Advanced ceramic materials have found many new applications in the automotive and other industries. To satisfy demands of higher temperatures and inert surfaces, new lubrication methods for these ceramics need explored and evaluated. This thesis focuses on a boundary lubrication method termed tribopolymerization -- the formation of polymers at the tribological interphase. The research evaluated new high-temperature classes of anti-wear additives. The work involved experiments on steel and alumina material pairs with a pin-on-disk tribometer used to explore the anti-wear capabilities of selected additives in the liquid phase at concentrations of 1% by weight in hexadecane. New additives included aromatic compounds with various pendant groups adding the design functionality necessary for in-situ polymerization. The amino, hydroxyl, acid, and ester functional groups underwent studies across several aromatic molecular compositions while new heterocyclic additives, in particular the readily available lactams, underwent exploratory tests as a new class under the tribopolymerization design approach. In concentrations of 1%, additives showed significant wear reductions of up to 99.9 %. Anti-wear behavior persisted in select cases at concentrations as low as 0.1% by weight. Compounds from two new classes demonstrated anti-wear behavior at 6x the frictional heat generation of standard exploratory conditions. This surprising effect partially filled a void in the effective range of operating conditions between 0.25 m/s, 40 N and 1.0 m/s, 160 N. Earlier work by Tritt found a complete absence of anti-wear behavior for the previous additive classes at the high-speed conditions. In addition, several individual compounds constituent to an A-R-A + B-R'-B condensation polymerization reaction demonstrated significant anti-wear behavior when used alone. In particular, the compound BTDA from DuPont's Kapton® exhibited higher wear reductions than any other new additive. These findings support tribopolymerization as an effective approach to boundary lubricant design. Low wear was often associated with an attached reaction debris layer. This finding is consistent with previous work involving tribopolymerization anti-wear additives with ceramics. Further research into the roles of the debris layer and tribochemistry will help in understanding the complex anti-wear behavior of these new high-temperature additive classes. / Master of Science

This paper aims to create a hard modification layer of WC/Co/Fe on the surface of SKD11 work steel by using a new closed-type method of surface electrical discharge coating with the self-made tool electrode and CNC electrical discharge machine. The tool electrode is the composition of a semi-sintered powder compacted electrode and a cooper rod. The sintered powder compacted electrode making process is first to mix the WC/Co and Fe powders uniformly at 8:1, 4:1, 2:1 and 1:1 in weight ratio. Continually, it will form the cylinder of 8mm in diameter and 18mm in length approximately by compacting in different pressure (50~200 MPa) and sintering temperature (300~900 ¢J). The EDM condition is 1~12A discharge current, 25~500£gs pulse time, and 50% duty factor. The electrical discharge machining is proceeding in kerosene with tool electrode as cathode and workpiece as anode. The result is as following. It can be concluded that the best condition to fabricate the sintered powder compacted electrode is 1:1 in weight ratio between WC/Co and Fe powders; with 200Mpa compacting pressure and sintering temperature at 900¢J, which results in lowest electrical resistivity. Under such condition, the area covered ratio can reach 100% at best EDM condition, which is pulse time £non = 50 £gs, rest time £noff = 50 £gs, 8A in current and 1.5 min in machining time. The surface hardness of workpiece increases with machining time. The surface hardness dramatically increases to Hv1500 as machining time over 1.5 min. The hardness of modification layer equals to the WC/Co particle itself which brings to the best wear ability. Moreover, the hardness of under surface in between 48 £gm is much higher than it of the SKD11 work steel. The hardness in between 30 £gm can reach up to Hv1200 in particular. The hardness of surface modification layer increases linearly with machining time. However, the limit of surface modification layer is about 30 £gm, and the needed time is below 5 min.

Made available in DSpace on 2014-06-11T19:28:20Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-03-05Bitstream added on 2014-06-13T19:57:38Z : No. of bitstreams: 1 araujojunior_ib_me_bauru.pdf: 1185170 bytes, checksum: e49c1ae91dff4591b5bc770366352cc9 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A indústria busca uma melhor otimização e performance de seus equipamentos, há muito notou-se a importância da contenção do desgaste para o aumento de vida útil dos componentes de máquinas. Em condições operacionais onde há o desgaste por abrasão, comumente faz-se o endurecimento da camada superficial ou a aplicação de uma liga mais nobre e de dureza mais elevada, visando conter este desgaste. A técnica também é chamada de revestimento. Entender melhor os parâmetros que influenciam nos resultados da aplicação destes revestimentos torna-se importante possibilitando menores perdas e uma maior economia, pois busca-se como alvo trabalhar com a melhor performance do revestimento. Objetivou-se neste trabalho o estudo das ligas a base de Cobalto que são aplicadas cada vez mais rotineiramente nas indústrias petroquímicas, onde os componentes e órgãos de máquinas estão expostos a condições severas de desgaste por abrasão e corrosão além da severidade dos trabalhos a altas temperaturas e pressão. Relacionando o desgaste, as ligas a base de Cobalto possuem uma posição destacada e a liga é conhecida comercialmente como “Stellite 6”. Em alguns trabalhos é chamada também de liga coringa por sua versatilidade e destaque em especial. Neste trabalho procurou-se variar as velocidades de resfriamento em cinco patamares, analisou-se a influência da diluição na micro-dureza e os efeitos da variação da velocidade de resfriamento no mecanismo de endurecimento. A aplicação do revestimento ocorreu em três camadas através do processo TIG. Verificamos ainda a interferência da diluição na dureza em cada camada de revestimento. A terceira e última camada foi a que apresentou maior dureza devido à menor diluição com o metal base principalmente no corpo de prova que possuía à menor velocidade de resfriamento devido ao tempo para a formação de precipitados e carbonetos na liga metálica. / The industry searchs a better optimization and performance of their equipment, long noted the importance of containment to increase the wear life of components of machines. In operating conditions where there is wear by abrasion, usually it is the hardening of the surface layer or the application of a more noble alloy and high hardness, wear it to contain. The technique also called hardfacing. Better understand the parameters that influence the results of applying these coatings becomes important because it enables lower losses and greater economy as it seeks to target work with the best performance of the coating. The objective of this research is complements the study of cobalt-based alloys that are applied more routinely in petrochemical industries, where the component units and machines are exposed to severe conditions of wear by abrasion and corrosion than the severity of the work at high temperatures and pressure. Relating the wear, the cobalt-based alloys have a prominent position and the league is known commercially as “Stellite 6”. Some work is also called the league wildcard for its versatility and highlight in particular. In this work we have tried to vary the speed of cooling in five steps, looked up the influence of dilution on micro hardness and the effects of variation in the rate of cooling in the hardening mechanism. The application of the coating occurred in three layers using the TIG process. We note also the interference of dilution in hardness in each layer of coating. The third and final layer was the one with higher hardness due to less dilution with the base metal mainly in the body of evidence that had the lowest rate of cooling due to the time for the formation of precipitates and carbides in the metal.

Detonation gun coatings of tungsten carbide have been widely recognised as one of the most effective anti-wear coatings for oilfield applications. However, very little fundamental tribological information exists for the material, which hinders coating development and the evolution of correct specifications. This study redresses this problem by conducting adhesive, abrasive and erosive tests upon the coating and relating the findings to the coated microstructure. The intention has been to simulate the in-service behaviour of parallel gate valves, which are used primarily to control flow in remote locations where reliability and freedom from maintenance are essential. Although problems with such valves are rare, costs associated with replacement are exceptionally high and therefore a high research priority has been placed on valves of this type. Currently, new designs of valve are tested using a pipe loop rig at BP Research Centre. However, such tests are both expensive and time consuming and with the increasing desire to bring products to market more quickly an alternative is sought. Probably, the area offering most scope for improvement is in material specification of the sealing surfaces and this work sets out to produce a first stage selection procedure for candidate materials. Uniquely, the study has taken one component, systematically categorised its failure mechanisms using non-destructive replication techniques and then reproduced them in the laboratory. The failure analysis has pointed to three-body abrasion, erosion and adhesion being the dominant failure modes and therefore, a suite of tribo-test methods have been developed to replicate them These are namely reciprocating diamond-on-flat, slurry erosion and reciprocating pin-on-plate tests. The material studied was a proprietary detonation gun coating of tungsten carbide, LW45, which is currently the most popular seal facing material specified for gate valves. A conformal contact geometry was chosen for the reciprocating pin-on-plate tests and problems with alignment were overcome by using a pre-test running-in procedure with 1 μm metallographic paste. Wear of LW45 occurring during the pin-on-plate test was not affected by test speed over the range selected, but was highly dependent upon load. Four different categories ranging from minimal wear to catastrophic wear have been identified. Extensive post test analysis using optical and scanning electron microscopy has further classified the failure that occurs into two groups, termed mild and severe. In the mild regime wear occurs by preferential removal of the binder phase, which is minimised on further sliding by protruding carbide particles. Eventually sufficient binder is removed for carbide fall-out to occur, upon which the cycle is repeated. A greater wear volume is produced by the severe wear mechanism which is caused by the interlinking of cracks present within the microstructure of the coating. To ensure operation in the mild regime, continuous sliding under operating pressures of above 7.84 MPa should be avoided. Abrasive wear simulated by the diamond-on-flat test increased with load. However, the failure mechanisms produced were independent of load and consist of a combination of plastic deformation and brittle fracture with plastic deformation representing the rate controlling step in the wear process. Slurry erosion tests have shown that LW45 wears by a brittle erosive mechanism and is therefore best able to resist erosion at low impingement angles. The volume loss per particle impact for LW45 is proportional to the kinetic energy of the impinging particles. The failure mechanism involved the growth of cracks in the microstructure by a fatigue action eventually leading to crack interlinking and material fall out. For all wear conditions, it is suggested that the removal of microcracking from the coating microstructure will lead to significant improvements in wear performance. A simplified design guide has been produced that gives a weighted importance to the various failure modes attributable to the respective tests. A significant improvement in performance was recorded by LW45 in comparison to typical substrate materials such as AISI 410 and Ferralium F255 stainless steels.

Lubrication is critical in order to achieve high efficiency and reliability of machine elements such as gears, bearings, and other moving mechanical assemblies (MMA). In space applications, tribological properties of lubricants are quickly growing more important. Traditional space systems such as satellites imply MMA such as gyroscopes, antenna pointing mechanisms, and solar array drives. These MMA operate in high vacuum (<10-5 Pa) under lightly loaded conditions. Modern space missions on the other hand, such as remotely operated vehicles used for in-situ Mars exploration relies on different types of MMA. In these robotic systems, electromechanical actuators are being used extensively to provide controlled motion. Gears and bearings in these actuators operate in an atmosphere mainly consisting of CO2 at ~10+3 Pa under heavily loaded contact conditions. In these conditions, the tribosystem is likely to operate in the boundary lubricated regime, with consequent risk of high friction and wear. High molecular weight fluids have significant heritage in space because of their low vapor pressure. They are currently employed as lubricants in a wide range of space applications, as they meet high demands on resistance to vacuum outgassing. Unfortunately, the large molecules are susceptible to degradation under heavy load. Ionic liquids (ILs) on the other hand, are synthetic fluids that consist entirely of ion pairs with opposing charge. The resulting ion bonds enable inherently low vapor pressure of the fluid without the need for a high molecular weight. For this reason ILs have been advocated as potential lubricants for space applications, but so far compatibility issues have hampered their use as lubricants. Countless IL variations are possible, and solutions are thus likely to exist. Constituent ions can be designed individually and combined in various configurations. However, the fundamental understanding of the lubricating mechanism of ionic liquids is still incomplete, and consequently the optimum molecular structure for IL lubricants remain unknown. In this thesis, a stepwise approach to molecular design of IL lubricants is described, and the resulting hydrocarbon-mimicking ionic liquids are evaluated in tribological experiments. In this thesis, the experiments focus on tribological performance, using steel-steel tribopairs in air environment under boundary lubrication (Paper I). Boundary film formation under a range of contact pressures and temperatures, is analyzed after tribotesting by optical profilometry, scanning electron microscopy (SEM), and energy dispersive X- iii ray spectroscopy (EDS) in Paper II. The analysis reveal formation of a highly effective boundary film based on silicate, that can be further enhanced by amine additives. This thesis demonstrates the feasibility of improving tribological performance of ionic liquids by molecular design. / Projekt: Rymdforskarskolan 2015

Grâce à ses propriétés d’antioxydant, d’anti-usure et éventuellement d’extrême pression le dithiophosphate de zinc (ZDDP) fait partie des additifs les plus utilisés dans les lubrifiants pour moteurs thermiques. De nos jours, dans un souci de respect de l’environnement, de nouveaux lubrifiants possédant de bonnes performances en lubrification (frottement faible et usure limitée) sont développés en prenant compte des limitations d’utilisations actuelles du ZDDP. L’idée étant de réduire dans ceux-ci les teneurs en phosphore et soufre (Normes euros VI), éléments essentiels du ZDDP qui endommagent les pots catalytiques. L’objectif de cette thèse est l’étude du comportement tribologique du phosphate de zinc di alkyl (ZP) en comparaison avec le ZDDP. La méthodologie expérimentale étudiée pour comprendre le mécanisme d’action de ces additifs, associe des essais de frottement à descaractérisations physico-chimiques des surfaces frottantes après essais.Cette comparaison a été effectuée en fonction de la température (25°C et 100°C), la vitesse de glissement (25, 50 et 100 mm/s) et la concentration en additif (200 et 600 ppm dephosphore). Les meilleures actions anti-usure sont obtenues avec le ZDDP pour une température de 100°C et une vitesse de glissement de 100 mm/s et le ZP pour une température de 25°C et une vitesse de glissement de 25 mm/s. Les analyses de surface XPS, AES, XANES et MET-EDX ont permis de mettre en évidence la présence d’un film protecteur constitué principalement de phosphate de zinc, ceci pour les deux additifs.Une synergie de comportement tribologique a été mise en évidence avec un lubrifiantconstitué de ZP (usure faible) et d’oléate d’urée (frottement faible). Des essais complémentaires sur un tribomètre dynamique ont permis d’étudier le niveau de frottement du tribofilm formé à partir du ZDDP. Le caractère visqueux du tribofilm de ZDDP a été mis en évidence. / Thanks to its antioxidant, anti-wear and extreme pressure properties, zinc dialkyldithiophosphate (ZDDP) is nowadays the most used anti-wear additives in engine oil. Due to environmental protection concerns, new lubricants with good tribological performances (low friction and low wear) are developed. This research aims to evaluate the current limitations of ZDDP and to find alternative environmentally friendly solutions. Thus, the target is to reduce the quantity of phosphorus and sulphur in lubricants, two essential elements of ZDDP molecule that damage catalytic. The objective of this thesis is to study tribological behavior of zinc phosphate di alkyl (ZP) in comparison to ZDDP. The experimental method performed is the coupling of friction test with surface physico-chemical characterisation of rubbing surface after tests.This comparison carried out according to the temperature (25°C and 100°C), the sliding speed (25, 50, 100 mm/s) and additives concentrations (200 and 600 ppm). The best anti-wear efficiency is obtained with the ZDDP additive at 100°C - 100 mm/s and with the ZP at 25°C - 25 mm/s. For both additives and under these conditions, tribofilms are mainly made of zinc phosphate.A tribological synergy are obtained with a lubricant contained ZP (low wear) and oleyl urea (low friction). Complementary tests were made on a original dynamic tribometer for a better understanding of ZDDP tribofilm friction behavior. The viscous character of ZDDP tribofilm was obtained.

Le dialkyldithiophosphate de zinc ( ZDDP ) est un additif anti-usure habituellement utilisé dans les lubrifiants moteurs. Dans des conditions sévères de frottement, les molécules de ZDDP forment sur les surfaces métalliques un film, appelé tribofilm, qui protège ces surfaces de l'adhésion et de l'abrasion. Les tribofilms sont principalement composés de polyphosphates de zinc dont la longueur des chaînes varie progressivement sur la hauteur du film. On trouve les chaînes de phosphate les plus courtes à la surface du métal et les chaînes de phosphate les plus longues au sommet du film. Plusieurs études ont été menées afin de comprendre le mécanisme par lequel l'additif peut conduire à la formation de ce gradient de phosphate. Pour améliorer la compréhension de ce mécanisme, nous nous concentrons dans cette étude sur l'influence de la pression, du cisaillement, de la nature des surfaces et de la température sur des composés de type orthophosphate de zinc et métaphosphate de zinc, utilisés pour modéliser le tribofilm de ZDDP. Des tests tribologiques ont été réalisés en régime de lubrification limite à partir de dispersions de ces polyphosphates de zinc dans de l'huile de base. L'effet de la pression seule a été étudié à l'aide d'une cellule à enclumes de diamant (CED) afin de découpler son effet de celui du cisaillement. La spectroscopie Raman a été utilisée pour suivre in-situ ou ex-situ, les changements de structures des poudres de polyphosphate de zinc. Ces expériences ont été réalisées sur ces composés afin d'identifier précisément la contrainte qui conduit à ce gradient de phosphate au sein d'un tribofilm. La pression seule, à induit uniquement des désordres structurels au sein des polyphosphates de zinc. Une dimérisation mineure a été observée pour l'orthophosphate de zinc mais, est peu significative pour expliquer les changements structurels observés dans un tribofilm. Lors des tests tribologiques, les phosphates ont montré une capacité à former des tribofilms. Une dépolymérisation du métaphosphate de zinc à été observée a l'issue de ces tests. Les grandes contraintes et conditions de déformation des essais tribologiques sont nécessaires pour induire une réaction tribochimique entre le métaphosphate de zinc et l'oxyde de fer conduisant à une dépolymérisation du phosphate dans le tribofilm. La réaction anti-usure et la formation de tribofilm est favorisée par les hautes températures (120 • C), et par certaines formes d'oxydes de fer. / Zinc dialkyldithiophosphate (ZDDP) is an anti-wear additive, commonly used in engine lubricants. Under severe conditions of friction, it forms a tribofilm on steel surfaces. ZDDP tribofilm is mainly composed of zinc polyphosphates and its structure varies gradually over the height of the film: short phosphate chains at the metal surface and longer phosphate chains at the top of the film. Several studies have been conducted to understand the mechanism by which the additive may lead to the formation of this gradient of the phosphate chain length. The influence of pressure, shear stress, nature surfaces and temperature on the structure of zinc orthophosphate and zinc metaphosphate were investigated, to improve the understanding of their action mechanism. Friction tests were carried out in boundary lubrication regime from dispersions of zinc polyphosphates in base oil. The effect of pressure alone was investigated using a Diamond Anvil Cell (DAC) in order to dissociate from the shear contribution. Raman spectroscopy was used to follow in situ or ex situ structural changes of the zinc polyphosphate powders. The experiments were carried out on these compounds to identify precisely the impact of stresses on them. Pressure alone induces only disordering in the structure of zinc polyphosphates, with only minor dimerization of the chain length in phosphates, and does not contribute significantly to the observed structural changes in tribofilms. Tribofilms obtained with both polyphosphates display a depolymerization of the zinc metaphosphate. The severe stress and strain conditions of the tribological tests are necessary to induce a tribochemical reaction between zinc metaphosphate and iron oxide, leading to a depolymerization of the phosphate in the tribofilm. The tribochemical reaction and anti-wear tribofilm formation are significantly enhanced by the modest temperature increase from ambient to 120°C, and by some kinds of iron oxides.