Passive Films Passive films are produced by the reaction between a metal and its environment. The films are very thin, usually about 1-5 nm thickness, and are barriers to transport of the reacting species; thus, they limit the rate of further reaction to a low value. Passive films can be formed on many metals; whether or not a passive film can form depends upon the particular environmental conditions. Pourbaix diagrams indicate the electrochemical potential and pH values that may support formation of passive films ‘on metals in water at 25°C. The compositions of the films have been extensively studied. Owing to their low thickness, they must be studied by experimental techniques which have excellent depth resolution, approximately, or preferably less than, 1 nm. These techniques include Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), glow discharge optical emission spectroscopy (GDOES), ellipsometry, electrochemical measurements, transmission electron microscopy (TEM), atomic force microscopy (AFM), low energy electron diffraction (LEED), X-ray near- energy ion scattering (MEIS). Such techniques provide information on the composition (AES, XPS, SIMS, GDOES, MEIS), morphology (TEM, AFM), ED, XANES) and thickness (ellipsometry, MEIS) of the films. edge absorption spectroscopy (XANES): medium structure (LE No technique is able to provide full information on all details of the composition, structure and morphology of a passive film, Further, many techniques expose the films to high vacuum, which may cause some changes to the film, for example loss of water. Thus, in general, the true nature of passive films is still a matter of debate. Nevertheless, it is usually recognized that the films are composed of oxides, hydroxides or oxyhydroxides, The composition of a passive film on a particular metal may also change with the conditions of formation, such as pH or temperature. Aive film may also consist of layers of material of differing compositions, for pas instance an inner oxide-rich layer above an outer hydroxide-rich layer. Flaws A passive film will contain relatively numerous flaws, even when formed on a metal of high purity. The flaws are local regions where the composition, structure and morphology of the film are modified compared with that developed upon the macroscopic surface of the metal. Flaws have been designated as mechanical, due to stresses associated with growth of film upon rough surfaces, or residual, due to the influence of segregated impurities in the metal on local film growth. Flaws are found in film material formed at grain boundaries, at impurity particles, at scratches in a metal surface. Most analytical techniques examine large areas of the specimen surface, compared with the thickness dimension of the passive film, and are insensitive to the presence of flaws. The flaws in the passive film may be important for the breakdown of passivity, for instance, if chloride ions are present in the solution, which can initiate pitting of the metal. Structure The structures of passive films are variable and for a particular film may change with time, Evidence is available for both amorphous or crystalline structures. Contaminant species Passive films may contain species derived from anions of the electrolyte. For example, a passive film formed on iron in an electrolyte containing borate ions may contain boron species. The concentration of such contaminant species in a passive film formed in an aqueous solution is generally low, typically no more than a few atomic percent. The roles of such species in film growth and in determining the properties of the film are generally ill-defined. These species probably have relatively small influences on the rate of film growth. However, evidence from thicker, anodic films suggests they may affect the stability of the film structure and the resistance of the film to hydration.Growth mechanism The growth of a passive film may involve several stages; for instance four stages have been identified in the growth of a passive film on iron. The first stage is the nucleation of film material on a bare metal surface, with formation of islands of film material, which grow to develop a continuous layer of film material of thickness approximately equal to the dimensions of the unit cell of the relevant oxide, hydroxide or oxyhydroxide. The second stage is a diffusion-controlled region in which the film thickens approximately parabolically with time. The third stage is probably a transition stage, between the second and final stages. The final stage is the steady- state growth of the passive film in which the film grows by a high-field conduction mechanism. In this last stage, the transport, by diffusion, of the reacting species through the passive film is driven by a high electric field. In this region, the thickness of the film is proportional to the potential drop across its thicknes The stages in the growth of passive films can be studied by electrochemical experiments, In the case of iron, the initial oxide film can be reduced electrochemically to produce a film-free metal. The potential of the iron is stepped to a new value of at which growth of the film can take place. Monitoring of the current as a function of time following the step change in the potential is a sensitive indicator of the processes occurring on the electrode, For example, a monolayer of iron contains about 10'° atoms cm, Assuming oxidation to charge state 2+, complete oxidation of the layer requires a charge of 3.2 x 10“ C cm”, Supposing that the oxidation takes place uniformly over 100 s, the current density corresponds to 3.2 wA cm?, which is readily measured. The growth of passive films involves electrochemical reactions, with transport of electrons and ions across the thickness of the film. The anodic reaction is the oxidation of the metal to form cations, which are incorporated into the passive film. The electron current occur due to either tunnelling or thermal emission. The electrons move from the metal to the surface of the film. The electron current results in reduction of oxygen or H’ ions at the film surface. Tunnelling is usually the dominantmechanism at room temperature, with thermal emission increasing in importance at higher temperatures. The current, J., due to tunnelling decreases rapidly with increasing thickness of the passive film: Je=Aexp(-L(vLe [I] in which A is a constant, L(t) is the thickness of the film at time t, and L¢ is the critical thickness at which the tunnelling current decreases significantly, Tunnelling is relatively easy when the film is very thin, i.e a few nm, The electrons tunnel from the metal, through the passive film, to form oxygen or hydrogen species adsorbed on the surface of the film. This electron transfer establishes an equilibrium contact-potential across the film, The transport of electron across the film is possible because it is energetically favourable for an electron to move from the metal to the electron levels of the absorbed species. The potential associated with the adsorbed species generates the thickne: ahigh electric field, E, acro: s of the film. The magnitude of the electric field is typically 10° - 10’ V cm’, For a particular ionic species in the film, the field it in the assists diffusion of these ions through the film in one direction and reduce opposite direction, At such high fields, ionic flux, J), due to a particular type of ion is almost completely in one direction, as movement of ions against the field is negligible. Then, to a good approximation, = Aexp(BE) [21 in which A and B are temperature dependent-constants. The film thickness increases due to the field-as d diffusion of ions leading to growth of the oxide at the film/environment interface, at the metal/film interface, or within the film, depending upon whether cations or anions are mobile, or both species. However, the electric field decreases as the film thickens because the contact potential remains constant. Thus, the tunnelling current reduces, Further, the ionic current also rapidly diminishes and the growth rate of the film is negligible. Therefore the thickness of the film remains low, typically 1-5 nm. If the material of the passive film has some solubilityin aqueous electrolytes, a steady state may exist in which the rate of formation of new film material equals the rate of dissolution of the film. Kinetics of growth of passive films The growth of passive films often follows a logarithmic rate law or an inverse logarithmic rate law. Logarithmic: d= A+B Int GB] Inverse logarithmic: 1/d= ky - ky Int 4] in which d is the thickness of the passive film, t is the time of growth and other parameters are constants for particular conditions of film growth. Stainless steel Chromium additions to steel improve the resistance to corrosion, with a progressive decrease in the corrosion rate as the amount of chromium reaches about 10 wi%, The improved behaviour is due to the formation of a chromium-rich passive film. Stainless steels have a strong tendency to passivate and require only low amounts of oxidizing species to develop passivity. Thus, they readily passivate in air or water. Passivity increases up to about 17 wt % chromium, hence many stainless steels contain about this level of alloying. Anodic Films Barrier-type anodic films Anodic films can be formed on so-called valve metals. These include Al, Ta, Nb, Mg, ', Bi, Ti, Hf, Zr and others. Anodic films can also be formed on semiconductors such as GaAs, InP, AlGaAs ete. The films are usually composed of insulating oxides e.g. AlOs, TayOs, WO; ete. Most anodic films are amorphous or microcrystalline instructure. Notable exceptions are those formed on Ti, Zr and Hf, which are crystalline. Anodic films on some metals, notably tantalum, aluminium, magnesium and titanium, have important practical applications, However, the growth of anodic oxides is of wider scientific interest, particularly with regard to mechanisms of oxide growth, In addition, the growth mechanisms of the anodic films may have similarities with that of passive films, which are of low thickness and hence, present more difficulties for experimental study. A bartier-type anodic film on aluminium, as observed by transmission electron microscopy using ultramicrotomy to cut a section of the film about 10 nm thick. The films are grown at constant current density or constant voltage usually in aqueous clectrolytes near ambient temperature. The most common morphology is barrier-type, with the films being of uniform thickness and free of porosity. The thicknesses of the films are normally <1 um. The electrolytes used to form barrier-type anodic films usually have relatively low reactivity with the oxide. The films therefore grow at high efficiency i.e. the current supplied by the power source is used to generate the ionic current in the oxide, with negligible electronic current in the oxide and negligible losses of ions from the film to the electrolyte. In reality, there are small losses of efficiency due to the presence of flaws in the films. The number of flaws depends upon factors such as the purity of the metal and the quality of the surface preparation,The reactivity of the oxide to the electrolyte depends upon the composition of the electrolyte and its pH. ‘The growth of the anodic film is duc to transport of ions across the film thickness, which is driven by a high electric field, E, of ~ 10°- 10" V em In the case of amorphous films, the cations and anions of the oxide migrate through the film. This leads to growth of oxide at the metal/oxide and oxide/electrolyte interfaces. The transport numbers are different for different types of amorphous oxide. For all amorphous oxides that have been examined by marker experiments, the transport number for anion species (i.e. O” ions) exceeds that for the cation species. ‘oxide | cation transport number ‘ALOs 042 TazOs 0.24 1b205 0.25 WO; 035 Bi2Oy O15 The available experimental evidence indicates that the ionic transport takes place by small-scale movements of ions, and does not involve short-circuit transport. An interesting feature of growth of amorphous anodic films is that the transport numbers of cations and anions change relatively little on changing the rate of film growth. ‘Thus, it appears that the movements of the cations and anions are linked: this is often termed co-operative transport In the case of crystalline films, primarily the anions of the oxide migrate through the film. This leads to growth of oxide mainly at the metal/oxide interface. Tracer experiments suggest transport of oxygen species by short-circuit paths through the oxide. However, less is known about the mechanism of growth of crystalline anodic film than that of amorphous anodic films.Ionic transport processes ~ tracer experiments - The mechanism of ionic transport can be investigated by tracer experiments. In a tracer experiment, a film is grown firstly in an O'-enriched environment. The same film is then grown to a greater thickness in an O'*-cnriched environment. The film composition is then analysed to determine the distributions of O'* and O'* through the film, which can be related to the mechanism of growth of the film, Transport of cations through the anodic film results in the growth of new layers of ns results film material at the film/electrolyte interface. Conversely, transport of ani in the growth of new layers of film material at the metal/film interface. New film material may also be formed within the thickness of the film if both cations and anions are mobile in the film, although experimental data indicate that film material is formed mainly at the metal/film and film/electrolyte interfaces. lonic transport in amorphous oxides may involve many separate movements of ions by small distances, for example, of the order of the lattice constant for a crystalline material. Such movements may be achieved by interstitial species, by vacancies or by complex defects. Alternatively, for crystalline oxides, ions may be transported along short- cireuit paths, such as grain boundaries or cracks. Tonic transport processes ~ marker experiments - A marker experiment is normally needed in order to determine which ions are migrating during the growth of an oxide film, (Passive films are too thin for investigation by marker experiments. Thus, the relative mobilities of the ions of the film are uncertain.) The marker experiments are normally carried out by ion-implanting a thin layer of xenon into a thin anodic film. ‘The film is then grown to a much greater thickness. The xenon forms very small bubbles in the initial thin film; the bubbles are immobile in the film as the film thickens during the second anodizing. The position of the xenon marker is then located by an appropriate analytical technique. In the case of amorphous films, the xenon is always found buried within the film, which indicates the migration of both anions and cations during the previous growth of the film. The relative magnitudes of the contributions of anions and cations to the total ionic current are given by the respective transport numbers. For relatively pure oxide films, the ratio of the depth of the marker to the thickness of the anodic film is equal to the cation transport number,provided that the film has been grown at high efficiency. In the case of crystalline films, the marker remains close to the film surface, indicating formation largely by inward migration of oxygen species. If the electrolyte is reactive towards the film, some of the migrating cations can be ejected to the electrolyte, due to the influence of the electric field, when they reach the surface of the film. The xenon marker is then located closer to the surface than found when the film grows at close to 100% efficiency. Determination of the cation transport number form the position of the marker is then erroneous. The loss of the cations to the electrolyte by field-assisted ejection should be distinguished from simple chemical dissolution. The rate of loss of cations from the film by chemical dissolution may be negligible compared with that in the presence of the field. Relative migration rates of ions in amorphous anodic oxide films - Studies of transport of contaminant species, derived from either the anions of the electrolyte or from an aluminium alloy substrate, in anodic alumina reveal a systematic behaviour for cation contaminant species, i.e. species which migrate outward in the growing. ‘The migration rate of such species exceeds that of Al” ions if the single metal-oxygen bond energy for the oxide of the contaminant element is less than that of the AI'*-O bond. Conversely, such species migrate more slowly than Al™ ions if the single metal-oxygen bond energy for the oxide of the contaminant element is greater than that of the Al’’-O bond. If the single metal-oxygen bond energy for the oxide of the contaminant element is particularly high, the contaminant species may be immobile in the growing film, Similar correlations of migration rates and bond energies apply in amorphous anodic films on tantalum and titanium,Barrier-type anodic film on an AI-W alloy illustrating the presence of tungsten species only in the inner two-thirds of the film thickness (dark region). The tungsten moves through the film more slowly than aluminium, Enrichment of tungsten can also be seen as a narrow dark band just beneath the anodic film. A xenon marker is also evident in the film as a row of small bubbles of light appearance near the outer region of the tungsten-containing layer. The transport in passive films formed on valve metals (metals that can be anodized) probably has similarity with the corresponding anodic oxides. However, it is possible that some passive films, for instance those on iron, are crystalline and form mainly by outward migration of cation species. There is no known example of an anodic oxide that grows by this mechanism.] The ionic current density, J, in the anodic film is given by the high-field conduction equation [2]. Thus, a constant current density requires that the electric field across the film is constant. The inverse of the electric field is the formation ratio. Typical values for current densities of 1 - 10 mA em” are: 1.2nm V" for alumina 1.6 nm V" for tantala 2.0 nm V" for titania ‘Thus, in the case of alumina, 1.2 nm of film are added for increase of the anodizing voltage by 1 V. Therefore, thicknesses of anodic films can be controlled with precision. However, in order to grow thick barrier-type films high voltages are 10required. For instance, a voltage of ~ 800 V would be required to grow an alumina film of thickness ~ 1 jum, In practice, the maximum voltage that can be applied is usually limited to much lower values by onset of dielectric breakdown during anodizing. Dielectric breakdown is manifested classically by sparking at the surface of the anodic film and evolution of oxygen gas, When diclectric breakdown commences, further increase in voltage is restricted. The dielectric breakdown voltage, Vg, increases as the concentration, ¢, of the electrolyte decreases. Vay=a-bloge 15] in which and b are constants. For instance, a decrease in the concentration of sodium tungstate electrolyte from 10" to 10“ M results in an increase in breakdown voltage of anodic alumina from about 280 to 650 V. The influence of current density on the breakdown voltage is negligible. Dielectric breakdown causes the formation of a highly flawed, relatively rough film, with film material modified by the high local temperatures generated by sparking The barrier anodic films on aluminium, tantalum and niobium find applications as dielectrics in electronics devices, and particularly capacitors. These films are grown below the dielectric breakdown voltages. Plasma electrolytic oxidation (PEO) Thick coatings, for instance to > 100 um, can be grown in the region of dielectric breakdown, (The process is called variously spark anodizing, plasma electrolytic oxidation, micro-arc oxidation). The coatings are of interest for protection of aluminium, magnesium and titanium against wear and corrosion, The coatings on titanium are also used for dental implants. Anodizing electrolytes are wide-ranging, but often contain silicate, phosphate and aluminate components. Coatings are formed under ac and de conditions. The coatings are porous; sealing with resins can be used to improve the corrosion resistance. The coatings contain high concentrations of species derived from the electrolyte as well as those derived from the substrate. Thecoatings can be amorphous, or with a significant crystalline content, The thickness of the coating is determined by the time of anodizing and the current density. Hardness values in excess of 2000 HV can be achieved. The efficiency of growth of the es to the coatings is usually low, for instance ~ 30%, due to oxygen evolution and los electrolyte. The coatings form at high voltage, requiring large power sources for supply of current and significant cooling facilities to remove heat that is generated in the el rolyte bath by the coating process. 500 400 300 Voltage (V) 200 109 0.050 M KOH + 0.025 M Na,SiO,SH,0 5 MINH,OH + 0.05 M (NH), HPO, ° 500 1000 1500 Time(s) Voltage time responses for anodizing aluminium at 5 A dm” in 0.05 M KOH + 0.025 M Naj$iO;.10H,O electrolyte at 293 K or 3 M NH,OH + 0.05 M (NH;):HPO. electrolyte at 293 K.‘Scanning electron micrographs of the PEO coating formed on aluminium for (a) 1800 s and (b) 3600 s 5 A dm” in 0.05 M KOH + 0.0025 M Na,Si0,.10H,0 electrolyte at 293 K. Porous anodic films PEO coatings are porous and are formed in electrolytes that support growth of barrier- type films at low voltages, due to limited reactivity of the anodic film and the electrolyte. Their growth mechanism is determined by processes occurring during dieleotric breakdown, when sparking is occurring on the anode. However, porous anodic films can also originate by field-enhanced reactivity of the electrolyte to the film material at voltages below the value for dielectric breakdown. The best-known, and practically the most useful example, occurs for anodic films formed on aluminium in either relatively acidic or relatively alkaline electrolytes. 2BThe resultant films are amorphous and have a morphology consisting of approximately hexagonal cells of alumina, with a central pore. The cells are aligned normal to the metal surface. The films can be grown to thicknesses of ~ 100 um. The pore then extends from the surface of the film almost to the metal/oxide interf: However, a thin barrier-type layer exists at the bottom of the pore. The diameter of the pores depends upon the conditions of growth of the oxide, but is typically in the range 10 - 100 nm. The thickness of the barrier layer at the base of the pore is in a similar range. Porous anodic film formed on aluminium in tartaric acid solution In the se of alumina, the onset of porous film growth coincides with the electrolyte being sufficiently reactive to prevent the formation of oxide at the film surface by outward migration of cations, i.e. all of the Al’ ions that migrate to the surface are lost to the electrolyte by field assisted ejection, The film/electrolyte interface then becomes unstable, and pores initiate due to field-assisted dissolution of the alumina, which can take place at rates that are 10° times faster than simple chemicaldissolution. The geometry of the pores enhances the local electric field, and the pores self-organize into a stable arrangement, The film then grows by adding new layers of alumina at the metal/film interface, with field-assisted dissolution of the alumina occurring at the base of the pores. If the film is grown at either a constant current or a constant voltage, the thickness of the barrier layer achieves a constant value. The anodizing voltage in the stage of steady-state porous film growth is below the value for dielectric breakdown Hence, the film can be thickened to high values compared with those achieved for barrier-type films, The material of the surface regions of the film is formed in th al stages of anodizing. Therefore, these regions are exposed to the electrolyte for much longer than the regions close to the metal, Chemical attack can lead to softening of the outer part of the film, and ultimately dissolution of the alumina, Such attack can limit the thickness of the film that can be grown under particular conditions. The attack can be reduced by anodizing at high current densities in low temperature electrolytes (termed hard anodizing, that produces films of hardness typically 300 - 700 HV). Voltage /V 4 95 6 7 8 9 HW NH 2 13 14 15 Time / min Typical voltage-time responses for sputtering-deposited niobium anodized at 10 A m ? in 10 wt% dibasic potassium phosphate in glycerol electrolyte at 453 K.Nanoporous anodic oxide film on niobium. Transmission electron micrographs of sputtering-deposited niobium anodized for 900 s at 10 A m* in 10 wt% dibasic potassium phosphate in glycerol electrolyte at 453 K. (a) Region with residual niobium. (b) Region of complete oxidation of the niobium. For this experiment, niobium was deposited as a thin layer on anodized aluminium. This method allows ins for transmission electron microscopy, which is not easily achieved with bulk niobium. Most of the niobium was oxidized to form the film. Sealing - Porous anodic alumina films are usually given a sealing treatment to improve the corrosion resistance of the anodized alloy. The simplest treatment involves immersion in water at ~ 100°C. This leads to hydration of the walls of the 16pores, forming a more voluminous product (pseudobochmite) that blocks the pores. Ageing leads to transformation to bayerite (Al(OH). Colouring - Porous alumina films can be coloured by organic dyes or by electrolytic deposition of metal within pores. Porous alumina films find applications in: architecture - cladding of buildings aerospace - corrosion and wear resistant finishes, pre-treatment in adhesive bonding automotive - finishing of aluminium sheet product by high speed anodizing general engineering - eg dies electronics/photonicisensors - a growing area, making use of the self-organizing features of the cells and their nanoscale dimension, There is evidence, but very restricted, for similar ,ie. celluar-type, porous anodic films on other metals. Transmission electron microscopy has suggested cellular-type porous anodic films on magnesium, Similar types of film have been produced on niobium and tantalum, the by anodizing in glycerol-based electrolytes at elevated temperature (~ 180°), The films are nanoporous, with pores of dimensions about 5 nm, The oxides can be produced at constant voltage of constant current. Very thick oxides can be produced at low voltages. Porous oxides can also be produced on niobium, titanium and zirconium in sulphuric acid/fluoride electrolyte, Such films are typically | than 1 um thick. Incorporation of species into anodic films from the electrolyte - The barrier-type and porous anodic oxides formed on valve metal usually contain low concentration of species derived form the anions of the electrolyte. For example, films formed in phosphate and tungstate electrolyte may contain ~ 1 - 5 at.% phosphorus and tungsten species respectively. These species migrate in the growing film, Cation species migrate outward. Anion species migrate inward. They can affect the properties of the film, for example resistance to crystallization, reactivity towards the electrolyte, resistance to hydration.Incorporation of species into anodic films from the substrate - Alloy and impurity elements in the sub: ate metal are incorporated into anodic films. They are usually incorporated as units of oxide and migrate outward in the film as a cation species. Second phase can have major local influences on the anodizing mechanism, frequently giving rise to defects that impair the film properties. For example, the hardness of anodic films produced by hard anodizing of aluminium alloys can be 50% lower than that of films on high purity aluminium, for similar conditions of film growth, The effects of alloying elements (mainly from studies of alumina films) are various: enrichment of alloying elements in the film stabilization of amorphous structures generation of oxygen gas within the film detachment of film material at the alloy/film interface film layers of differing composition porosity altered chemical resistance of the film material heterogeneity of film composition non-uniform thickness reduction of efficiency coloured finishes reduction in corrosion resistance reduction in hardness reduction in film thicknessBubbles of high pressure oxygen in a barrier-type anodic film on an Al-Cu alloy. The film was stripped from the alloy and viewed by transmission electron microscopy. An anodic film formed by anodizing a layer of aluminium on top of a layer of tungsten, The tungsten starts to oxidize when the aluminium has been fully oxidized. The tungsten oxide penetrate the alumina layer due to its low resistance for flow of ionic current. Selforganizing characteristics of porous anodic films - there is a large research activity developing aimed at producing perfect ordering of cells of porous anodicfilms, with most work being carried out on alumina, In the ideal case, the cells are of uniform size and organized in an hexagonal arrangement (like a honey-comb). The self-organizing tendency of the pore morphology is a natural consequence of the high- field growth and dissolution processes that take place during growth of the oxide. However, the initiation of pores is affected by the local chemistry and topography of the metal surface, so the pores may at first have a much more random distribution, To attain better ordering, a porous oxide is formed on the aluminium, then removed by chemical dissolution. A new oxide is then grown at a slow rate on the stripped aluminium surface. The new oxide usually has greatly improved ordering of the pores. Such oxides are of interest for their optical properties and for impregnation with materials for various gas sensing, biotemplating, catalytic and electronic applications, for which ordered nanoscale porosity is an important factor in performance. Anodic films on semiconductors - the growth of barrier-type anodic films on semiconductors, such as InP, GaP, GaAs, InAIAs is similar to that on solid-solution valve metal alloys. The films are amorphous and grow with formation ratios typically about 2.0 nm V7. The films are often layered in composition, since the cation species migrate through the film at differing rates, with migration rates correlating with bond energies of constituent oxide species. For instance, in the case of GaP, the film consists of an outer layer of Ga,O, and an inner layer containing units of both Ga;O; and POs, Oxygen bubbles can form within some film, by oxidation of the O ions of the film material; for instance, such bubbles, with nanoscale dimensions and associated high pressures, are present in films on InP, Some films dissolve at relatively high rates in aqueous electrolytes and cannot be formed at low current densities. In some cases, an induction period precedes growth of the anodic film, the period reducing with increase in the current density. The oxides are important for the manufacture of electronic devices.