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Abstract
A review is given of anodic alumina film formation on aluminium, with barrier and porous films developed by anodic polarization in an
appropriate electrolyte. Initial consideration of barrier-type films, using marker and tracers, allows definition of the locations of film growth
and consideration of the transport processes under the high electric field. From this base, the effects of altering film growth conditions,
generally using acid electrolytes, to generate porous anodic films are considered, with be resultant films of defined morphology thickening as
a result of the dynamic equilibrium between film growth at the metal–film interface and field assisted dissolution at the pore base–electrolyte
interface. Means for characterising the developed films are presented as well as applications of the porous, amorphous film material. q 1997
Elsevier Science S.A.
Keywords: Anodic alumina; Fabrication; Characterization; Electrochemistry
1. Introduction
ple, relatively large diameter pores are generated by density–time behaviour, depending on the mode of anodiz-
anodizing at high voltages in phosphoric acid compared with ing, enables the progress of anodic film formation to be
the fine pores in the anodic films which are developed rapidly followed [9].
by anodizing in sulphuric acid. Inert xenon marker layers are employed, following the
In this paper, the main theme is porous anodic films on initially successful procedure developed for their direct
aluminium which includes mechanisms of film growth, pore observation [10], with implantation carried out at an energy
development and propagation; procedures for determining as of 5 keV and dose of 1=1018 ions mmy2. Pre-formed anodic
precisely as possible the resultant film morphology, compo- films, of thickness about 12 nm, are developed initially on
sition and structure are also introduced. Finally, applications the electropolished aluminium substrate, allowing the
of porous anodic films are given, including membranes and, implant to be incorporated almost entirely within the anodic
keying layers; decorative, wear-resistant and protection treat- alumina film. Reanodizing, after implantation, revealed the
ments for aluminium are also considered. expected voltage–time or current density–time behaviour,
As indicated previously, the main focus is porous anodic indicating little, if any, influence of the implant on the ionic
films on aluminium; however, in order to provide the basis transport processes during reanodizing. The procedure indi-
for consideration of ionic transport phenomena in amorphous cated eliminated the anomalous film growth evident for ano-
alumina and interfacial processes, initial consideration is dizing implanted aluminium and the spreading of the implant
given to barrier-type films on aluminium, formed generally, region as a result of film growth.
but not exclusively, in near-neutral aqueous electrolytes. The After film growth, various analytical procedures may be
interfacial processes of importance in the formation of a par- employed to characterize film morphology, composition and
ticular film-type proceed at the film–electrolyte or pore base– structure. In the first case, morphological features are
electrolyte interface, with the ionic migration mechanism observed directly using transmission electron microscopy;
within the alumina film awaiting clarification. Relatively thus plan views of the anodic films are made by stripping the
recent studies have shown that very significant enrichments film from the scored substrate by amalgamation in mercuric
of alloying elements may develop over nanoscale dimensions chloride solution. Cross-sections of the anodic film, attached
immediately beneath the anodic film [8]. An overview of to the aluminium substrate, are generated by ultramicrotomy
this behaviour is also presented, since it has broad implica- using LKB, Dupont, RMC or Reichert ultramicrotomes in
tions on the surface treatment of aluminium alloys as well as the usual manner [11]. Briefly, the encapsulated specimens
possible relevance to anodic oxidation of electronic materials are trimmed initially with a glass knife and final sections, of
more generally, i.e. compounds. thicknesses as low as 7 nm, are generated with a diamond
In order to provide full coverage of the subject, including knife; the resultant sections are collected from the water bath
experimental details, interpretation and discussion, a series at the rear of the diamond knife and examined in Philips and
of publications is necessary, involving electrochemical, elec- Jeol electron microscopes at acceleration voltages between
tron-optical and surface analytical procedures.Consequently, 100 and 200 kV.
here an overview is given, assisted by use of appropriate Film compositions are determined frequently by Ruther-
schematic diagrams. The information provided has been gen- ford backscattering spectroscopy of a-particles (and related
erated largely in the Corrosion and Protection Centre at nuclear methods) using a 7.0 MeV Van de Graaff generator;
UMIST, and due acknowledgement is given to the contribu- when necessary and to avoid overlapping yields from the
tions of colleagues, research assistants and research students; underlying aluminium, window techniques are utilized [12].
further, the significant contributions of the many workers in Additionally, Auger electron spectroscopy with ion etching
this field over considerable periods of time are also acknowl- and X-ray photoelectron spectroscopy with chemical section-
edged here. ing are used for in-depth elemental profiles and appropriate
valency discrimination respectively [13]; such information
is also supported by analytical transmission electron micros-
2. Experimental copy, with suitable electron probes allowing appropriate res-
olution and count rate.
For marker and tracer studies during anodizing to produce Structural probing of the generally amorphous alumina
barrier films and in the growth of porous anodic films gen- films is undertaken by X-ray absorption studies (XAS) [14]
erally, spade electrodes of superpure aluminium (impurities: and with magic angle spinning nuclear magnetic resonance
Cu, 0.003 wt.%; Si, 0.002 wt.%; Fe, 0.004 wt.%) are nor- (MAS-NMR) [15]. Generally X-ray absorption spectra of
mally employed. Prior to anodizing, various surface pretreat- films are recorded on various beamlines at the SRS at Dar-
ments are used but, in many cases, electropolishing in a esbury. For example, spectra for Mo, W and Cr edges are
perchloric acid–ethanol mixture at 20 V for 5 min at temper- recorded in the fluorescence mode, with specimens mounted
atures less than 298 K is employed to develop a reproducible at an angle of 458 to the incident beam. Acquisition of Al, S
surface finish. Anodizing is then performed at constant cur- and P K-edge data requires the samples to be mounted in
rent density or constant voltage in various electrolytes of ultra high vacuum. The X-ray absorption is measured by
different pH values; the resultant voltage–time or current recording the total electrons yield as the drain current from
the sample, whilst the incident flux is measured as the drain anodizing of aluminium reveals that the film thickens at about
current from a beryllium foil intersecting the X-ray beam. 1.2 nm Vy1. In order to maintain the constant field strength,
Model compound data are also generated in the total electron the voltage must increase as the film thickens. The field also
yield mode, with the samples being prepared by grinding and serves to provide highly uniform film growth, with the devel-
then dispersion on a copper substrate. High resolution 27Al oping film smoothing the roughness of the initial aluminium
MAS-NMR are obtained at 93.8 M Hz on a Brucker MSL surface. Uniform film thickening is terminated eventually by
360 (8 4ST) spectrometer. For NMR analysis, the oxide dielectric breakdown, with visible sparking observed fre-
sample is removed from the aluminium substrate by the amal- quently over the anodic film surface.
gamation procedure indicated previously. About 100 mg of
film material is necessary for analysis, requiring anodizing of 3.1.1. Marker and tracer studies
sufficient specimens of appropriate exposed surface area. As an initial step in understanding the complex ionic trans-
In appropriate situations, the aluminium ion concentration port processes in amorphous solids, inert marker experiments
in the electrolyte after anodizing, or through film dissolution assist in defining the locations of film growth. Fig. 3 indicates
in the absence of the field, i.e. chemical dissolution, is deter- marker locations for transport solely by cation egress
mined by atomic emission spectroscopy. Aluminium detec- (Fig. 3(a)), anion ingress (Fig. 3(b)) and combined cation
tion limits are of the order of 50–100 ppb using the allied egress and anion ingress (Fig. 3(c)). For aluminium, ano-
inductively coupled argon plasma facility. dized under high current efficiency conditions, the last is
revealed by transmission electron microscopy of ultramicro-
tomed sections of anodic films incorporating an immobile
3. Results and interpretation and inert xenon marker. The xenon is revealed directly as gas
bubbles within the film section; the distribution and unifor-
3.1. Barrier-type anodic alumina films mity of the xenon has changed little from its presence in the
initial pre-formed film. Further, the presence of xenon as
As indicated previously, the barrier films of Fig. 1(a) are discrete bubbles, i.e. not an integral part of the film ‘structure’,
considered initially, to provide the base for understanding the also provides further justification for its immobility. Addi-
development of the porous anodic alumina film. For galva- tional experiments using g/g9 nuclei as markers confirm the
nostatic anodizing, the resultant voltage–time behaviour immobility of the xenon marker and the aluminium cation
(Fig. 2) reveals an initial voltage surge of about 2.0 V, indic- transport number of about 0.4 for film growth at high current
ative of the prior presence of an air-formed film of thickness efficiency [17]. The cation transport number is determined
2.5 nm on the electropolished aluminium surface. Thereafter, from the ratio of the film thickness developed above the
the voltage rises linearly with time as the relatively compact marker to the total film thickness.
film thickens uniformly with time. The driving force for film The uniformity of the marker within the film section and
growth is high field ionic conduction [16], which may be its limited spreading across the film thickness also suggest
expressed simply as isAexp(BE), where i is the anodic strongly that the alumina film develops simultaneously and
current density (typically in the mA range), A and B are only at the film–electrolyte and metal–film interfaces by Al3q
temperature dependent constants, and E is the field strength egress and O2y/OHy ingress under the high field, i.e. no
(the ratio of the potential drop across the alumina film to the growth of film occurs within the film section, which would
film thickness). Clearly, films grown at constant current den- reveal a non-uniform marker layer distribution.
sity develop at a constant field strength, of the order of 106– Tracer studies [18] utilize a mobile species, with its loca-
107 V cmy1; further, the reciprocal of the field strength for tion or distribution within the film determined as a result of
an incremental increase in film thickness. A classic example
is the determination of 16O and 18O profiles as a result of
anodizing initially in a normal aqueous electrolyte, followed
2Alq3H2O™Al2O3q6Hyq6e
The adsorbed anions or resultant electrolyte species are
then incorporated uniformly and at relatively low levels into
the alumina film material developed by Al3q egress. The fate
of the adsorbed/incorporated species within the alumina film
material then depends on the consequences of the action of
the electric field on the incorporated species. Thus, it is sug-
gested that B2O3 units are incorporated, with the electric field
strength being insufficient to break B–O bonds, unlike Al–O
bonds; hence an immobile species results. Conversely, the
field strips oxygen atoms from WO3, resulting in the gener-
ation of W6q cations, which move outwards at a slower rate
than that of Al3q ions under the field. For PO34y anions, these
remain unaffected by the high field and migrate inwards, at a
rate less than that of O2y/OHy ions. For the anodic films
considered, of density 3.1=103 kg my3, typical averagecom-
positions are:
Al2O3.07"0.03B0.06"0.01 (Al2O30.030"0.005(B2O2.4"1.2))
Al2O3.17"0.02P0.072"0.06 (Al2O2.99"0.040.074"0.006(AlPO4))
Al2O3.051"0.0008W0.0146"0.0001 (Al2O30.015"0.001(WO3"1))
Fig. 5. Schematic diagram showing influence of reduced current efficiency
of film formation ((a)–(c)) on the voltage–time response and position of
3.1.2. Film growth at reduced current efficiency an implanted marker in the film section. At 100% current efficiency, for
For film growth at high current efficiency, i.e. 100%, the anodizing at 5 mA cmy2, the slope of the V–t curve of (a) is 2.3 V sy1; this
reduces to about 1.4 V sy1 (c) prior to porous anodic film formation.
voltage–time response of Fig. 2 reveals a slope of 2.3 V sy1
for anodizing at 5 mA cmy2. Interestingly, as the current ions detected in solution for (b), and with an increased con-
density employed for anodizing is reduced the slope of the centration for (c). Further, if the aluminium ion concentra-
voltage–time curve shows a proportionate reduction; how- tion in solution is transformed into an effective filmthickness,
ever, below a certain current density, an increased amount of the marker would be located at the usual position for film
charge is required to achieve a selected voltage, or film thick- growth at high current efficiency, i.e. at a location of 0.4 of
ness, implying a decrease in current efficiency from 100%. the film thickness measured from the film–electrolyte inter-
With further reduction in current density, the efficiency face (Fig. 5(d)–5(f)).
decreases, until a so-called critical current densityisachieved, Direct interpretation thus indicates that, for all growth con-
when a porous anodic film results [24]. Broadly, similar ditions, Al3q egress and O2y/OHy ingress occur under the
behaviour is evident when the electrolyte pH is reduced from high field. However, the fate of the outwardly mobile Al3q
near-neutral levels. ions at the film–electrolyte interface depends upon the partic-
Understanding the previous behaviour is assisted by the ular interfacial conditions. Thus, at high current efficiency,
observation of the locations of marker layers within the all outwardly mobile Al3q ions form film material at the film–
anodic film sections. Thus, Fig. 5 considers anodizing at con- electrolyte interface; conversely, at the critical current den-
stant current density in a typical neutral solution (a), and sity, all outwardly mobile Al3q ions are ejected directly into
solutions of progressively reduced pH (b) and (c). As the the solution from the film–electrolyte interface [24,25]. For
solution pH is reduced, an increasing time and hence, charge intermediate conditions of solution pH and/or current den-
are required to form films to the selected final voltage and sity, a proportion of the outwardly Al3q ions are lost to the
thickness. Observations of the resultant film sections and electrolyte. Dissolution (chemical) of the alumina film mate-
associated xenon marker reveals that the implanted xenon rial is relatively insignificant, and the presence aluminium
location moves outwards, towards the film–electrolyte inter- ions in solution results from direct ejection. This is readily
face, indicating a progressive reduction in the apparent trans- tested by reanodizing the film formed under the condition,
port number of aluminium cations. Indeed, at the so-called (c) to increased voltage when the marker remains located at
critical current density, the marker is located in the alumina the film–electrolyte interface. If film dissolution per se is
film material adjacent to the film–electrolyte interface,imply- important, the marker would have been lost by successive
ing an apparent cation transport number of zero. removal of the film material by dissolution proceeding
Parallel studies of the electrolyte composition for anodiz- inwards from the film–electrolyte interface.
ing under the conditions of Fig. 5 revealed the absence of At the critical current density, when the apparent cation
aluminium ions in solution for condition (a), with aluminium transport number is zero, the alumina film material develops
4. Concluding remarks
Lastly, the porous alumina material, sufficiently modified, or [12] P. Skeldon, K. Shimizu, G.E. Thompson and G.C. Wood, Surf. Int.
tailor-made, may be penetrated by many various materials, Anal., 5 (1983) 247, 252.
[13] Y. Xu, G.E. Thompson and G.C. Wood, Corros. Sci., 27 (1987) 83.
perhaps providing novel devices for future consideration. [14] J. Robinson, G.E. Thompson, K. Shimizu, K. Hebert and G.E.
Thompson (eds.), Oxide Films on Metals and Alloys, Proc. Vol. 94–
25, The Electrochemical Society Inc., Pennington, NJ, 1994.
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