Regarding the higher demand of the total joint replacement (TJR) and revision surgeries in recent years, an implant material should provide much longer lifetime without failure. Nickel titanium (NiTi) is the most popular shape memory alloy in the industry, especially in medical devices due to its unique mechanical properties such as pseudo-elasticity, damping capacity, shape memory and good biocompatibility. However, concerns of nickel ion release of this alloy still exist if it is implanted for a prolonged period of time. Nickel is well known for the possibility of causing allergic response and degeneration of muscle tissue as well as being carcinogenic for the human body beyond a certain threshold. Therefore, drastically improving the surface properties (e.g. wear resistance) of NiTi is a vital step for its adoption as orthopaedic implants. To overcome the above-mentioned risks, different surface treatment techniques have been proposed and investigated, such as Physical Vapour Deposition (PVD), Chemical Vapour Deposition (CVD), ion implantation, plasma spraying, etc. Yet all of these techniques have similar limitations such as high treatment temperature, poor metallurgical bonding between coated film and substrate, and lower flexibility and efficiency. As a result, laser gas nitriding would be an ideal treatment method as it could overcome these drawbacks. Moreover, the shape memory effect and pseudo-elasticity of NiTi from a reversible phase transformation between the martensitic phase and the austenitic phase are very sensitive to heat. Hence, NiTi implant is subjected to the following provisions of the thermo-mechanical treatment process, and this implant provides desired characteristics. It is important to suggest a surface treatment, which would not disturb the original build-in properties. As a result, the low-temperature methods for substrate have to be employed on the surface of NiTi. This present study aims to investigate the feasibility of applying diffusion laser gas nitriding technique to improve the wettability and wear resistance of NiTi as well as establish the optimization technique. The current report summaries the result of laser nitrided NiTi by continuous-wave (CW) fibre laser in nitrogen environment. The microstructure, surface morphology, wettability, wear resistance of the coating layer has been analysed using scanning electron microscopy (SEM), X-ray diffractometry (XRD), sessile drop technique, 3-D profile measurement and reciprocating wear test. The resulting surface layer is free of cracks, and the wetting behaviour is better than the bare NiTi. The wear resistance of the optimised nitride sample with different hatch patterns is also evaluated using reciprocating wear testing against ultra-high-molecular-weight polyethylene (UHMWPE) in Hanks’ solution. The results indicate that the wear rates of the nitride samples and the UHMWPE counter-part were both significantly reduced. It is concluded that the diffusion laser gas nitriding is a potential low-temperature treatment technique to improve the surface properties of NiTi. This technique can be applied to a femoral head or a bone fixation plates with relatively large surface area and movable components.

Laser surface modification involves rapid melting and solidification is an elegant technique used for locally tailoring the surface morphology of alumina in order to enhance its abrasive characteristics. COMSOL Multiphysics® based heat transfer modeling and experimental approaches were designed and used in this study for single and multiple laser tracks to achieve densely-packed multi-facet grains via temperature history, cooling rate, solidification, scanning electron micrographs, and wear rate. Multi-facet grains were produced at the center of laser track with primary dendrites extending toward the edge of single laser track. The multiple laser tracks study indicates the grain/dendrite size increases as the laser energy density increases resulting in multiplying the abrasive edges which in turn enhance the abrasive qualities.

Laser surface modification of AZ31B Magnesium alloy changes surface composition and roughness to provide improved surface bio-wettability. Laser processing resulted in phase transformation and grain refinement due to rapid quenching effect. Furthermore, instantaneous heating and vaporization resulted in removal of material, leading the textured surface generation. A study was conducted on a continuum-wave diode-pumped ytterbium laser to create multiple tracks for determining the resulting bio-wettability. Five different laser input powers were processed on Mg alloy, and then examined by XRD, SEM, optical profilometer, and contact angle measurement. A finite element based heat transfer model was developed using COMSOL multi-physics package to predict the temperature evolution during laser processing. The thermal histories predicted by the model are used to evaluate the cooling rates and solidification rate and the associated changes in the microstructure. The surface energy of laser surface modification samples can be calculated by measuring the contact angle with 3 different standard liquid (D.I water, Formamide, and 1-Bromonaphthalen). The bio-wettability of the laser surface modification samples can be conducted by simulated body fluid contact angle measurement. The results of SEM, 3D morphology, XRD, and contact angle measurement show that the grain size and roughness play role for wetting behavior of laser processing Mg samples. Surface with low roughness and large grain size performs as hydrophilicity. On the contrast, surface with high roughness and small grain size performs as hydrophobicity.

The present work studies the microstructure and corrosion behaviour of 25 vol.% SiCp/AA2124-T4 metal matrix composites (MMCs) and AA2124-T4 aluminium alloy; and also the capability of excimer laser surface melting (LSM) to improve the corrosion resistance of the SiCp/AA2124 MMC and the monolithic alloy (MA). Microstructural characterization has shown significant influence of the presence and size of SiC particles on the fine Al2Cu precipitate and Mg segregation at SiC/Al interfacial regions. Such precipitates are revealed to be active sites for corrosion initiation in the MMCs, while the preferential sites for corrosion initiation in the MA are the coarse intermetallics. Corrosion evaluation performed in a 0.6 M NaCl solution suggests that the corrosion resistance of the MMC reinforced with micrometre-sized SiC particles is inferior to that of the MA and the MMC reinforced with submicrometre-sized SiC particles. The submicrometre-sized SiC particles have little adverse effect on the corrosion resistance of the MMC due to the reduced interfacial precipitates. Thin films of up to several micrometres have been achieved by excimer LSM on both the MMC and the MA. The surface roughness and the thickness of the melted layer increase with increasing laser fluence. High number of pulses (40 P) results in significant porosity in the MA and networks of cracking in the MMC. A homogeneous layer without chemical segregation except the Cu-rich segregation bands has been obtained on the MA; while complex microstructures are observed for the MMC, including the Cu-rich segregation bands, Al-Si eutectic structure and microsegregation-free structure laid in sequence from the bottom of the melted layer to the top surface. The modelling work suggest that the presence of SiC particles gives rise in high temperatures in the melt pool, which is useful to explain the materials responses upon laser irradiation, such as decomposition of SiC, evaporation of matrix alloy, and oxides formation. The fast cooling rate up to 1011 K/s is responsible for the formation of microsegregation-free structure. Corrosion evaluation has indicated improvement of corrosion resistance of the MMC and the MA after excimer LSM due to the reduction of the intermetallics. For the laser-melted MA, the corrosion behaviour is governed by the surface morphology and the porosity. The significant rippled structure obtained under high laser fluence could lead to crevice corrosion in the valley between the ripples whilst the pores could provide penetrating routes for the chloride solution to reach the Cu-rich segregation bands, leading to the delamination of the melted layer. For the laser-melted MMC, corrosion mainly initiated at the SiC remnants, which are rich in Si. The corrosion sites of the laser-melted MMC are in the form of small cracked blisters.

This thesis describes the formation of and applications of self-assembled structures on metals. Primarily the focus of this PhD project is on the formation of surfaces structures on stainless steel (AISI 304) but other metals have been studied. Laser generated surface structures have been applied to the modification of wettability and reflectivity with a view towards developing these processes for industrial applications. Compared to conventional techniques for the modification of wettabililty, lasers offer the advantage of being a relatively simple technique for the modification of surface structure, reducing the need for complex processes. It is hoped that investigations into the reduction of surface reflectivity will have applications in the conversion of solar energy into useable power in the form of solar thermal energy. The production of self assembled structures is demonstrated using diode pumped solid state (DPSS) Nd:YVO4 lasers operating at wavelengths of 532 and 1064 nm. It is shown that the production of surface microstructures is highly dependant on the correct laser fluence and requires multiple pulses and processing passes. At 1064 nm wavelengths, it has been found highly reproducible surface structures can be formed by carefully controlling laser fluence and scanning speed while keeping the optical arrangement relatively simple. In addition to microstructure formation, the use of ultrafast femtosecond lasers, operating at 400 and 800 nm wavelengths has verified the production of laser induced periodic surface structures. Additionally, the stationary method used to produce these surfaces has been adapted to cover large surface areas with sub wavelength ripple structures with periods of ~295nm and 600nm. Applications of laser surface microstructures on metals have been studied in an effort to produce hydrophobic and superhydrophobic surfaces on metals. It has been found that the roughness change produced by laser processing induces composite wetting when water droplets are introduced to the surface. Contact angle measurements and small angle XRD analysis of laser processed stainless steel (AISI 304) have shown that surface wettability decreased over a period of approximately one month, leading to steady contact angles of over 140°. This is attributed to the formation of a magnetite (Fe3O4) oxide layer in the period after laser processing. The effect of surface microstructure on surface reflectivity has also been studied. It was found that laser induced surface microstructures on copper can decrease surface reflectivity by almost 90%. A comparative study of the effects of surface roughness and chemistry on the optical absorption of copper is given, finding that these surfaces are competitive with contemporary coatings.

Internal combustion (IC) engines used in road transport applications employ pistons to convert gas pressure into mechanical work. Frictional losses abound within IC engines, where only 38- 51% of available fuel energy results in useful mechanical work. Piston-bore and ring-bore conjunctions are fairly equally responsible for circa 30% of all engine friction - equivalent to 1.6% of the input fuel each. Therefore, reduction in piston assembly friction would have a direct impact on specific performance and / or fuel consumption. In motorsport, power outputs and duty cycles greatly exceed road applications. Consequently, these engines have a shorter useful life and a high premium is placed on measures which would increase the output power without further reducing engine life. Reduction of friction offers such an opportunity, which may be achieved by improved tribological design in terms of reduced contact area or enhanced lubrication or both. However, the developments in the motorsport sector are typically reactive due to a lack of relative performance or an ad-hoc reliance, based upon a limited number of actual engine tests in order to determine if any improvement can be achieved as the result of some predetermined action. A representative scientific model generally does not exist and as such, investigated parameters are often driven by the supply chain with the promise of improvement. In cylinder investigations are usually limited to bore surface finish, bore and piston geometrical form, piston skirt coatings and the lubricant employed. Of these investigated areas newly emerging surface coatings are arguably seen as predominate. This thesis highlights a scientific approach which has been developed to optimise piston-bore performance. Pre-existing methods of screening and benchmarking alterations have been retained such as engine testing. However, this has been placed in the context of validation of scientifically driven development. A multi-physics numerical model is developed, which combines piston inertial dynamics, as well as thermo-structural strains within a thermoelastohydrodynamic tribological framework. Experimental tests were performed to validate the findings of numerical models. These tests include film thickness measurement and incylinder friction measurement, as well as the numerically-indicated beneficial surface modifications. Experimental testing was performed on an in-house motored engine at Capricorn Automotive, a dynamometer mounted single-cylinder 'fired' engine at Loughborough University, as well as on other engines belonging to third party clients of Capricorn. The diversity of tests was to ascertain the generic nature of any findings. The multi-physics multi-scale combined numerical-experimental investigation is the main contribution of this thesis to knowledge. One major finding of the thesis is the significant role that bulk thermo-structural deformation makes on the contact conformity of piston skirt to cylinder liner contact, thus advising piston skirt design. Another key finding is the beneficial role of textured surfaces in the retention of reservoirs of lubricant, thus reducing friction.

The control of cell adhesion to synthetic polymers is a key factor in tissue engineering, resting on the ability to direct specific cell types to adhere and proliferate in order to stimulate tissue reconstruction. But often the surface properties are compromised for the sake of the bulk properties, leading to surfaces that do not support sufficiently the level of bioactivity required and accordingly the polymeric biomaterial will fail clinically. Laser treatment offers a unique means of enhancing the osteoblast cell response of the surface of a polymeric biomaterial, whilst keeping the already sufficient bulk properties intact. To this end, infra-red (IR) and ultraviolet (UV) lasers have been employed to modify the wettability characteristics of nylon 6,6, as wetting is often the primary factor dictating the adhesion and bonding potential of materials, as a route to enhancing the surface in terms of osteoblast cell response. What is more, modifying wettability characteristics in this way is a highly attractive means of estimating the biofunctionality of a polymer. IR (CO2) and UV (F2 and KrF excimer) lasers were employed to carry out two different processes: laser whole area irradiative processing and laser-induced patterning. With both CO2 and the excimer lasers changes in the wettability characteristics could be effected with subsequent enhancement of osteoblast cell response. This was also the case with both laser-induced patterning and laser whole area irradiative processing. Essentially, an approach has been established whereby the osteoblast cell response on the surfaces of laser treated nylon 6,6 can be predicted through the laser-induced wettability characteristics modification, particularly for the laser whole area irradiative processed nylon 6,6. This ultimately allows one to determine the osteoblast cell response of the laser surface treated nylon 6,6 surfaces directly from the laser operating parameters. In concurrence with established wetting theory the laser whole area irradiative processing of the nylon 6,6 surfaces caused increased surface roughness, increased surface oxygen content, increased polar component, γP , and increased total surface energy, γT ; thereby generating surfaces displaying reduced contact angle, θ, making the nylon 6,6 surfaces more hydrophilic. The laser-induced patterned samples differed from current theory insofar as the nylon 6,6 surfaces became less hydrophilic due to an increase in θ despite an increase in surface roughness, an increase in surface oxygen content, an increase in γP and an increase in γT . This phenomena can be explained by the transition in wetting regimes from a Wenzel regime to a mixed-state wetting regime. Nevertheless, collation of the wettability characteristics results revealed that θ was a strong correlative decreasing function of both γP and γT , indicating that surface energy played a large role in determining the wetting nature of the nylon 6,6. It was found that for all laser whole area irradiative processed nylon 6,6 surfaces the osteoblast cell response was an increasing correlative and therefore predictive function of θ and was a decreasing function of γP . To an extent, the surface oxygen content and surface roughness could be used indirectly to foretell the osteoblast cell response of the nylon 6,6 surfaces. This is on account of the CO2 and KrF excimer laser whole area irradiative processing bringing about increased surface toxicity, which above a certain level hindered the osteoblast cell response. For the laser-induced patterned nylon 6,6 samples there did not appear to be any particular correlative trend between the modified surface parameters and osteoblast cell response. This can be accounted for by the transition in wetting regimes. Another important factor is that cell morphologies were modulated over all samples which suggests that varying surface parameters on account of laser surface treatment gave rise to variations in cell signaling. It was determined that θ, γP and γT all had very strong correlative relationships with the cytotoxicity. The cytotoxicity reduced upon an increase in θ until a minimum constant was achieved, whereas the cytotoxicity remained constant at low γP and γT until a point at which the cytotoxicity began to increase. These results are noteworthy as they allow one to deduce that, with constant cytotoxicity levels, the osteoblast cell response appeared to be modulated by the wettability characteristics. But once the cytotoxicity increased, the toxicity began to dominate and so negated the identified positive wettability characteristic correlations with osteoblast cell response. Practically, the surface roughness and surface oxygen content could be implemented indirectly to estimate the cytotoxicity. Increase in cytotoxicity was the result of the laser processing with higher fluences generating excessive melting. As a result of this, it is possible to deduce that there was a maximum threshold fluence, beyond which the toxicity of the nylon 6,6 began to dominate, giving rise to a less enhanced osteoblast cell response. On account of the correlative trends which have been identified between the laser surface treatment, wettability characteristics and osteoblast cell response of nylon 6,6 it is likely for one to have the ability to estimate the osteoblast cell response in vitro. This is significant as it indicates that laser surface modification of polymeric materials could have tremendous potential for application within the field of regenerative medicine.

A comprehensive, transient three-dimensional model of a single-pass laser surface alloying process has been developed and used to examine the heat, momentum and species transport phenomena. A numerical study is performed in a co-ordinate system moving with the laser at a constant scanning speed. In this model a fixed grid enthalpy-porosity approach is used, which predicts the evolutionary pool development. In this model two extreme cases of alloying element and base metal combinations are considered based on their relative melting points. One extreme case is for an alloying element with its melting point much lower than that of the base metal. In this case the alloying element melts almost instantaneously. Hence it is assumed that the alloying element introduced on the melt pool surface is in the molten state. Thus, while solving the species conservation equation a species flux condition is used on the entire melt pool surface. This case is analysed for aluminium alloying element on iron base metal. The final species distribution in the melt pool as well as in the solidified alloy is predicted. The other extreme case is studied for an alloying element with its melting point relatively higher than that of the base metal. In this case all the alloying element particles on the melt pool surface will not melt. Only those particles which fall in the region on the melt pool surface where the local temperature is higher than the melting point of the alloying element will melt. The particles which fall away from this region are advected into the melt pool, due to a strong Marangoni convection on the melt pool surface. If a particle is advected into the inner region in the melt pool (where the temperature is higher than its melting point), it starts melting and thus the molten species mass gets distributed. Hence, the species flux condition at the entire surface of the melt pool is not valid. The particles are tracked in the melt pool by assuming the alloying particles to be spherical in shape and moving without any relative velocity with the surrounding fluid. Simultaneously, the temperature field inside the spherical particle is solved by assuming its surface temperature to be the local temperature in the melt pool. The amount of particle mass that fuses as it passes through a particular control volume is noted. The same procedure is repeated for a large number of particles initiated at various locations on the pool surface, and a statistical distribution of the species mass source in the entire pool is obtained. This species mass source distribution is then used to solve the species conservation equation. Nickel alloying element on aluminium base metal is used to illustrate this case. The numerical results obtained from the two cases are compared with the available experimental results. A qualitative matching is found between the numerical and experimental results.

The increased demand in stringent requirements on engineered surfaces in the aerospace and manufacturing industries drove the need for developing advanced surface engineering techniques such as chemical etching, plasma etching, corona discharge and laser surface texturing in order to alter material surface physical and chemical properties. Among these techniques, laser surface texturing has been identified as one of the most efficient and effective surface treatment/ texturing techniques which utilizes laser ablation to meet the demand of practical engineering requirements. This thesis details three practical engineering challenges in the field of paint adhesion, dust adhesion and tribology performance of SPF sheet forming dies in which case the problems and motivation for development came from projects by industrial partner collaborations with BAe Systems, Rolls-Royce and Dyson Ltd. The proposed solutions to these challenges are formulated around laser surface texturing techniques using excimer and femtosecond lasers on three engineering materials which are CFRP, ABS polymer and HR4 nickel alloy. As ablation is the main mechanism used in laser surface texturing techniques in achieving surface property changes, the understanding of laser beam interaction with materials is crucial. The fundamental understanding of laser beam interaction with different materials has been researched since the use of lasers in practical engineering applications by which laser material interaction parameters such as ablation threshold, incubation coefficient and optical penetration depth are of primary interest in addition to the ablation rate. Currently the published literatures are either material specific or laser specific with minimal or zero comparison between different types of lasers and materials as such which limits the understanding of laser beam interaction with materials. In addition, laser beam interaction with polymers has always been done using ultraviolet wavelength lasers. In this thesis, the interaction between two types of lasers and three types of materials which includes metals and polymers are presented through comparison and discussion between different interactions. It has been discovered that the ablation threshold value is lower for ABSinteraction with excimer laser as compared to the interaction with femtosecond laser due to the difference in the ablation mechanism. The optical penetration depth value is higher for ABS interaction with the excimer laser as compared to the interaction with the femtosecond laser due to differences in the photon energy of the laser beam of different wavelength. Two ablation rate curves were identified on ABS interaction with infrared wavelength femtosecond laser beams which has not been reported before. Chemical composition of the laser treated layer changes through chain scission process, creating free radical carbons that reacted with oxygen, nitrogen and water vapour in air creating oxygen and nitrogen rich functional groups which increased with increasing laser fluence and number of pulses. Laser ablation is known for its capability of altering surface morphology and surface chemistry of materials through excitation of electrons causing bond scission or melt where materials are vaporised, ejected or undergo chemical compositional changes. In the case of polymers, addition of oxygen and nitrogen rich functional groups are identified whereas in the case of metals, changes in crystallographic, orientation and oxidation states are identified. Such changes are deemed ideal for applications such as adhesion where it is mainly used for bonding and joining of similar or dissimilar materials. In this research, excimer laser surface treatment showed improvement in CFRP paint adhesion where a better adhesion is achieved than sand-papered surfaces. Paint adhesion of CFRP surfaces is affected by surface contaminants, surface chemical composition and surface roughness where the degree of inuence is in the respective order. In addition, excimer and femtosecond laser surface treated ABS also improved dust adhesion. The main factors that affect the ABS surface dust adhesion performance are surface roughness and surface chemical composition. The increase in surface roughness increases the surface area available for dust to adhere to. In addition, it also increases the drag coefficient of the air flow results in a higher removal force exerted by the air flow onto the dust particles through changes in the localised aerodynamic flow. The increase in polar functional groups increases the adhesion of the dust particles onto the surface due to an induced dipole moment by the charged dust particles. Laser micro-dimpled surfaces have been reported to be effective in reducing friction coefficient and wear rate of surfaces under oil lubricated conformal contact conditions where the dimples act as reservoirs to store lubricant and wear particles. But such surfaces have not been extensively researched under non-conformal contact conditions for different lubricated environments. In addition, there are contradictory results found between published literatures which observe under similar wear environments and conditions but with different dimple geometry. Hence a detailed investigation on dimpled surfaces under non-conformal contact conditions is being carried out. Laser surface texturing of 100 μm size dimples shows a reduction in nickel alloy wear rate under dry and oil lubricated environments. A higher dimple area ratio reduces the wear rate under dry condition with abrasive wear as the main wear mechanism. Under oil lubricated environments, the friction coefficient is dependent on the surface contact pressure, sliding speed and the viscosity of the lubricant and the wear rate is dependent on the film thickness which correlates to the friction coefficient. The wear rate of a dimpled surface is dependent on three factors which are the dimple diameter to contact area diameter ratio, depth of the dimple produced and the density of the dimples. Positive results are obtained in all three engineering applications indicating the feasibility of laser surface texturing techniques in providing suitable material surface properties for these applications.

Les émissions de polluants dans l’atmosphère représentent l’un des objectifs majeurs à l'heure actuelle. Dans le domaine automobile, la réduction des émissions de CO2 repose en partie sur l’amélioration du rendement moteur. Pour ce faire, ces travaux de thèse sur la texturation de surface à micro et nano échelle proposent de diminuer les pertes par frottements dans les moteurs thermiques alternatifs à combustion interne. Le poste moteur retenu dans cette thèse est le segment/piston/chemise car près de 40 % des pertes par frottement y sont générées. On s’intéresse à la texturation par LASER femtoseconde de cavités sur la surface du segment coup de feu. Le comportement tribologique de surfaces texturées est étudié en régime ElastoHydroDynamique (EHD) et Limite. En régime EHD, la capacité de formation d’un film lubrifiant et le contrôle du frottement en surface texturée indique un comportement tribologique dépendant du couplage entre les paramètres expérimentaux - cinématique des surfaces, pression de contact, taux de rétention en huile et temps de résidence des textures dans le contact et les paramètres géométriques - diamètre, profondeur, densité de textures. En régime Limite, l’influence des textures sur le comportement tribologique a permis de confirmer l’hypothèse sur le rôle de piégeage des débris par les cavités et de mettre en évidence des configurations de réseaux réduisant le coefficient de frottement pour des profondeurs faibles. / Nowadays pollutant emissions in the atmosphere are at stake. In the field of automotive industry, the reduction of CO2 emissions lies mostly on improving engine efficiency. This study about textured surface on micro- and nano-scale aims to diminish the friction losses in internal combustion engine.The main element is the piston ring pack because of the creation of 40 percent in friction losses. This analysis consists in LASER texturing with cavities on the surface of the first piston ring. The tribological behavior of textured surfaces is lead in Boundary and ElastoHydroDynamic (EHD) regime. In EHD regime the impact on load capacity of lubricant and frictional behavior in textured surface show linking between experimental parameters as surfaces cinematic, contact pressure, retention volume of oil, the dwelling time of cavities and the geometrical parameters as diameter, cavity depth and cavity density. In Boundary lubrication, the effect of cavities on tribological behavior has led to confirm the hypothesis of trapped debris in the cavities and to make in evidence swallow network of cavities reducing friction coefficient.