Es wurden die Zusammenhänge zwischen den Herstellungsbedingungen und dem nanostrukturellen Aufbau von Multischichten, mit Rücksicht auf das mechanische Verhalten aufgeklärt. Dazu wurden durch plasmaunterstützte Gasphasenabscheidung (PACVD) Hartmetallsubstrate mit Viellagen beschichtet und vorrangig mittels analytischer Transmissionselektronenmikroskopie (TEM) charakterisiert. Als Schichkomponenten wurden hauptsächlich TiN und Al2O3 untersucht, daneben aber auch Schichtsysteme der Komponenten AlON, (TiAl)N, und (Ti,Al)ON. Darüber hinaus wurden noch TiC-aC (TiC mit amorphem Kohlenstoffanteil)-Schichten einbezogen. Ziel waren gleichmäßige Multischichten mit Korngrößen von einigen Nanometern, geringer Testur und geringer Mikrorissdichte, die hart sind und gut haften. Die TEM-Untersuchungen dienten insbesondere der Aufklärung der Nanostruktur in den Interface-Bereichen der Schichtsysteme, wobei an Hand der Elektronenenergie-Verlustspektroskopie (EELS) sowohl element- als auch phasenspezifische Signale ausgewertet wurden. Zur verbesserten Bewertung der anfallenden Datenmengen wurden z. T. faktoranalytische Methoden eingesetzt. Je nach Prozessführung der Schichtherstellung kommt es in den Interface-Bereichen zur Durchmischung der Komponenten. Insbesondere führt diffundierender Sauerstoff zur Bildung von TiO2, was sich nachteilig auf die Qualität der Schichten auswirkt. Die Tiefe der "gestörten" Zonen begrenzt die wünschenswerte Verringerung der Einzelschichtdicken. Als wirkungsvolle Gegenmaßnahme hat sich der Einbau von Kohlenstoff erwiesen, wodurch sich dünnere Einzelschichten verwirklichen lassen.

published_or_final_version / Environmental Management / Master / Master of Science in Environmental Management

published_or_final_version / Urban Design / Master / Master of Urban Design

Various compounds were studied with solid-state 119Sn and 31P NMR spectroscopy and quantum chemical calculations. Connections were made between the shielding tensors and the geometric and electronic structures of the molecules. First, the 119Sn chemical shielding anisotropy of various para substituted tetraaryl tin compounds was shown to be dependent on the tilt angle of the phenyl rings. Tetrakis(o-tolyl) tin did not have the shielding anisotropy predicted by the tilt angle of the rings. It was suggested that ortho substitution distorts the structures of the phenyl rings causing the discrepancy. Analysis of the solid-state 31P NMR spectra of triphenylphosphorane ylides, Ph3P=CHC(O)R, determined that increasing the electron-donating effects of the R group decreased the δ33 component. Theoretical calculations showed that the component lay along the ylidic bond and was dependent on the difference in phosphorus-carbon bond lengths between the phenyl and ylidic bonds. Another study concerned the solid-state 31P NMR of the series of triphenylphosphine derivatives, PPh3-x(o-tolyl)x where x = 0 to 3. The addition of ortho methyl groups changed the position of the δ11 component which could be the result of the change in energy gap between the lone pair (HOMO) and σ* anti-bonding (LUMO). The solid-state 31P NMR spectra of deuterated piperazinium phosphonate and phosphonic acid were influenced by the shielding, dipolar and spin-spin interactions, as well as, second order quadrupolar effects. The spectrum of deuterated piperazinium phosphonate had a chemical shielding anisotropy of 130 ppm, an effective dipolar coupling of 2500 kHz and a one-bond phosphorus-deuterium J coupling of 90 Hz. The phosphorus-deuterium bond length was predicted to be 1.44(2) Å. A deuterium quadrupolar coupling constant of 104 kHz was obtained from the CP/MAS 2H spectrum. The non-axial symmetry of phosphonic acid complicated the analysis of the 31P spectrum. Phosphorus-deuterium bond lengths of 1.44(5) Å and 1.40(4) Å were obtained for the two inequivalent sites in the unit cell.

A custom-built surface sol-gel pumping system was built for applying conformal sol-gel based coatings with controlled thicknesses on three-dimensional (3-D) nanostructured templates. The 3-D templates utilized in this work were derived from biological species, such as diatoms and butterfly wings, as well as a synthetic photoresist polymer (SU-8). Tin oxide coatings were applied on silica-based diatom frustules using the automated surface sol-gel pumping system. An organic dendrimer method was developed for amplifying hydroxyl groups on the silica-based frustule surfaces to enhance the surface sol-gel deposition process. Conformal tin oxide coatings with controlled thicknesses were obtained on the hydroxyl amplified frustule surfaces; however, little if any deposition was observed on the frustules that were not subjected to the hydroxyl amplification process. The automated surface sol-gel system was also utilized to apply multicomponent tin oxide-doped titania alkoxide chemistries on the wing scales of a blue Morpho butterfly. The alkoxide solutions reacted directly with the OH functionalities provided by the native chitin chemistry of the scales. The tin oxide served as a rutile nucleating agent which allowed the titania to completely crystallize in the high refractive index rutile titania phase with doping concentrations of tin oxide as low as 7 mol % after annealing at 450oC. The tin oxide-doped titania coatings were both nanocrystalline and nanothick and replicated the nanostructured scales with a high degree of precision. Undoped titania coatings applied on the scales required a heat treatment of 900oC to crystallize the coating in the rutile titania phase which led to adverse coarsening effects which destroyed the nanostructed features of the scales. Tin oxide-doped titania coatings were also deposited on 3-D SU-8 photonic crystal structures. The coating was crystallized in an acidic solution at 80oC which led to the formation of rutile titania inverse opal photonic crystal structures which maintained the overall structure and ordering of the template. Barium titanate and europium-doped barium titanate coatings were applied on diatom frustules using a conventional reflux/evaporation deposition process. The silica-based diatom frustules had to first be converted into magnesia/silicon composite replicas using a gas/solid displacement reaction to render the template chemically compatible with the barium titanate-based coating. Conformal titanate-based coatings were obtained on the magnesia frustule replicas possessing uncontrolled thicknesses and excess inorganic particles using the reflux/evaporation deposition process. The europium-doped barium titanate coated frustules exhibited bright red photoluminescent properties upon stimulation with an ultraviolet light source.

When loss of material due to sliding of two solids is promoted/prevented, in the presence of chemically reacting liquid or gas, tribochemical wear is said to occur. Tribochemical wear, in which corrosive media promotes material loss, is a serious concern in a variety of applications like machining, bio-implants, gas turbine engines etc. The most pervasive corrosive media encountered in applications are water and air. Air also contains water vapour along with oxygen, both of which adsorb and react with most materials, thus influencing their wear behaviour. The need for higher operating temperatures and compression ratios in gas turbine engines require development of high temperature wear resistant coatings to protect their soft metallic components. Ti based nitride coatings with Ti, Al, Si, Cr, Ta, Nb, V are known for wear resistance because of their high hardness which is second only to diamond and c-BN. High O affinity of these elements, induce the coatings to form passive oxide scale up to reasonably high temperatures and offer superior corrosion and oxidation resistance. However, sliding can remove the passivating layer, exposing the native surface to the environment which can lead to enhanced tribochemical wear. Oxidation resistance under static conditions does not guarantee low tribochemical wear; however, the tribochemical reactions causing the corrosion are of interest. Another concern is that sliding in unison with high temperatures can activate processes like enhanced diffusion, phase transformations in nitride coatings as well as in the substrate. Hence one of our objectives is to perform wear tests at high temperatures to understand the dominant mechanisms that affect wear in nitride coatings. Wear tests in the range of room temperature up to the oxidation limit of these coatings are designed.In this study TiN and high aluminium containing TiAlN coatings are chosen to study understand the wear behaviour as function of temperature up to 800°C [1]–[3]. In order to study wear of coatings, it is necessary to identify the best possible materials and methods. Though under the targeted application the coatings have to perform under fretting tests, pin on disk configuration is used which simplifies the analysis and gives deeper insight into the wear mechanism. Coated ball is used as the pin which is stationary unlike many earlier studies where the coating is applied on the rotating disk. The purpose of keeping the pin stationary is to minimize the counter-face wear and, instead, accelerate wear in these hard coatings. This method also enables easy and accurate measurement of wear depth and volume by using an optical microscope, while the conventional coated disk method requires profilometry and statistically sound measurements. To enable coating performance, substrate should not undergo much loss of strength before 800°C and hence aerospace grade IN718 alloy is chosen as the substrate which softens slowly beyond 650°C. Alumina is used as counter-face, since it has high hardness, excellent mechanical, chemical and thermal stability. In the current study, TiAlN coating is tested for wear in the range of room temperature to 800°C. Figure 1 represents the data obtained from the wear experiments. It is found that the wear is higher with large scatter at room temperature while it remains constant from 200- 750°C. Two important observations are made, firstly that the TiAlN is susceptible to some kind of a corrosive wear at room temperature which depended on the timing of the tests and secondly that the coating shows a surprisingly constant wear behaviour over the temperature range of 200-750°C. The scatter at room temperature is found to be linked with seasonal fluctuation of humidity which is verified by performing tests under controlled humidity conditions. Water vapour and oxygen are potential reacting gases present in air. Oxidation and oxidative wear is known to occur in many materials as temperatures increase which seem to be linked to thermal activation of oxidation. However lower wear at 200°C and above compared to room temperatures suggests something else to be happening .It is evident then that between room temperature and 200°C lies a transition of some kind in the tribochemical reaction which is responsible for the observed wear behaviour of TiAlN. A detailed study to understand this transition is then undertaken for the composition of TiN coatings so that benchmarking and comparison with TiAlN is possible. Also if the wear behaviour of TiN is found similar to TiAlN then it would indicate a general phenomenon which can be extended to Ti based nitrides. Figure 1 Wear rate as a variation of temperature for TiAlN coatings In contrast to low temperature wear behaviour of TiAlN, a constant wear in the range of 200-750°C is surprising because the primary suspect which is oxidation is thermally activated. The oxide scale though expected to be thin at low temperatures, has to increase in thickness with temperature due to increased diffusion and reaction rates. The oxide scale also undergoes a change in morphology and composition which indicate a lower oxidation resistance as temperature increases. A preliminary characterization of the wear scar on the ball shows that the oxide inside the worn region is thinner than the oxide outside at 750°C. The amount of O within the wear scar is similar to levels observed on as deposited surface while the surface outside the wear scar shows oxidation and discolouration. The results suggest that oxidation inside worn region at high temperatures might be slower than the expected parabolic oxidation occurring outside the wear region. It is speculated that a double layer oxide is formed with TiO2 towards the surface and Al2O3 towards the nitride which is responsible for the lower wear at high temperature. This is supported by the fact that larger amount of Ti is found in the wear debris as temperature inceases. Superficial surface cracks appear at higher loads at temperatures as low as 600°C but they affect wear only above 800°C due to substrate softening. This shows that the coatings are still limited by the substrate softening temperature and could be used at higher temperatures. Tribo-reaction in metals, nitrides and carbides can be brought about in the presence of O2 or water vapour. Tribochemical wear of SiN, SiC, TiN, TiAlN, alumina and most other ceramics at room temperature are found to depend on humidity[4]–[6]. But only tribo-oxidation due to O2 is found to operate at high temperatures[7], [8]. Notwithstanding, it is known that SiC and SiN are more resistant to attack from O2 above 800°C than from steam. Hence the role played by water vapour is found to be convoluted. Moreover, relative humidity is the frequently mentioned quantity with regard tribochemical wear at room temperatures. It should be noted that relative humidity is not a measure of chemical activity of water vapour. Rather the water vapour pressure which represents the chemical activity of water, is not given much importance in the earlier studies. In this study, the importance of humidity, water vapour pressure and temperature in influencing wear, is studied by performing controlled wear tests on TiN. To explore the effect of temperature and water vapour pressure, TiN is tested varying temperature range of 28 °C to 90°C and water vapour pressure in the range of 3-35 mm-of-Hg. Wear tests are conducted keeping temperature constant with varying water vapour pressure and vice versa. The results show that, wear increased with humidity/vapour pressure at a fixed temperature but wear dropped drastically with increase in temperature at constant vapour pressure up to a critical temperature beyond which wear remained constant. This is one of the major unexpected findings since temperature is expected to increase wear volume. Also the critical temperature is found to shift to higher temperatures as water vapour pressures increased. It was suspected that capillary condensation was playing a role in the wear which was later verified. The whole wear behaviour is shown to be correlated with the amount of capillary condensed water. The large radius of curvature of the asperities on the polished coating surface and the smooth surface formed on the counter-face due to debris compaction form conditions favourable for capillary condensation. Any two hydrophilic surfaces which come in contact can form capillary condensation to occur at the cusps formed around the contact. However a threshold pore size of about 1nm existed below which condensation did not influence wear. Another observation is that the water vapour did not affect wear significantly in the absence of condensation for TiN coatings. As temperatures increased condensation became unfavourable, but the high vapour pressure present showed no signs of wear enhancement. This is surprising and unexpected compared to earlier reports.[9], [10] On contrary tests in liquid water showed expected behaviour for tribochemical reaction i.e wear increased with temperature. The wear in liquid water is highest when compared studies in air at any given temperature. The X-ray electron emission spectroscopy (XPS) analysis is performed to understand the surface reactions. It appears that O2 forms a barrier oxide which protects the nitride from reacting with water vapour. However when condensation occurs or in water, the oxygen and water collude into forming softer hydroxide layer which is easily removed. Though chemically water and water vapour are same, they affect wear in TiN very differently. Summarising the synopsis, exploration into high temperature wear of TiAlN reveals that it can handle oxidative wear upto 750°C showing constant wear over the temperature range of 200-750°C. Reduction in residual stresses and substrate softening may be responsible for higher wear at higher loads since the cracking is observed at 5N is absent at 3N. The substrate is expected to soften above 650°C but this does not necessarily affect wear until the load is increased or the temperature is sufficiently high. However TiAlN and TiN coatings showed susceptibility to tribo-corrosion in water and high humidity at room temperature. At high humidity, condensation of water leads to increase in wear. The dependence of wear on humidity is found to be because of capillary condensation. The negligible dependence of wear on humidity in the absence of condensation is ascribed to formation of oxide layer due to reaction with O2 and coating. The oxide barrier formed due to atmospheric O2 protects the coating from reacting with the water vapour. The oxide barrier on TiN forms faster indicating O2 reaction to be faster than the reaction with water vapour. In the presence of capillary condensation or water, O2 is depleted from contacting surfaces thus hindering the formation of the barrier oxide, increasing wear. As temperature increases the condensation becomes unfavourable and barrier oxide dominates the wear mechanism upto high temperatures which is dominated by oxidative wear.

Submitted by Pedro Silva Filho (pfsilva@ipen.br) on 2017-11-22T16:42:40Z No. of bitstreams: 0 / Made available in DSpace on 2017-11-22T16:42:40Z (GMT). No. of bitstreams: 0 / Neste trabalho foi estudado o efeito da adição de íons haletos (Cl-, Br- e I-) sobre a morfologia das nanopartículas de Pt na produção de catalisadores de Pt/C e PtSnO2/C. Foi desenvolvida uma metodologia de síntese simples capaz de produzir nanopartículas de Pt predominantemente cúbicas com orientação preferencial Pt(100), diretamente suportadas em carbono sem o uso de agentes estabilizantes. Brometo de potássio foi utilizado como agente direcionador de superfície para obtenção do material preferencialmente orientado. O controle de adição do precursor de Pt e de KBr foi crucial para obter nanocubos de Pt de 8 nm bem dispersos sobre o suporte. Na preparação dos catalisadores de PtSnO2/C, o processo de adição do SnCl2 também foi decisivo na obtenção das nanopartículas de Pt com tamanho e morfologia de interesse. Nanocubos de Pt coexistindo com SnO2 disperso foram exclusivamente obtidos ao adicionar o SnCl2 na etapa final da síntese, quando as nanopartículas cúbicas de Pt já estavam formadas. Enriquecidos de domínios Pt(100), os materiais em forma cúbica de Pt/C e PtSnO2/C se mostraram menos afetados pelo acúmulo dos intermediários indesejados provenientes da reação de eletro-oxidação de etanol e foram mais tolerantes ao envenenamento por monóxido de carbono. Resultados similares foram observados para a oxidação de CO e metanol, utilizados como apoio para compreensão da eletro-oxidação de etanol. O efeito morfológico destes materiais no desempenho elétrico em célula a combustível de etanol direto foi avaliado. Pt/C e PtSnO2/C contendo nanopartículas de Pt com orientação preferencial Pt(100) forneceram maiores valores de densidade de potência e de seletividade para CO2 comparados aos catalisadores de Pt/C e PtSnO2/C com nanopartículas de Pt sem orientação preferencial. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Neste trabalho foi investigada a eletrooxidação de etanol sobre eletrodos nanoparticulados binários Pt-M1 (M1 = Sn ou Re) e ternários Pt-M1-M2 (M1 e M2 = Sn e Re) suportados em carbono. Estes materiais foram preparados pelo método da redução por álcool e foram caracterizados por difração de raios-X e microscopia eletrônica de varredura associada a EDX. Os eletrodos foram montados utilizando-se a técnica de camada ultrafina. Os resultados eletroquímicos mostraram que a adição dos diferentes metais à platina aumentou a atividade catalítica tanto dos eletrodos binários quanto dos ternários. Os testes realizados na célula unitária mostraram que a presença de Sn nos catalisadores binário e de Sn e Re nos catalisadores ternários aumentou significativamente o desempenho da célula quando comparada ao ânodo de Pt pura suportada em carbono, preparado pela metodologia da redução do álcool ou ao comercial da E-TEK. O catalisador Pt70Sn10Re20/C foi o que apresentou a melhor densidade de corrente assim como a melhor densidade de potência com um valor máximo alcançado de aproximadamente 40 mW cm-2 durante a operação da célula a combustível a 90 oC. / In this work was investigated the electrooxidation of ethanol on nanostructured binary Pt-M1 (M1 = Sn or Re) and ternary Pt-M1-M2 (M1 and M2 = Re and Sn) electrodes supported on carbon. These materials were prepared by the alcohol reduction method and were characterized by X-ray diffraction and scanning electron microscopy associated to EDX. The ultra-thin layer technology was used to assemble the electrode. The electrochemical results showed that the addition of different metals to platinum increased the catalytic activity of the binary and ternary electrodes. Tests conducted in unitary fuel cell showed that the presence of Sn in the binary catalysts and Sn and Re in the ternary catalysts increased significantly the performance of the cell when compared to pure Pt anode supported on carbon, prepared by the alcohol methodology or the commercial E-TEK. The catalyst Pt70Sn10Re20/C presented the best current density as well the better power density with a maximum value of ca. 40 mW cm-2 reached during the operation of the fuel cell at 90 oC.

O presente trabalho teve como objetivo principal avaliar o efeito dos recobrimentos TiN e TiAlN depositados por PVD a plasma na liga Ti-6Al-4V sob condições de fluência a 600 °C e corrosão em meios contendo cloreto a 25, 60 e 80 °C. O trabalho foi complementado com análises microestruturais e dos revestimentos superficiais utilizando-se as técnicas de difração de raios X, microscopias óptica, eletrônica de varredura e de transmissão, medidas de microdureza e oxidação isotérmica. Os resultados permitiram concluir que a liga Ti-6Al-4V constituída pela configuração de Widmanstätten apresentou dureza média de 343 HV para a condição como recebida. Após os tratamentos por PVD a plasma observou-se um recobrimento à base de TiN de espessura de 2,2 ?m e composição igual a Ti0,7N. O recobrimento a base de TiAlN/TiAlCrN apresentou espessura em torno de 6 ?m e composição igual a (Ti0,38Al0,62)N/(Ti0,31Al0,50Cr0,19)N. As medidas do potencial em circuito aberto e polarização mostraram que a liga Ti-6Al-4V apresentou comportamento ativo com transição ativo-passiva em solução HCl e comportamento passivo em solução NaCl a 25, 60 e 80 °C. As amostras recobertas por TiN e TiAlN/TiAlCrN apresentaram comportamento passivo nas duas soluções corrosivas e em todas as temperaturas estudadas. A amostra revestida por TiN depositado por PVD apresentou os menores valores de taxa secundária em fluência para tensões maiores que 222 MPa, contudo a amostra nitretada a plasma apresentou maiores valores de vida útil e níveis de ductilidade. A análise conjunta dos expoentes de tensão, energia de ativação e estrutura de discordâncias indicaram que o principal mecanismo de deformação por fluência foi controlado por escalagem de discordâncias. O cálculo do parâmetro de tolerância ao dano (W) contribuiu para indicar que os revestimentos TiN e TiAlN/TiAlCrN, apesar de protegerem a superfície da oxidação, diminuíram a capacidade de deformação plástica ao longo do estágio terciário e vida útil da liga Ti-6Al-4V, reduzindo a ductilidade. Finalmente, os tratamentos superficiais utilizados neste trabalho foram eficientes por seu efeito de proteção através da deposição de um elemento cerâmico mais estável na superfície e não por transformações causadas na microestrutura. / This study aimed to evaluate the effect of the plasma-assisted PVD TiN and TiAlN/TiAlCrN coatings in the Ti-6Al-4V alloy under creep conditions at 600 °C and under corrosion conditions in environments containing chloride at 25, 60 and 80 °C. The study was complemented by microstructural and surface coatings analysis using XRD, optical, scanning and transmission electron microscopy, microhardness and isothermal oxidation. The results showed that the Ti-6Al- 4V alloy with Widmanstätten morphology presented an average hardness of 343 HV for as received condition. After treatment by plasma PVD, it was observed a TiN based coating, with 2,2 ?m and composition of Ti0,7N. The TiAlN/TiAlCrN based coating presented 6 ?m of thickness and composition of (Ti0,38Al0,62)N/(Ti0,31Al0,50Cr0,19)N. Anodic polarization and open circuit potential showed that Ti-6Al-4V alloy had active behavior with active - passive transition in HCl solution and passive behavior in NaCl solution at 25, 60 and 80 °C. The TiN and TiAlN/TiAlCrN coated samples showed passive behavior in both corrosive solutions and at all studied temperatures. The TiN coated sample showed the lowest values of secondary creep rate for stresses greater than 222 MPa, however, the plasma nitrided sample showed higher levels of service life and ductility. The analysis of stress exponents, activation energy and dislocations structures indicated that the main mechanism of creep was controlled by climbing dislocations. The damage tolerance parameter (W) calculation contributed to indicate that TiN and TiAlN/TiAlCrN coatings, although protect the surface from oxidation, decreased plastic deformation ability throughout tertiary stage and service life of the Ti-6Al-4V alloy, decreasing ductility. Finally, the surface treatments, used in this study, were efficient for their protective effect by depositing a more stable ceramic compound on surface and not by transformations caused on microstructure.

A tendência mundial de se buscar a sustentabilidade econômica tem causado uma crescente demanda por novas técnicas e novos materiais que gerem: aumento da produtividade, maior velocidade de operação, aumento da vida útil de ferramentas e matrizes, e que reduzam o custo ambiental atual. Nesta busca a modificação de superfícies metálicas é um campo promissor e o bombardeamento com íons de Xe+ tem sido utilizada para texturizar a superfície do substrato, seja para o aumento da aderência de revestimentos com grande dureza ou para melhorar a difusão de N. Neste estudo são relatados os resultados obtidos de ensaios de dureza, desgaste, DRX (fases e tensão residual) e microscopias MEV, AFM e MET, efetuadas em amostras de aço 100Cr6 (globulizada) modificadas superficialmente por meio de bombardeamento com íons de Xe+ e revestimento duplex. Para esse fim, foram preparadas amostras combinando: bombardeamento com íons de Xe+ com energia de 400 e 1000 eV; implantação de N por feixe de íons e plasma pulsado; e deposição do revestimento de TiN por sputtering com diferentes temperaturas em um sistema reativo com N2-IBSD. Uma análise desses resultados permitiu constatar que o bombardeamento de íons de Xe+ gera refinamento de grãos, texturização, e aumenta a densidade de defeitos na estrutura cristalina na superfície tratada em função da energia utilizada. O bombardeamento de Xe+ com energia de 1000 eV melhorou o aprisionamento de nitrogênio e a difusão a 380°C (via feixe de íons) o que levou a formação dos nitretos γ\'-Fe4N e ε-Fe2-3N. Enquanto que com energia de 400 eV levou a formação apenas do nitreto γ\'-Fe4N. As propriedades adquiridas na combinação dos pré-tratamentos de bombardeamento de Xe+ com energia de 400 eV, nitretação a plasma pulsado (520°C) e a deposição do filme de TiN (500°C/240 min) levaram ao melhor desempenho no ensaio de desgaste. / The global trend of seeking economic sustainability has caused a growing demand for new materials that generate: increased productivity, higher operating speed, increased service life of tools and dies, and to reduce the current environmental cost. In this search, the modification of metallic surfaces is a promising field and bombardment Xe+ ions has been used to texture the surface of the substrate, is to increase the tack coatings with high hardness or to improve the N diffusion. In this study are reported the results obtained from testing the hardness, wear, XRD (phase and residual stress) and microscopy SEM, AFM and TEM, made in 100Cr6 steel samples (globulized) surface modified by bombardment with Xe+ and duplex coating. To this end, samples were prepared by combining: bombardment Xe+ ions with energy of 400 and 1000 eV; N implantation by ion beam and pulsed plasma; and deposition of the TiN coating by sputtering at different temperatures in a N2 reaction system-IBSD. An analysis of these results helped to confirm that the bombardment of Xe+ ions produces grain refinement, texturing, and increases the defect density in the crystalline structure of the surface treated according to the energy used. Bombardment of Xe+ ions with energy 1000 eV improved nitrogen trapping and diffusion to 380°C (via ion beam) which led to the formation of γ\'-Fe4N and ε-Fe2-3N nitrides. Whereas with energy 400 eV led to the formation of only γ\'-nitride Fe4N. The properties acquired in the combination of the pre-treatments of Xe+ ions bombardment at 400 eV, pulsed plasma nitriding (520°C) and the deposition of TiN coating (500°C/240 min) leads to a superior performance in wear test.