep and fatigue properties of a development single crystal superalloy, SRR 99. Creep testing and crystal rotation experiments have been made on SRR 99 and an earlier development alloy, SRR 9. Fatigue experiments at elevated temperatures have been carried out on both notched and un-notched specimens of alloy SRR 99. To aid in this analysis, several analytical techniques have been employed including Laue x-ray orientation analysis, measurement of strain by photographic methods and microstructural examination. Crystal rotation experiments have indicated that shear of 1 precipitates by lbrace111rbrace< 112> slip systems is operative during primary creep deformation at temperatures of 750oC and 850oC. The effect of orientation variation obtained by standard casting practices was not found to be significant. Creep rupture was found to be associated with multiple crack initiation from micropores. Fatigue crack initiation in un-notched specimens was found to be related to microporosity and microstructural defects. Failure was predominantly by crystallographic crack growth on lbrace111rbrace planes. The use of linear elastic fracture mechanics to describe fatigue crack propagation in alloy SRR 99 was found to be acceptable at temperatures up to 850oC. Variation of temperature, frequency and crystal orientation was found to have only moderate effect upon crack propagation rates.

The use of enzymes in organic solvents in polytransesterification reactions

The aim of this research project was to identify the factors affecting the porcine pancreatic lipase (PPL.)-catalysed polytransesterification of a diester and a diol in organic solvents. It was hoped that by modifying reaction conditions a commercially acceptable polymer molecular weight (Mn) of 20,000 daltons might be attained. Exploratory investigations were carried out using 1,4-butanediolibis(2,2,2- trichloroethyl) adipate and glutarate systems in diethyl ether, with and without molecular sieves. It was found that molecular sieves promoted the reaction by reducing hydrolysis of the ester end-groups, resulting in polymer molecular weights between 1.2 and 2.2 times greater than those obtainable without molecular sieves. Investigations were then concentrated on the PPL-catalysed polytransesterification of 1,4-butanediol with divinyl adipate. The particular advantage of this system is that the reaction is irreversible. The effects of varying substrate concentration, mass of drying agent, reaction solvent, reaction temperature, mass of enzyme and also enzyme immobilisation on the 1,4-butanediolidivinyl adipate system were investigated. The highest molecular weight polymer obtained for the PPL-catalysed polytransesterification of 1,4-butanedial with divinyl adipate in diethyl ether was Mn -8,000. In higher boiling ether solvents molecular weights as high as Mn -9,200 were obtained for this system at elevated temperatures. It was found that the major factor limiting polymerisation was the low solubility of the polymer in the solvent which resulted in precipitation of the polymer onto the surface of the enzyme.

Oxidation and stabilisation chemistry of metallocene-based polyolefins during melt processing

Metallocene catalyzed linear low density polyethylene (m-LLDPE) is a new generation of olefin copolymer. Based on the more recently developed metallocene-type catalysts, m-LLDPE can be synthesized with exactly controlled short chain branches and stereo-regular microstructure. The unique properties of these polymers have led to their applications in many areas. As a result, it is important to have a good understanding of the oxidation mechanism of m-LLDPE during melt processing in order to develop more effective stabilisation systems and continue to increase the performance of the material. The primary objectives of this work were, firstly, to investigate the oxidative degradation mechanisms of m-LLDPE polymers having different comonomer (I-octene) content during melt processing. Secondly, to examine the effectiveness of some commercial antioxidants on the stabilisation of m-LLDPE melt. A Ziegler-polymerized LLDPE (z-LLDPE) based on the same comonomer was chosen and processed under the same conditions for comparison with the metallocene polymers. The LLDPE polymers were processed using an internal mixer (torque rheometer, TR) and a co-rotating twin-screw extruder (TSE). The effects of processing variables (time, temperature) on the rheological (MI, MWD, rheometry) and molecular (unsaturation type and content, carbonyl compounds, chain branching) characteristics of the processed polymers were examined. It was found that the catalyst type (metallocene or Ziegler) and comonomer content of the polymers have great impact on their oxidative degradation behavior (crosslinking or chain scission) during melt processing. The metallocene polymers mainly underwent chain scission at lower temperature (<220°C) but crosslinking became predominant at higher temperature for both TR and TSE processed polymers. Generally, the more comonomers the m-LLDPE contains, a larger extent of chain scission can be expected. In contrast, crosslinking reactions were shown to be always dominant in the case of the Ziegler LLDPE. Furthermore, it is clear that the molecular weight distribution (MWD) of all LLDPE became broader after processing and tended generally to be broader at elevated temperatures and more extrusion passes. So, it can be concluded that crosslinking and chain scission are temperature dependent and occur simultaneously as competing reactions during melt processing. Vinyl is considered to be the most important unsaturated group leading to polymer crosslinking as its concentration in all the LLDPE decreased after processing. Carbonyl compounds were produced during LLDPE melt processing and ketones were shown to be the most imp0l1ant carbonyl-containing products in all processed polymers. The carbonyl concentration generally increased with temperature and extrusion passes, and the higher carbonyl content fonned in processed z-LLDPE and m-LLDPE polymers having higher comonomer content indicates their higher susceptibility of oxidative degradation. Hindered phenol and lactone antioxidants were shown to be effective in the stabilization of m-LLDPE melt when they were singly used in TSE extrusion. The combination of hindered phenol and phosphite has synergistic effect on m-LLDPE stabilization and the phenol-phosphite-Iactone mixture imparted the polymers with good stability during extrusion, especially for m-LLDPE with higher comonomer content.

An assessment of the performance of high density polyethylene copolymers for natural gas distribution pipes

The total thermoplastics pipe market in west Europe is estimated at 900,000 metric tonnes for 1977 and is projected to grow to some 1.3 million tonnes of predominantly PVC and polyolefins pipe by 1985. By that time, polyethylene for gas distribution pipe and fittings will represent some 30% of the total polyethylene pipe market. The performance characteristics of a high density polyethylene are significantly influenced by both molecular weight and type of comonomer; the major influences being in the long-term hoop stress resistance and the environmental stress cracking resistance. Minor amounts of hexene-1 are more effective than comonomers lower in the homologous series, although there is some sacrifice of density related properties. A synergistic improvement is obtained by combining molecular weight increase with copolymerisation. The Long-term design strength of polyethylene copolymers can be determined from hoop stress measurement at elevated temperatures and by means of a separation factor of approximate value 22, extrapolation can be made to room temperature performance for a water environment. A polyethylene of black composition has a sufficiently improved performance over yellow pigmented pipe to cast doubts on the validity of internationally specifying yellow coded pipe for gas distribution service. The chemical environment (condensate formation) that can exist in natural gas distribution networks has a deleterious effect on the pipe performance the reduction amounting to at least two decades in log time. Desorption of such condensate is very slow and the influence of the more aggressive aromatic components is to lead to premature stress cracking. For natural gas distribution purposes, the design stress rating should be 39 Kg/cm2 for polyethylenes in the molecular weight range of 150 - 200,000 and 55 Kg/cm2 for higher molecular weight materials.

Characterisation and oxidative stability of speciality plant seed oils

The past decade has seen an influx of speciality plant seed oils arriving into the market place. The need to characterise these oils has become an important aspect of the oil industry. The characterisation of the oils allows for the physical and chemical properties of the oil to be determined. Speciality oils were characterised based on their lipid and fatty acid profiles and categorised as monounsaturated rich (oleic acid as the major acyl components e.g. Moringa and Marula oil), linoleic acid rich (Grape seed and Evening Primrose oil) or linolenic acid rich (Flaxseed and Kiwi oil). The quality of the oils was evaluated by determining the free fatty acid content, the peroxide value (that measures initial oxidation) and p-anisidine values (that determines secondary oxidation products containing the carbonyl function). A reference database was constructed for the oils in order to compare batches of oils for their overall quality including oxidative stability. For some of the speciality oils, the stereochemistry of the triacylglycerols was determined. Calophyllum, Coffee, Poppy and Sea Buckthorn oils stereochemistry was determined. The oils were enriched with saturated and/or a monounsaturated fatty acids at position sn-1 and sn-3. The sn-2 position of the four oils was esterified with a polyunsaturated and/or a monounsaturated fatty acid indicating that they follow a typical acylation pathway and no novel acylation activity was evident from these studies (e.g enrichment of saturates at the sn-2 position). The oxidative stability of the oils was evaluated at 18oC and 60oC and the effect of adding a-tocopherol at commercially used level i.e 750ppm was assessed. The addition of 750ppm of a-tocopherol at 18oC increased the oxidative stability of Brown flax, Moringa, Wheat germ and Yangu oils. At 60oC Brown Flax, Manketti and Pomegranate oil polymerised after 48 hours. The addition of 750ppm a-tocopherol delayed the onset of polymerisation by up to 48 hours in Brown Flax seed oil. Pomegranate oil showed a high resistance to oxidation, and was blended into other speciality oils at 1%. Pomegranate oil increased the oxidative stability of Yangu oil at 18oC. The addition of Pomegranate oil to Wheat germ oil at 60oC, decreased the peroxide content by 10%. In Manketti and Brown Flaxseed oil at elevated temperatures, Pomegranate oil delayed the onset of polymerisation. Preliminary studies of Pomegranate oil blending to Moringa and Borage oil showed it to be more effective than a-tocopherol for certain oils. The antioxidant effects observed following the addition of Pomegranate oil may be due to its conjugated linolenic acid fatty acid, punicic acid.

Use of colour image analysis for assessment of fire damaged concrete

The aim of this project was to carry out a fundamental study to assess the potential of colour image analysis for use in investigations of fire damaged concrete. This involved:(a) Quantification (rather than purely visual assessment) of colour change as an indicator of the thermal history of concrete.(b) Quantification of the nature and intensity of crack development as an indication of the thermal history of concrete, supporting and in addition to, colour change observations.(c) Further understanding of changes in the physical and chemical properties of aggregate and mortar matrix after heating.(d) An indication of the relationship between cracking and non-destructive methods of testing e.g. UPV or Schmidt hammer. Results showed that colour image analysis could be used to quantify the colour changes found when concrete is heated. Development of red colour coincided with significant reduction in compressive strength. Such measurements may be used to determine the thermal history of concrete by providing information regarding the temperature distribution that existed at the height of a fire. The actual colours observed depended on the types of cement and aggregate that were used to make the concrete. With some aggregates it may be more appropriate to only analyse the mortar matrix. Petrographic techniques may also be used to determine the nature and density of cracks developing at elevated temperatures and values of crack density correlate well with measurements of residual compressive strength. Small differences in crack density were observed with different cements and aggregates, although good correlations were always found with the residual compressive strength. Taken together these two techniques can provide further useful information for the evaluation of fire damaged concrete. This is especially so since petrographic analysis can also provide information on the quality of the original concrete such as cement content and water / cement ratio. Concretes made with blended cements tended to produce small differences in physical and chemical properties compared to those made with unblended cements. There is some evidence to suggest that a coarsening of pore structure in blended cements may lead to onset of cracking at lower temperatures. The use of DTA/TGA was of little use in assessing the thermal history of concrete made with blended cements. Corner spalling and sloughing off, as observed in columns, was effectively reproduced in tests on small scale specimens and the crack distributions measured. Relationships between compressive strength/cracking and non-destructive methods of testing are discussed and an outline procedure for site investigations of fire damaged concrete is described.

Lateral instability of slender reinforced concrete columns in a fire environment

The research concerns the development and application of an analytical computer program, SAFE-ROC, that models material behaviour and structural behaviour of a slender reinforced concrete column that is part of an overall structure and is subjected to elevated temperatures as a result of exposure to fire. The analysis approach used in SAFE-RCC is non-linear. Computer calculations are used that take account of restraint and continuity, and the interaction of the column with the surrounding structure during the fire. Within a given time step an iterative approach is used to find a deformed shape for the column which results in equilibrium between the forces associated with the external loads and internal stresses and degradation. Non-linear geometric effects are taken into account by updating the geometry of the structure during deformation. The structural response program SAFE-ROC includes a total strain model which takes account of the compatibility of strain due to temperature and loading. The total strain model represents a constitutive law that governs the material behaviour for concrete and steel. The material behaviour models employed for concrete and steel take account of the dimensional changes caused by the temperature differentials and changes in the material mechanical properties with changes in temperature. Non-linear stress-strain laws are used that take account of loading to a strain greater than that corresponding to the peak stress of the concrete stress-strain relation, and model the inelastic deformation associated with unloading of the steel stress-strain relation. The cross section temperatures caused by the fire environment are obtained by a preceding non-linear thermal analysis, a computer program FIRES-T.

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.

Fatigue crack initiation and propagation from defects in aluminium welds

Fatigue crack initiation and propagation in aluminium butt welds has been investigated. It is shown that the initiation of cracks from both buried defects and. from the weld reinforcement may be quantified by predictive laws based on either linear elastic fracture mechanics, or on Neuber's rule of stress and strain ooncentrations. The former is preferable on the grounds of theoretical models of crack tip plasticity, although either may be used as the basis of an effeotive design criteria against crack initiation. Fatigue lives fol1owing initiation were found to follow predictions based on the integration of a Paris type power law. The effect of residual stresses from the welding operation on both initiation and propagation was accounted for by a Forman type equation. This incorporated the notional stress ratio produced by the residual stresses after various heat treatments. A fracture mechanics analysis was found to be useful in describing the fatigue behaviour of the weldments at increased temperatures up to 300°C. It is pointed out, however, that the complex interaction of residual stresses, frequency, and changes in fracture mode necessitate great caution in the application of any general design criteria against crack initiation and growth at elevated. temperatures.