Application of wear resistant coatings by the brush plating technique

The development of cobalt molybdenum and cobalt tungsten brush plating electrolytes is described. Their optimum compositions and operating conditions for commercial applications have been determined. The effects of composition, pH, applied voltage, stylus speed and pressure upon deposit composition and efficiency have been investigated. Transmission and Scanning Electron Microscopy have been employed to study the cobalt alloy deposits produced. Evaluation of the wear resistant properties of the cobalt alloys developed in this work was carried out in the laboratory using a pin and disc technique and a simulated hot forging test, and by industrial trials involving the "on site" plating of hot forging dies and cold pressing tools. It was concluded that the electrolytes developed in tl1is work enabled cobalt alloys containing 6% Mo or 8% W to be deposited at 17-20V. Brush plated cobalt deposits possessed a mixed CPU and FCC crystallographic structure at room temperature. The application of 13µm of either of the cobalt alloys resulted in improved wear performance in both pin and disc and simulated hot forging tests. The results of the industrial trials indicated that by the use of these alloys, the life of hot forging dies may be increased by 20-100%. A commercial forging organisation is using electrolytes developed in this work to coat dies prior to forging nimonic alloys. Reductions in forging temperature and improved forging qualities have been reported. Cold pressing tools coated with the alloys showed a reduced tendency to "pick-up" and scoring of the pressed panels. Reports of a reduced need for lubrication of panels before pressing have also been received.

Wear behavior of plasma electrolytic oxidation (PEO) and hybrid coatings of PEO and laser on MRI 230D magnesium alloy

Wear resistant coatings were produced on a permanent mould cast MRI 230D Mg alloy by (a) PEO in silicate based electrolyte, (b) PEO in phosphate based electrolyte, (c) hybrid coatings of silicate PEO followed by laser surface alloying (LSA) with Al and Al(2)O(3), and (d) hybrid coatings of phosphate PEO followed by LSA with Al and Al(2)O(3). Microstructural characterization of the coatings was carried out by scanning electron microscopy (SEM) and X(ray diffraction. The tribological behavior of the coatings was investigated under dry sliding condition using linearly reciprocating ball-on-flat wear test. Both the PEO coatings exhibited a friction coefficient of about 0.8 and hybrid coatings exhibited a value of about 0.5 against the AISI 52100 steel ball as the friction partner, which were slightly reduced with the increase in applied load. The PEO coatings sustained the test without failure at 2 N load but failed at 5 N load due to micro-fracture caused by high contact stresses. The hybrid coatings did not get completely worn off at 2 N load but were completely removed exposing the substrate at 5 N load. The PEO coatings exhibited better wear resistance than the hybrid coatings and silicate PEO coatings exhibited better wear resistance than the phosphate PEO coatings. Both the PEO coatings melted/decomposed on laser irradiation and all the hybrid coatings exhibited similar microstructure and wear behavior irrespective of the nature of the primary PEO coating or laser energies. SEM examination of worn surfaces indicated abrasive wear combined with adhesive wear for all the specimens. The surface of the ball exhibited a discontinuous transfer layer after the wear test. (C) 2011 Elsevier B.V. All rights reserved.

Nanoindentation of thin-film-substrate system: Determination of film hardness and Young's modulus

In the present paper, the hardness and Young's modulus of film-substrate systems are determined by means of nanoindentation experiments and modified models. Aluminum film and two kinds of substrates; i.e. glass and silicon, are studied. Nanoindentation XP II and continuous stiffness mode are used during the experiments. In order to avoid the influence of the Oliver and Pharr method used in the experiments, the experiment data are analyzed with the constant Young's modulus assumption and the equal hardness assumption. The volume fraction model (CZ model) proposed by Fabes et al. (1992) is used and modified to analyze the measured hardness. The method proposed by Doerner and Nix (DN formula) (1986) is modified to analyze the measured Young's modulus. Two kinds of modified empirical formula are used to predict the present experiment results and those in the literature, which include the results of two kinds of systems, i.e., a soft film on a hard substrate and a hard film on a soft substrate. In the modified CZ model, the indentation influence angle, phi, is considered as a relevant physical parameter, which embodies the effects of the indenter tip radius, pile-up or sink-in phenomena and deformation of film and substrate.

Recubrimientos autolubricantes cuasicristalinos tipo composite depositados mediante proyección térmica para aplicaciones espaciales y de alta temperatura

Los recubrimientos lubricantes sólidos son requeridos para reducir la fricción y prevenir el desgaste en componentes que operan a altas temperaturas o en vacío (vehículos espaciales, industria química, motores diésel, turbinas aeronáuticas y de generación de energía…). Los lubricantes líquidos pierden sus características cuando las condiciones de presión, temperatura o ambientales son severas (oxidación, inestabilidad térmica, volatilidad,…), por ejemplo los aceites minerales convencionales se descomponen a temperaturas próximas a 200 ºC. Por tanto, la única manera de poder conseguir una adecuada lubricación a temperaturas extremas es por medio de sólidos, que cada vez más, se aplican en forma de recubrimientos. Estos recubrimientos podrían ser empleados en componentes de vehículos espaciales reutilizables, donde se pueden alcanzar, en la reentrada en la atmósfera, temperaturas de 700 ºC (bisagras, rodamientos, articulaciones y zonas de sellado en las superficies de control, y rodamientos de las turbobombas y las cajas de engranajes). Dichos recubrimientos también deberían ser capaces de proporcionar una lubricación efectiva a bajas temperaturas para las operaciones en tierra, para las operaciones de arranque en frío, incluso en el espacio. El conjunto de requisitos que tendrían que satisfacer las capas tribológicas relacionadas con estas condiciones extremas es muy diverso, lo que hace que el concepto de capas tipo composite (aquéllas constituidas por varios componentes) sea, en principio, muy adecuado para estas aplicaciones. Recubrimientos composite proyectados térmicamente constituidos por una matriz dura y conteniendo lubricantes sólidos pueden ser una buena solución desde el punto de vista tribológico. El “Lewis Research Centre” de la NASA ha estado desarrollando recubrimientos autolubricantes tipo composite, constituidos por la combinación de materiales duros como el carburo de cromo, junto con lubricantes sólidos como plata o la eutéctica de fluoruros de calcio y bario, en una matriz de NiCr, para su uso en aplicaciones terrestres a alta temperatura. Estos recubrimientos han sido aplicados mediante proyección térmica, siendo denominados como series PS100, PS200, PS300 y PS400, reduciendo de forma significativa el coeficiente de fricción y mejorando la resistencia al desgaste en un amplio margen de temperaturas. Otra nueva familia de materiales con comportamiento tribológico prometedor son las aleaciones cuasicristalinas (QC). Presentan características muy atractivas: alta dureza, baja fricción, alto límite elástico de compresión... Son muy frágiles como materiales másicos, por lo que se intentan aplicar en forma de recubrimientos. Se pueden depositar mediante proyección térmica. Algunos de estos materiales cuasicristalinos, como AlCoFeCr, poseen coeficientes de dilatación próximos al de los materiales metálicos, alta estabilidad térmica, baja conductividad térmica y una elevada resistencia a la oxidación y a la corrosión en caliente. En esta tesis se han desarrollado recubrimientos tipo composite conteniendo cuasicristales como componente antidesgaste, NiCr como componente tenaz, y Ag y la eutéctica de BaF2-CaF2, como lubricantes sólidos. Estos recubrimientos han sido depositados con diferentes composiciones (denominadas TH100, TH103, TH200, TH400, TH600…) mediante distintos procesos de proyección térmica: plasma en aire (PS), plasma en baja presión (LPPS) y combustión a alta velocidad (HVOF). Los recubrimientos se han generado sobre el sustrato X-750, una superaleación base níquel, endurecible por precipitación, con muy buena resistencia mecánica y a la oxidación hasta temperaturas de 870 ºC y, además, es empleada en aplicaciones aeroespaciales e industriales. Los recubrimientos han sido caracterizados microestructuralmente en INTA (Instituto Nacional de Técnica Aeroespacial), mediante SEM-EDS (Scanning Electronic Microscopy-Energy Dispersive Spectroscopy) y XRD (X-Ray Diffraction), y tribológicamente mediante medidas de microdureza y ensayos en tribómetro POD (Pin On Disc) para determinar los coeficientes de fricción y de desgaste. Los recubrimientos han sido ensayados tribológicamente a alta temperatura en INTA y en vacío en AMTTARC (Aerospace and Space Materials Technology Testhouse – Austrian Research Centres), en Seibersdorf (Austria). Se ha estudiado la influencia de la carga normal aplicada, la velocidad lineal y el material del pin. De entre las diferentes series de recubrimientos cuasicristalinos tipo composite desarrolladas, dos de ellas, TH100 y TH103 han presentado una excelente calidad microestructural (baja porosidad, distribución uniforme de fases…) y se han mostrado como excelentes recubrimientos antidesgaste. Sin embargo, estas capas presentan un pobre comportamiento como autolubricantes a temperatura ambiente, aunque mejoran mucho a alta temperatura o en vacío. Los resultados del trabajo presentado en esta tesis han proporcionado nuevo conocimiento respecto al comportamiento tribológico de recubrimientos autolubricantes cuasicristalinos tipo composite depositados por proyección térmica. Sin embargo, dichos resultados, aunque son muy prometedores, no han puesto de manifiesto el adecuado comportamiento autolubricante que se pretendía y, además, como ocurre en cualquier trabajo de investigación, durante el desarrollo del mismo siempre aparecen nuevas dudas por resolver. Se proponen nuevas líneas de trabajo futuro que complementen los resultados obtenidos y que puedan encaminar hacia la obtención de un recubrimiento que mejore su comportamiento autolubricante. ABSTRACT Solid lubricant coatings are required to reduce friction and prevent wear in components that operate at high temperatures or under vacuum (space vehicles, chemical industry, diesel engines, power generation turbines and aeronautical turbines, for instance). In these cases neither greases nor liquid lubricants can be employed and the only practicable approach to lubrication in such conditions is by means of solids. These are increasingly applied in the form of coatings which should exhibit low shear strength, whilst maintaining their chemical stability at extremes temperatures and in the space environment. In the space field, these coatings would be employed in re-usable space plane applications, such as elevon hinges, where temperatures of 700 ºC are reached during re-entry into the Earth’s atmosphere. These coatings should also be capable of providing effective lubrication at lower temperatures since “cold start” operation may be necessary, even in the space environment. The diverse and sometimes conflictive requirements in high temperature and space-related tribological coatings make the concept of composite coatings highly suitable for these applications. Thermal-sprayed composites containing solid lubricants in a hard matrix perform well tribologically. NASA‘s Lewis Research Centre had developed self-lubricating composite coatings for terrestrial use, comprising hard materials like chromium carbide as well as solid lubricant additives such as silver and BaF2-CaF2 eutectic on a Ni-Cr matrix. These coatings series, named PS100, PS200, PS300 and PS400, are applied by thermal spray and significantly reduce friction coefficients, improving wear resistance over a wide temperature range. Quasicrystalline alloys (QC) constitute a new family of materials with promising tribological behaviour. Some QC materials exhibit a combination of adequate antifriction properties: low friction coefficient, high hardness and high yield strength under compression, and can be easily produced as coatings on top of metallic and non-metallic materials. Among these QC alloys, AlCoFeCr has high hardness (700 HV0.1), a thermal expansion coefficient close to that of metals, high thermal stability, low thermal conductivity and good oxidation and hot corrosion resistance. However most QC materials have the disadvantage of being very brittle. In order to take advantage of the excellent tribological properties of QCs, thick composite lubricant coatings were prepared containing them as the hard phase for wear resistance, Ag and BaF2-CaF2 eutectic as lubricating materials and NiCr as the tough component. These coatings were deposited in different composition mixtures (named TH100, TH103, TH200, TH400, TH600…) by different thermal spray processes: air plasma spray (PS), low pressure plasma spray (LPPS) and high velocity oxy-fuel (HVOF), on X-750 substrates. X-750 is an age-hardenable nickel-base superalloy with very good strength and a good resistance to oxidising combustion gas environments at temperatures up to about 870 ºC and it is widely used in aerospace and industrial applications. Coatings have been characterized microstructurally, at INTA (National Institute for Aerospace Technology), by means of SEM-EDS (Scanning Electronic Microscopy- Energy Dispersive Spectroscopy) and XRD (X-Ray Diffraction), and tribologically by microhardness measurements and pin-on-disc testing to determine friction coefficients as well as wear resistance. The coatings were tested tribologically at high temperature at INTA and under vacuum at AMTT-ARC (Aerospace and Space Materials Technology Testhouse – Austrian Research Centres), in Seibersdorf (Austria). Different loads, linear speeds and pin materials were studied. TH100 and TH103 QC alloy matrix composite coatings were deposited by HVOF with excellent microstructural quality (low porosity, uniform phase distribution) and showed to be excellent wear resistant coatings. However these QC alloy matrix composite coatings are poor as a self-lubricant at room temperature but much better at high temperature or in vacuum. The results from the work performed within the scope of this thesis have provided new knowledge concerning the tribological behavior of self-lubricating quasicrystalline composite coatings deposited by thermal spraying. Although these results are very promising, they have not shown an adequate self-lubricating behavior as was intended, and also, as in any research, the results have in addition raised new questions. Future work is suggested to complement the results of this thesis in order to improve the selflubricating behaviour of the coatings.

Role of carbon nanotube dispersion in fracture toughening of plasma sprayed aluminum oxide-carbon nanotube nanocomposite coating

Aluminum oxide (Al2O3, or alumina) is a conventional ceramic known for applications such as wear resistant coatings, thermal liners, heaters, crucibles, dielectric systems, etc. However applications of Al 2O3 are limited owing to its inherent brittleness. Due to its excellent mechanical properties and bending strength, carbon nanotubes (CNT) is an ideal reinforcement for Al2O3 matrix to improve its fracture toughness. The role of CNT dispersion in the fracture toughening of the plasma sprayed Al2O3-CNT nanocomposite coating is discussed in the current work. Pretreatment of powder feedstock is required for dispersing CNTs in the matrix. Four coatings namely spray dried Al2O 3 (A-SD), Al2O3 blended with 4wt.% CNT (A4C-B), composite spray dried Al2O3-4wt.% CNT (A4C-SD) and composite spray dried A1203-8wt.% CNT (A8C-SD), are synthesized by plasma spraying. Owing to extreme temperatures and velocities involved in the plasma spraying of ceramics, retention of CNTs in the resulting coatings necessitates optimizing plasma processing parameters using an inflight particle diagnostic sensor. A bimodal microstructure was obtained in the matrix that consists of fully melted and resolidified structure and solid state sintered structure. CNTs are retained both in the fully melted region and solid-state sintered regions of processed coatings. Fracture toughness of A-SD, A4C-B, A4C-SD and A8C-SD coatings was 3.22, 3.86, 4.60 and 5.04 MPa m1/2 respectively. This affirms the improvement of fracture toughness from 20% (in A4C-B coating) to 43% (in A4C-SD coating) when compared to the A-SD coating because of the CNT dispersion. Fracture toughness improvement from 43% (in A4C-SD) to 57% (in A8C-SD) coating is evinced because of the CNT content. Reinforcement by CNTs is described by its bridging, anchoring, hook formation, impact alignment, fusion with splat, and mesh formation. The Al2O3/CNT interface is critical in assisting the stress transfer and utilizing excellent mechanical properties of CNTs. Mathematical and computational modeling using ab-initio principle is applied to understand the wetting behavior at the Al2O 3/CNT interface. Contrasting storage modulus was obtained by nanoindentation (∼210, 250, 250-350 and 325-420 GPa in A-SD, A4C-B, A4C-SD, and A8C-SD coatings respectively) depicting the toughening associated with CNT content and dispersion.

Role of carbon nanotube dispersion in fracture toughening of plasma sprayed aluminum oxide - carbon nanotube nanocomposite coating

Aluminum oxide (A1203, or alumina) is a conventional ceramic known for applications such as wear resistant coatings, thermal liners, heaters, crucibles, dielectric systems, etc. However applications of A1203 are limited owing to its inherent brittleness. Due to its excellent mechanical properties and bending strength, carbon nanotubes (CNT) is an ideal reinforcement for A1203 matrix to improve its fracture toughness. The role of CNT dispersion in the fracture toughening of the plasma sprayed A1203-CNT nanocomposite coating is discussed in the current work. Pretreatment of powder feedstock is required for dispersing CNTs in the matrix. Four coatings namely spray dried A1203 (A-SD), A1203 blended with 4wt.% CNT (A4C-B), composite spray dried A1203-4wt.% CNT (A4C-SD) and composite spray dried A1203-8wt.% CNT (A8CSD), are synthesized by plasma spraying. Owing to extreme temperatures and velocities involved in the plasma spraying of ceramics, retention of CNTs in the resulting coatings necessitates optimizing plasma processing parameters using an inflight particle diagnostic sensor. A bimodal microstructure was obtained in the matrix that consists of fully melted and resolidified structure and solid state sintered structure. CNTs are retained both in the fully melted region and solid-state sintered regions of processed coatings. Fracture toughness of A-SD, A4C-B, A4C-SD and A8C-SD coatings was 3.22, 3.86, 4.60 and 5.04 MPa m1/2 respectively. This affirms the improvement of fracture toughness from 20 % (in A4C-B coating) to 43% (in A4C-SD coating) when compared to the A-SD coating because of the CNT dispersion. Fracture toughness improvement from 43 % (in A4C-SD) to 57% (in A8C-SD) coating is evinced because of the CNT content. Reinforcement by CNTs is described by its bridging, anchoring, hook formation, impact alignment, fusion with splat, and mesh formation. The A1203/CNT interface is critical in assisting the stress transfer and utilizing excellent mechanical properties of CNTs. Mathematical and computational modeling using ab-initio principle is applied to understand the wetting behavior at the A1203/CNTinterface. Contrasting storage modulus was obtained by nanoindentation (~ 210, 250, 250-350 and 325-420 GPa in A-SD, A4C-B, A4C-SD, and A8C-SD coatings respectively) depicting the toughening associated with CNT content and dispersion.

Fretting wear study of Cu-10 wt% TiB2 and Cu-10 wt% TiB2-10 wt% Pb composites

In developing materials with better tribological properties, it is always conceived that the addition of softer phase would result in better frictional behavior. In order to address this issue, we report here the results of fretting wear study on Cu-10 wt% TiB2 and Cu-10 wt% TiB2-10 wt% Pb composites, sintered using spark plasma sintering (SPS) technique. It was found out that the addition of softer phase i.e. 10 wt % Pb to Cu-10 wt% TiB2 composites has not resulted in the lowering of the coefficient of friction (COF). The combination of steady state COF (0.6) and wear rate (10(-3) mm(3)/N-m) was measured and such properties are even better than that obtained with TiB2 coatings reported in the literature. For Cu-10 wt% TiB2 sintered at different temperature, a lower wear resistance with increase in hardness is being measured. An attempt has been made to correlate the observed wear behavior with the surface and subsurface deformation. The formation of a wear-resistant delaminated tribolayer consisting of TiB2 particles and ultrafine oxide debris (Cu, Fe, Ti)(x)O-y was the reason assigned for the observed low wear rate of these composites. (C) 2013 Elsevier B.V. All rights reserved.

Tribological Testing of Some Potential PVD and CVD Coatings for Steel Wire Drawing Dies

Cemented carbide is today the most frequently used drawing die material in steel wire drawing applications. This is mainly due to the possibility to obtain a broad combination of hardness and toughness thus meeting the requirements concerning strength, crack resistance and wear resistance set by the wire drawing process. However, the increasing cost of cemented carbide in combination with the possibility to increase the wear resistance of steel through the deposition of wear resistant CVD and PVD coatings have enhanced the interest to replace cemented carbide drawing dies with CVD and PVD coated steel wire drawing dies. In the present study, the possibility to replace cemented carbide wire drawing dies with CVD and PVD coated steel drawing dies have been investigated by tribological characterisation, i.e. pin-on-disc and scratch testing, in combination with post-test observations of the tribo surfaces using scanning electron microscopy, energy dispersive X-ray spectroscopy and 3D surface profilometry. Based on the results obtained, CVD and PVD coatings aimed to provide improved tribological performance of steel wire drawing dies should display a smooth surface topography, a high wear resistance, a high fracture toughness (i.e. a high cracking and chipping resistance) and intrinsic low friction properties in contact with the wire material. Also, the steel substrate used must display a sufficient load carrying capacity and resistance to thermal softening. Of the CVD and PVD coatings evaluated in the tribological tests, a CVD TiC and a PVD CrC/C coating displayed the most promising results.

Effects of high temperature plasma immersion ion implantation on wear resistance of Ti-Si-B sintered alloys

Although titanium and its alloys own good mechanical properties and excellent corrosion resistance, these materials present poor tribological properties for specific applications that require wear resistance. In order to produce wear-resistant surfaces, this work is aimed at achieving improvement of wear characteristics in Ti-Si-B alloys by means of high temperature nitrogen plasma immersion ion implantation (PIII). These alloys were produced by powder metallurgy using high energy ball milling and hot pressing. Scanning electron microscopy (SEM) and X-ray diffraction identified the presence of α-titanium, Ti6Si2B, Ti5Si3, TiB and Ti3Si phases. Wear tests were carried out with a ball-on-disk tribometer to evaluate the friction coefficient and wear rate in treated and untreated samples. The worn profiles were measured by visible light microscopy and examined by SEM in order to determine the wear rates and wear mechanisms. Ti-7.5Si-22.5B alloy presented the highest wear resistance amongst the untreated alloys produced in this work. High temperature PIII was effective to reduce the wear rate and friction coefficient of all the Ti-Si-B sintered alloys. © 2013 Elsevier B.V.

Corrosion studies on the plasma-sprayed nanostructured titanium dioxide coating

Purpose: The purpose of this paper is to report the resistance of plasma-sprayed titanium dioxide (TiO2) nanostructured coatings in a corrosive environment.----- Design/methodology/approach: Weight loss studies are performed according to ASTM G31 specifications in 3.5?wt% NaCl. Electrochemical polarization resistance measurements are made according to ASTM G59-91 specifications. Corrosion resistance in a humid and corrosive environment is determined by exposing the samples in a salt spray chamber for 100?h. Microstructural studies are carried out using an atomic force microscope and scanning electron microscope.----- Findings: The nanostructured TiO2 coatings offer good resistance to corrosion, as shown by the results of immersion, electrochemical and salt spray studies. The corrosion resistance of the coating is dictated primarily by the geometry of splat lamellae, density of unmelted nanoparticles, magnitude of porosity and surface homogeneity.----- Practical implications: The TiO2 nanostructured coatings show promising potential for use as abrasion, wear-resistant and thermal barrier coatings for service in harsh environments.----- Originality/value: The paper relates the corrosion resistance of nanostructured TiO2 coatings to their structure and surface morphology.

Microstructure-hardness-fretting wear resistance correlation in ultrafine grained Cu-TiB2-Pb composites

The retention of the desired combination of mechanical/tribological properties in ultrafine grained materials presents important challenges in the field of bulk metallic composites. In order to address this aspect, the present work demonstrates how one can achieve a good combination of hardness and wear resistance in Cu-Pb-TiB2 composites, consolidated by spark plasma sintering at low temperatures ( < 500 degrees C). Transmission electron microscope (TEM) studies reveal ultrafine grains of Cu (100-400 nm) with coarser TiB2 particles (1-2 mu m) along with fine scale Pb dispersoid at triple junctions or at the grain boundaries of Cu. Importantly, a high hardness of around 2.2 GPa and relative density of close to 90% relative density (rho(theo)) have been achieved for Cu-15 wt% TiB2-10 wt% Pb composite. Such property theo, combination has never been reported for any Cu-based nanocomposite, by conventional processing route. In reference to the tribological performance, fretting wear tests were conducted on the sintered nanocomposites and a good combination of steady state COF (0.6-0.7) and wear rate (10-4 mm(3)/N m) were measured. An inverse relationship between wear rate and hardness was recorded and this commensurates well with Archard's relationship of abrasive wear. The formation of a wear-resistant delaminated tribolayer consisting of TiB2 particles and ultrafine oxide debris, (Cu, Fe, Ti)(x)O-y as confirmed from subsurface imaging using focused ion beam microscopy has been identified as the key factors for the low wear rate of these composites. (C) 2014 Elsevier B.V. All rights reserved.