Surface & Coatings Technology 200 (2006) 4530 4537 www.elsevier.

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Changes in the specific surface area of porous aluminium oxide films during sealing
M.J. Bartolome*, V. Lopez, E. Escudero, G. Caruana, J.A. Gonzalez
National Centre for Metallurgical Research (CSIC), Avda. Gregorio del Amo, No. 8 28040 Madrid, Spain Received 25 October 2004; accepted in revised form 22 March 2005 Available online 11 May 2005

Abstract This paper analyses the information on anodic film sealing and autosealing ageing processes which can be provided by thermogravimetry and gas adsorption porosimetry techniques that are much less widely used in this type of study than electrochemical impedance spectroscopy (EIS) or scanning and transmission electron microscopy (SEM and TEM). During the porous wall dissolution stage, the pore volume is approximately doubled due to the dissolution of anhydrous alumina in the hexagonal cell walls, forming a bayerite gel that precipitates upon reaching the saturation point. The pore diameter increases from 140 150 to 200 220 A and its specific surface area grows from approximately 20 m2/g to around 30 m2/g. The informations obtained by thermogravimetry, porosimetry, EIS and TEM are complementary and concordant, allowing an estimation of the effects of the dissolution and precipitation stages, which can be directly and quantitatively visualised by SEM. D 2005 Elsevier B.V. All rights reserved.
Keywords: Aluminium; Anodisation; Sealing; Autosealing; Ageing

1. Introduction The anodising of aluminium and its alloys develops porous oxide films which, since about 70 years ago, are sealed in boiling deionised or distilled water (HTS: hydrothermal sealing) in order to preserve their appearance and protect them from corrosion [1,2]. The great dissemination and importance of this procedure explains why many researchers over the years have dedicated efforts to studying the sealing mechanism [3 8]. One of the first theories on HTS was put forward in 1962 by Hoar and Wood [3] who, based on impedance studies, proposed as essential phases of sealing the formation of a boehmite plug at the outer end of the pores and the progressive movement of the hexagonal cell walls towards the interior of the pores until they finally become plugged along their entire length.

* Corresponding author. Tel.: +34 9 1 5538900; fax: +34 9 1 5347425. E-mail address: mjbartolome@cenim.csic.es (M.J. Bartolome). 0257-8972/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2005.03.019

The sealing process involves a complex mechanism which consists of a series of stages that lead to the formation of layers with different strata: an outer layer of acicular boehmite crystals; an intermediate layer of a high density hydrated oxide; a more internal and much thicker layer which retains a porous cell structure; and the innermost layer, known as the barrier layer, which is extremely thin and pore-free [1,2]. The work of Wefers [4], based on gravimetric techniques, X-ray diffraction and scanning and transmission electron microscopy, and of UMIST researchers, preferentially using TEM [5 8], represent highly valuable contributions to the understanding of the subtle structural changes that take place during the sealing process. Apart from pore plugging, which enormously reduces the absorbent capacity of unsealed anodic films, preventing their soiling and degradation due to the penetration of corrosive substances from the environment, the changes that most influence the properties of anodic films are those which affect the porous layer, whose thickness amply exceeds the combined thickness of all the other sublayers.

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The processes that take place during HTS involve the dissolution of anhydrous alumina from the pore walls, the formation of a hydrated alumina gel inside the pores, the saturation and subsequent precipitation of alumina hydrates, which eventually plug the entire length of the pores [4 8], and the final process of crystallisation and agglomeration that can continue over months and years [5,9 12]. The present work analyses the information on anodic film sealing and autosealing ageing processes which can be provided by thermogravimetry and gas adsorption porosimetry, techniques that are much less widely used in this type of study than electrochemical impedance spectroscopy (EIS) or scanning and transmission electron microscopy (SEM and TEM).

2. Experimental methodology 2.1. Materials used Aluminium specimens of commercial purity, 99.5% Al, were anodised in industrial conditions in an 18 wt.% sulphuric acid solution at 20 -C and 1.5 A/dm2. The oxide layer thickness, except in some experiments, was always 20 Am. The specimens were subjected to different sealing times in boiling deionised water or to slow autosealing processes at room temperature in humidity saturated environments. 2.2. Test methods Impedance diagrams were recorded for the sealed and unsealed anodised specimens, immediately after anodising and sealing and after different ageing times. A surface area of 1 cm2 was exposed to the impedance test solution, i.e. an unstirred and aerated 3.5% K2SO4 solution at 25 T 1 -C, applying a frequency range from 1 mHz to 100 kHz and using the same equipment and test cell as previously reported [9 12]. To obtain complementary information to that supplied by the electrochemical tests, the different anodic film types, once separated from the metallic substrate by dissolution of the latter in HgCl2 solution, were subjected to thermogravimetric tests, gas adsorption porosimetry, TEM and SEM. In order to examine sections parallel to the surface plane in the transmission electron microscope, specimens were prepared by ion beam thinning of the anodic films previously separated from the metallic substrate. As the thinners ion beam acted on both faces, the cross sections of the cells and pores correspond approximately to the centre of the anodic films. The thinned specimens were directly observed in a JEOL JEM 2010 transmission electron microscope. The scanning electron microscope was used to examine cross sections of the coating and sections parallel to the surface plane.

The cross sections were obtained by tensile fracture of the oxide layer and allowed examination of the entire length of the pores in the coating. The sections parallel to the surface plane were obtained by polishing with 1 Am diamond paste and finishing with magnesia. Three sections were studied, situated approximately 1 Am from the outer surface of the coating, at an intermediate point, and 2 Am from the inner surface. The polished specimens were attacked in 10% phosphoric acid solution for 30 s, washed in alcohol in an ultrasonic bath, metallised with gold or platinum in vacuum, and observed in a JEOL JSM 6500F scanning electron microscope. Metallising the specimens reduces the effect of charging of the observed surface by the electron beam and improves the images contrast quality. Thermogravimetric tests were carried out using a Perkin Elmer TGS-II thermobalance, with a sensitivity of 0.2 Ag, expressing mass variations directly as a percentage of the original mass. Two types of experiments were performed: 1. In air at 100 cm3/min, with a heating rate of 10 -C/min between 25 and 700 -C. 2. In nitrogen, in the same conditions but after degassing for 17 h at room temperature, with a vacuum of 5 10 3 mm Hg in order to extract the water that had not yet reacted with alumina. By the analysis of N2 adsorption desorption isotherms, gas adsorption porosimetry allowed the determination of the specific surface area of the anodic oxides with different sealing or autosealing grades and the measurement of the diameter and the volume of their pores. The specific surface area was obtained by application of the BET transform to the first points of the isotherm [13], at relative pressures of less than 0.2, taking 0.162 nm2 as the transverse area value of the adsorbed N2 molecule. The volume and distribution

Fig. 1. Thermogravimetry of a film sealed for 1 min in boiling water, obtained after prior degassing at room temperature with 5 10 3 mm Hg (the lower line is the derivative).

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Fig. 2. Thermogravimetry of an unsealed film aged for 7 days at high relative humidity, obtained in the same conditions as the preceding figure.

Fig. 3. Sample as in Fig. 1 thermoanalysed in air atmosphere without prior degassing.

of the pores were obtained by the adsorption desorption data (hysteresis loop) at relative pressures of more than 0.4.

3. Results 3.1. Thermogravimetry for different HTS or autosealing grades Figs. 1 and 2 present, respectively, thermograms of anodic films sealed for 1 min in boiling water and unsealed but aged for 7 days at high relative humidity, obtained after prior degassing at room temperature with 5 10 3 mm Hg. Both present identical behaviour, with an increasingly rapid transfer of water up to 230 -C, as is shown by the minimum of the derived curve. After this an increasingly slow loss is detected, which represents only 0.60% between 330 and 600 -C. The total losses are 7.16% and 7.13%, respectively (Table 1). The samples thermoanalysed in an air atmosphere without prior degassing, which also include two specimens sealed for 45 and 120 min in boiling deionised water, present a different behaviour, as can be seen in Figs. 3 6 and in Table 1, which summarises the results. In the specimens sealed for 1 min or aged for 7 days in a humidity cabinet, a rapid initial mass loss is recorded, with two maximum rates situated at approximately 170 and 275 -C
Table 1 Results of the thermoanalyses performed Sample 1 min* 7 days* 1 min 7 days 45 min 120 min Loss, % 25 230 -C 7.71 9.51 25 330 -C 6.59 6.56 8.95 10.38

(Figs. 3 and 4). Finally, a very slow process takes place between 450 and 650 -C, in which a small amount of mass is lost, less than 2%, giving total losses of 16 19% (Table 1). In the specimens sealed for 45 and 120 min, a rapid initial loss is detected, with one single step, and the final slow sector, with much lower overall losses, of 9 12% (Figs. 5 and 6 and Table 1). 3.2. Measurement of gas adsorption porosimetry Table 2 summarises the changes in the specific surface area of porous aluminium oxides caused by sealing or autosealing. It can be seen that industrial sealing approximately reduces the surface area from 17 to 2.5 m2/g and that prolonged autosealing in a humidity cabinet reduces it much more. In contrast, it is noted that very fast sealing or short autosealing times substantially increase the specific surface area. 3.3. Impedance measurements Fig. 7 shows the typical impedance diagrams of an anodic film in unsealed state and another after 45 min of traditional hydrothermal sealing (2.5 min/Am of thickness) in boiling deionised water. It can be seen that in a wide frequency range the impedance of the sealed and unsealed anodic films differs by 2 3 orders of magnitude, making

230 450 -C 7.28 7.45

330 600 -C 0.57 0.57

450 650 -C 1.41 1.86 0.51 1.22

Total 7.16 7.13 16.4 18.82 9.46 11.6

*Degassed for 17 h at room temperature and 5 10 3 mm Hg.

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Fig. 4. Sample as in Fig. 2 thermoanalysed in air atmosphere without prior degassing.

Fig. 6. Anodic film sealed for 120 min in boiling water and thermoanalysed in air atmosphere without prior degassing (the lower line is the derivative).

EIS a very sensitive tool to discern sealing quality or to detect changes in the characteristics of the barrier and porous layers. This figure also shows in schematic form how the capacitance of the barrier and porous layers, C b and C p, can be estimated by extrapolation of the straight line regions to the angular frequency x = 1 and how the porous layer resistance, R p, can be estimated from the impedance value corresponding to the minimum phase angle [12]. During the first days or weeks of ageing in humid environments, the porous layer resistance of the sealed specimens often presents a significant decrease, passing through a not very accentuated minimum as can be seen in Fig. 8, which displays the results obtained during the exposure of recently sealed and unsealed anodic films in a humidity cabinet at room temperature. Subsequently, a notable increase in the impedance occurs due to the effect of changes caused by the ageing of the porous layer. 3.4. Scanning and transmission electron microscopy tests Though SEM and especially TEM are the techniques that have contributed most to the knowledge of the

structure of anodic films formed on aluminium and its alloys, they are used here as comparative tools to evaluate the importance of the information supplied by thermogravimetry and gas adsorption porosimetry. In this sense, the micrograph in Fig. 9, obtained by TEM for a section parallel to the surface, displays the hexagonal structure of the porous layer and allows approximate estimation of the size of the cells and the diameter of the pores and from their measurements the structural characteristics are summarised in Table 3. The micrographs in Figs. 10 and 11, obtained by SEM, show the structures of the anodic coatings in unsealed state and with a conventional HTS of 45 min, respectively, for the case of sections situated at a depth of 5 Am parallel to outer surface. Attention is drawn to the evidently larger diameter of the pores in the sealed product, compared with the unsealed oxide obtained in identical anodising conditions. Fig. 12 presents a cross section with insufficient resolution of the unsealed anodic coating, while Figs. 13 and 14 show cross sections at greater magnification of the unsealed anodic coating in the central area and adjacent to the base metal, respectively, in which it is possible to appreciate many microstructural details such as the approximate pore diameter, hexagonal cell wall thickness and barrier layer thickness.
Table 2 Results of the N2 adsorption porosimetry Specimen type Unsealed anodic film Sealed for 1 min Sealed for 45 min Aged for 6 days Aged for 14 days Aged for 2 months S BET (m2 g 1) 17.3 32.5 2.46 34.6 18.8 0.39 V pore (cm3 g 1) 0.073 0.186 0.0064 0.199 0.139 0.00058 / p (A) 168 229 104 230 296 59

Fig. 5. Anodic film sealed for 45 min in boiling water and thermoanalysed in air atmosphere without prior degassing (the lower line is the derivative).

S BET: specific surface area (BET transform), V pore: specific pore volume and / p: pore diameter.

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Fig. 9. Micrograph obtained by TEM of a section parallel to the surface plane of an ionically thinned unsealed anodic film.

has been completely destroyed, and the plugging of the pores along their entire length due to the effect of HTS.
Fig. 7. Bode diagrams obtained for unsealed (>) and sealed (?) anodic layers using the EIS technique. The porous and barrier layer capacitance, C p and C b, were calculated by extrapolation of the straight segments to x = 1. The porous layer resistance, R p, was taken as the Z value corresponding to the minimum phase angle.

4. Discussion 4.1. Dissolution precipitation stages verified by the different techniques Bearing in mind that bayerite (Al2O3I3H2O) is the Al hydroxide that is stable at room temperature [14], the gel that fills most of the pores after HTS, or that which is slowly formed by autosealing at room temperature, must essentially be composed by this substance, which will eventually saturate the solution and precipitate. In the case of sealing for a few minutes at water boiling point, or autosealing for a few days at room temperature, the water that penetrates the pores will not form boehmite due to the lack of time in the first case and to the too low temperature in the second. Inside the pores, an unsaturated bayerite gel with a very high proportion of water forms [4], which explains why a considerable part is eliminated during degassing prior to thermoanalysis, as is shown by the data in Table 1 and the differences between Figs. 1 and 2 obtained with prior degassing and Figs. 3 and 4 without degassing. From the micrographs of the unsealed coating (Fig. 9) a pore diameter of 140 A and a diagonal of the hexagonal cells of 355 A are estimated allowing to deduce the structural characteristics of the anodic film that are summarised in Table 3. These data fit rather well with the results obtained recently by other researchers for films formed in sulphuric acid under identical voltage [15]. A porosity of 18.8% is calculated and so the 2.4 g/cm3 of

Finally, Fig. 15 shows a cross section of the outer part of the sealed anodic film while Fig. 16 shows the central part of the same coating. The essential differences compared with the unsealed coating are the formation of an acicular pseudoboehmite surface layer, an intermediate compact layer immediately below, in which the porous structure

Fig. 8. Variation in the porous layer resistance of unsealed and sealed anodic films (boiling in deionised water for 45 min) exposed to a highly humid atmosphere (humidity cabinet).

M.J. Bartolome et al. / Surface & Coatings Technology 200 (2006) 4530 4537 Table 3 Cell characteristics of anodic films formed in sulphuric acid solutions Oxide type Unsealed oxide Sealed oxide / pi (A) 140 CD (A) 355 355 C s (cm2) 8.18 10 8.18 10 12
12

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Sps (m2 g 1) 20.6 30.1*

V p (%) 18.8 40*

/ pf (A) 204 (1.46 / pi)

*After the dissolution stage and before the precipitation stage. / pi: initial pore diameter; CD: cell diagonal; C s: cell surface; Sps: specific surface; V p: pore volume/anodic layer volume; and / pf: final pore diameter.

density attributed to unsealed anodic films [16] is converted to 3.0 g/cm3 for the cell walls. As bayerite has a density of 2.4 g/cm3, the pore must be widened to a final diameter that is 1.46 times the initial value. Thus the specific surface area would pass from 20.6 to 30.1 m2/g and the porosity from 18.8% to 40%, before the occurrence of precipitation and the plugging of the entire length of the pores. The above data coincides almost exactly with that obtained by gas adsorption porosimetry (Table 2). N2 adsorption tests were programmed to determine the relationship between adsorbent properties and the sealing or autosealing grade, in the belief that the specific surface area would decrease continuously as these grades increased. However, before the expected reduction in the porosity of the anodic films, a significant increase takes place in the volume of the pores and consequently in the specific surface area of the films (Table 2). This type of response is a logical consequence of the central stages of the sealing mechanism proposed by Wefers and the UMIST researchers, specifically the stages of dissolution and precipitation. With the progress of sealing or autosealing, the specific surface area is enormously reduced, cancelling the absorbent capacity of the unsealed anodic films, as it is witnessed by the data for the samples sealed for 45 min and, above all, for the sample autosealed for 2 months in a humid atmosphere (Table 2). The impedance diagrams offer an indirect demonstration of this mechanism. As the pore section is duplicated in the dissolution stage, so the section that conducts electrical signals in the porous layer is also duplicated. As a consequence, the porous layer resistance of the sealed

coatings decreases to approximately 50% during the first month (Fig. 8). Subsequently the precipitation stage gives rise to opposing changes, with a progressive increase in the porous layer resistance, which is maintained for very long time periods up to years and decades [9 12]. This increase in R p takes place even in the unsealed anodic films due to the effect of self-sealing in humid atmospheres (Fig. 8). The plugging of 40% of the porosity (Table 3) with bayerite, after the dissolution and precipitation stages, would represent 36.9% of the anodic film mass, which should lose a quantity of water equivalent to 8.5% of its weight in order to dehydrate to boehmite during the thermogravimetric measurements; these values very approximately agree with the losses of the anodic films sealed for 45 and 120 min (Figs. 5 and 6 and Table 1). 4.2. Experimental check of the widening of the pores during sealing and formation of acicular and intermediate layers The micrographs in Figs. 10 and 11, obtained by SEM for the unsealed and sealed anodic films, respectively, reveal that the average diameter of 147 A at the end of anodising leads, during 45 min of traditional HTS, to a structure with plugged pores of an average diameter of 216 A, which represents a widening of 47%, almost identical to the value of 46% calculated from the TEM micrograph (Fig. 9 and Table 3), supposing that the pores are plugged by the dissolution of anhydrous alumina from the walls and the subsequent precipitation of bayerite, once the saturation point is reached.

Fig. 10. SEM micrograph of an unsealed anodic film.

Fig. 11. SEM micrograph of a sealed anodic film.

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Fig. 12. SEM view of cross section obtained by tensile fracture of the unsealed anodic coating.

Fig. 14. Cross section in the zone of the barrier layer of the same coating than that of Fig. 12, but at greater magnification.

The advantage of SEM over thermogravimetry, gas adsorption porosimetry and EIS techniques is that it allows a precise visual quantitative check to verify the dissolution and precipitation stages of the sealing mechanism, while the other techniques only allow their deduction. For instance, in the unsealed anodic films it is possible to note the tubular form of the pores, with straight and smooth walls (Figs. 12 and 13), which are opened on the outer surface of the coating, and to reveal the hemispheric shape of the bottom of the pores, in normal development at the metallic surface, separated from the latter by the so-called barrier layer which develops a humped form (Fig. 14). After the sealing treatment, the coating experiences a transformation of the oxide layer which affects the entire length of the pores and is most intense in the outer portion of the coating, where the porous structure has completely disappeared, being replaced by a compact oxide layer (intermediate layer), and acicular-shape microcrystals have formed on the plane of the outer surface (Fig. 15). The

thickness of the compact oxide layer formed on the outer surface of the coating is of the order of 0.25 Am. In more internal zones some roughness is observed on the surface of the pore walls, along with precipitation of an agglomeration of microscopic particles in their interior (Fig. 16). 4.3. Crystallisation, agglomeration and ageing stages In the unsealed samples, R p is not initially detected because its value is so low that it does not control the impedance in any frequency interval (Figs. 7 and 8). With the advance of autosealing, whose kinetics depend on the environmental humidity and temperature, R p starts to be determined after 1 2 weeks in a humidity cabinet at room temperature (Fig. 8). After some months, autosealing equals the behaviour of the sealed and unsealed specimens [17]. The great sensitivity of EIS has allowed to show that the

Fig. 13. Cross section in the central zone of the same coating than that of Fig. 12, but at greater magnification.

Fig. 15. SEM view of the surface portion of the coating showing an external sublayer of acicular-shape microcrystals and a more internal compact oxide sublayer, known as intermediate layer.

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& The calculations of the specific surface area and the volume of the pores from the micrographs obtained by TEM yield values that are in very good agreement with those obtained by porosimetry and, almost exactly, with the widening of the pore during sealing that is shown by the micrographs obtained by SEM. & Examination in the scanning electron microscope allows a study of the morphology and dimensions of the pores in the anodic coatings and their plugging by effect of the hydrothermal treatment. & SEM observation also highlights the stages of pore wall dissolution and the formation of an acicular pseudoboehmite surface layer and an intermediate layer immediately below, in which the porous structure has been completely destroyed.
Fig. 16. Cross section of the sealed anodized coating in the central zone.

Acknowledgements changes inside the anodic layers take place over years or decades [9 12,17]. Wood and OSullivan suggest that ageing effects could be due to long-term aggregation processes, with agglomeration and growth of the largest crystals at the cost of the smallest, evolving towards states of lower energy [5]. Therefore, in addition to the traditionally accepted stages of the sealing mechanism, it would be necessary to add another one of great importance, i.e. the ageing of the anodic films [10]. This work was supported by the Comision Interministe rial de Ciencia y Tecnologa (CICYT) of Spain within the framework of Project MAT2003-02217.

References
[1] S. Wernick, R. Pinner, P. Sheasby, The surface treatments of aluminium and its alloys, 5th Edition, ASM International and Finishing Publications Ltd. Metals Park, Ohio, 1987, pp. 773. [2] A.W. Brace, The Technology of Anodizing Aluminium, Technicopy Ltd., Stonehouse, Glos, England, 1979, p. 1. [3] T.P. Hoar, G.C. Wood, Electrochim. Acta 7 (1962) 333. [4] K. Wefers, Aluminium 49 (8) (1973) 553; K. Wefers, Aluminium 49 (9) (1973) 622. [5] G.C. Wood, J.P. OSullivan, J. Electrochem. Soc. 116 (1969) 1351. [6] G.E. Thompson, R.C. Furneaux, G.C. Wood, Trans. Inst. Met. Finish. 53 (1975) 97. [7] Y. Xu, G.E. Thompson, G.C. Wood, Electrochim. Acta 27 (1982) 1623. [8] R.C. Furneaux, G.C. Wood, Trans. Inst. Met. Finish. 60 (1982) 14. [9] J.A. Gonzalez, V. Lopez, E. Otero, A. Bautista, R. Lizarbe, C. Barba, J.L. Baldonedo, Corros. Sci. 39 (1997) 1109. [10] J.A. Gonzalez, V. Lopez, E. Otero, A. Bautista, J. Electrochem. Soc. 147 (2000) 984. [11] V. Lopez, J.A. Gonzalez, E. Otero, E. Escudero, M. Morcillo, Surf. Coat. Technol. 153 (2002) 235. [12] J.A. Gonzalez, V. Lopez, A. Bautista, E. Otero, X.R. Novoa, Appl. Electrochem. 29 (1999) 229. [13] S. Brunauer, P.H. Emmet, E. Teller, J. Am. Chem. Soc. 60 (1938) 309. [14] E. F. Barkmann, Anodized aluminium, Ed. ASTM-STP 388, Philadelphia, PA 19103, 1965, p. 85. [15] S. Ono, N. Masuko, Surf. Coat. Technol. 169 170 (2003) 139. [16] A.J. Dowell, D.R. Gabe, Aluminium Finishing 14 (4) (1994) 15. [17] R. Lizarbe, J.A. Gonzalez, E. Otero, V. Lopez, Aluminium 69 (1993) 548.

5. Conclusions & The mass losses recorded in the thermogravimetric analysis of the sealed anodic films are very probably due to the dehydration of the bayerite that fills the pores in order to form boehmite. & The halving of the porous layer resistance of the sealed anodic films during the first days of ageing, clearly revealed by EIS, is due to the widening of the pores in the dissolution stage. & Supposing that the plugging of the pores takes place by the dissolution of the alumina walls to saturate the solution with bayerite and by the precipitation of the latter, the final diameter of the pores would be 1.46 times the initial diameter and the final section of the pores would be approximately twice the initial section. & The increase in the specific surface area and the volume of the pores for short sealing times or autosealing and their great reduction for longer times are convincing proofs of the successive stages of pore wall dissolution, gel condensation and hydrated alumina precipitation.