INTRODUCTION

Aluminum is a highly reactive metal and it is coated with a thin layer of oxide, when it is left in air even for a short time. This oxide layer is very useful and protects the aluminum from further atmospheric attack. The thickness of this oxide layer is purposely increased in industry by an electrolytic process called anodizing. Anodizing of aluminum comprises electrochemical conversion of the surface to aluminum oxide, with the aluminum serving as the anode in an aqueous electrolyte and the oxygen being provided by the electrolytic dissociation of water. Although the electrolyte is not consumed directly in anodic film formation, it has an important influence on film properties and usefulness [1].

1.1

Theory of Anodizing

Generally, the coating formed is essentially aluminum oxide [2], although there is definite evidence that anions of certain electrolytes may be absorbed [3]. An oxide coating is formed when aluminum is made the anode in certain electrolyte and oxygen is liberated at its surface [4]. Actually, as the reaction process continues, the oxide grows into the metal. It is interesting to note that the last formed oxide is extremely thin and nonporous and is located at the metal interface. This layer is known as the barrier layer [5]. The electrolyte and the formation voltage affect the thickness of this layer. The barrier layer is 10 to 14 thick for each volt employed [6]. The barrier layer is extremely thin when compared to the total oxide coating thickness. However, it does have a significant effect on both the resistance to corrosion and the electrical properties of the coating. The formation of the oxide coating is better understood in this way, that the first formed oxide layer is located at the extreme outer surface and is relatively porous because of its long contact with the electrolyte. The temperature and duration of treatment (time) as well as the type of electrolyte, determine the amount of solvent action on the coating. Another interesting point is the porosity of the anodic coating between the barrier layer and the first formed oxide layer. It has been determined that the pores in this area

have both definite size and number, depending on several variables, such as voltage and the electrolyte used [7]. There are billions of pores per square inch and consequently their diameter is extremely small. As the voltage increases, the size and number of cells decreases [8].The structure of the porous type of anodic oxide coating comprise of hexagonal columns, each with a central pore which reaches down to a thin compact barrier layer which is continuously formed and transformed into the porous form during the process[9]. The coating weight per given unit of area reveals a number of interesting characteristics of the oxide film and is dependent on both the thickness and porosity of the coating. Coatings resulting from the electrochemical anodic processes may be thin and dense or thick and porous, depending on the conditions employed. It naturally follows that the porosity of these coatings determines adsorptive characteristics, as well as abrasion resistance. In the latter case, coatings with a smaller number of small diameter pores will have higher resistance to abrasion than coatings with a large number of large diameter pores. This is true, because as the density of the coating increases the amount of oxide formed also increases, thus improving the abrasion resistance of the coating. The coloring substances such as organic dyestuffs could be used in conjunction with the oxide coating, making possible a wide variety of decorative effects [10]. In addition to colorants, it is possible to impregnate the porous oxide films with chromates or silicates for increased corrosion resistance or to impregnate with light sensitive materials [11, 12]. Most oxide coatings are sealed to make them non adsorbent [13]. Sealing is accomplished by treatment in near boiling water. This converts oxide lining of the pores from amorphous oxide to a monohydrate with subsequent increase in volume. This increase in mass or volume tends to close the pore openings and render the coating nonadsorptive or sealed. In addition to water, a number of other sealants may be used, the most important being those used in sealing coloured oxide coatings. Since most of the colorants used are water soluble, it must be assumed that an appreciable amount of the dyestuff would be leached from the coating when sealed in boiling water. The coloured oxide coatings therefore are sealed in near-boiling solution of nickel or cobalt acetates [14].

Speiser points out that three different reactions may take place in nickel or cobalt acetate sealing [15]. 1. 2. 3. Pores are closed by hydration, as in water sealing. Due to hydrolysis, hydroxide precipitation take place in the pores, this prevents bleeding of the dyestuff. A new metal complex is formed as a result of a chemical reaction between nickel and/or cobalt and the dye molecules. It is important that the use of nickel and/or cobalt acetate as sealants will prevent bleeding and form a new metal complex with the dye molecule. In most cases this new metal complex offers greater resistance to fading; however, as Wernick and Pinner point out, sometimes the dyestuff does not react with nickel or cobalt or the metal complex formed may be less lightfast [16].The oxide coating impregnated with chromates offers an important means of increasing the resistance to corrosion of the oxide coating [17].

1.2

Applications of Anodized Aluminum

The properties of anodic oxide [18-22] coating on aluminum are unique among

metal finishes and it is used in different important applications [23-24].

1.2.1 Anodizing as an Undercoat for Organic Coatings

This was the first large scale application and was based on the invention of the chromic acid (Bengough-Stuart) anodizing process. It was adopted as a standard finish for aluminum aircraft components and is still specified in the DEF 151 specifications. This combination of an organic finish with an anodic coating ensures maximum life for the paint coupled with an underlying protective coating to provide further protection in the event of any paint failure. Excellent service, even during sea water immersion, is provided by sulphuric acid coatings, preferably sealed in a dichromate solution and then coated with an appropriate grade of paint.

1.2.2 Corrosion Resistant Coatings

The unpainted chromic acid coatings have high resistance to salt spray corrosion especially when physically sealed with lanolin. The use of this combination was also

approved for aircraft components where painting would have interfered with the operational use of the coating. The sulphuric acid coatings have been widely accepted for the treatment of aluminum exposed to marine and industrial atmospheres. After the invention of steam sealing and hot water sealing, anodized aluminum is also used for external and indoor building components. Some typical examples of this class of work are: windows, patio doors, curtain walling, partition systems, double glazing frames, canopies, grilles, fascias and shop fronts. Many defence items that must survive long storage periods and others that need general protection in a tropical or marine environment are protected by anodizing. These include shell cases, tank armour, rocket components and fuses.

1.2.3 Coloured Anodizing

The ability of anodic coatings to absorb dyestuffs, a wide range of coloured aluminum was produced. Early applications include ash trays, decorative metal ware such as fruit bowls, tea trollies and paneling for indoor use. Large scale items included escalator metalwork and column castings in banks and stores. Electrolytic colours [25] can be produced in many shades by using different colouring electrolytes. The majority of this class of work is produced in nickel cobalt or tin solutions, all of which provide a range of light bronze to black shades having excellent light fastness. The building industry is the largest outlet.

1.2.4 Anti-Marking Applications

When unanodized aluminum alloys were introduced to the metal work market for such applications as balustrades and grab rails, the public complained of the grayish marking on light coloured clothing or gloves that came into contact with the metal. Anodizing provided a complete answer to this problem and was adopted for example for all the metal work in buses and coaches. The successful promotion of aluminum knitting needles has been entirely due to the use of anodizing which prevents marking of the wool or the knitters fingers.

1.2.5 Lighting Equipment

Sulphuric acid anodizing was used to protect the surfaces of floodlights. The initial loss of total reflectivity was acceptable because this lower value was maintained

for year of service where as plain aluminum continuously corroded and declined in performance. The anodized surface was easier to clean than corroded plain aluminum.

1.2.6 Heat Reflection and Radiation

Anodizing has long been used for aluminum electric fire reflectors. The Dimplex unit with its heated silica tube is found in many homes. The easily cleaned surface withstands the humidity of bathrooms and is an efficient reflector of radiant heat provided that the anodic coating is restricted to about 1m. The heat-radiating properties of thick coatings have been applied in the manufacture of heat sinks for electronic equipment. The coatings are often dyed black to increase their heat emissivity. Reflectors for infra-red stoving ovens for paint have also been made in bright anodized aluminum where reflectivity is only surpassed by gold [20-21].

1.2.7 Wear resistance and Lubrication

The anodic coating is much harder than the basis aluminum metal so that the general resistance to wear and marking is greatly increased by anodizing. Before hydration sealing became available the physical sealing with oils, waxes etc, led to the rise of sealing with lubricating oils of coating used for engineering purposes where an oil-wet table surface was an advantage. The principal application in this field was on anodized aluminum pistons for petrol and diesel engines. Sealing with graphite suspensions was also adopted. Hard anodic coatings are being very successfully used in cigarette manufacturing machines, hydraulic cylinders, coin-operated machine slides, textile spinning guides and cine-camera components.

1.2.8 Electrical Insulation

Although the anodic oxide coating is a good electrical insulator, the danger of local breakdown due to minor defects has limited the extensive use of anodized wire. However continuously anodized aluminum strip has for many years been adopted for winding electromagnets and some types of transformers where weight saving is important. The oxide coating is much more resistant to heat than organic insulating media and is therefore selected for high-temperature environments.

1.3

Factors Influencing the Choice of Anodizing Processes

The properties of anodized aluminum depend on a combination of the following

factors [24, 26, 27]. 5

(i) (ii) (iii) (iv)

The aluminum alloy Pre-treatment processes The anodizing process Post-anodizing processes A very wide range of chemical solutions have been used or proposed as anodizing

electrolytes. Most electrolytes are acidic, but some alkaline solutions have been investigated. The greatest tonnage of anodizing is produced in sulphuric acid based solutions but other acids are used on a commercial scale to obtain special types of coatings.

(a)

Chromic Acid Anodizing

Chromic acid was employed in first commercial anodizing process invented in

1923 by Bengough and Stuart [27-30]. Aluminum oxide films produced are thin and are usually opaque grey in colour. It is still widely specified for the treatment of aircraft components for different reasons. 1. 2. 3. 4. 5. It provides good base for subsequent painting. The minimum amount of aluminum is converted during the process, thus reducing any loss of metal thickness on thin stressed sheet components. The loss in fatigue resistance is lower than in the case of sulphuric acid. If chromic acid becomes trapped in, for example, riveted or overlapping joints it is less likely than sulphuric acid to cause corrosion. It is also used for crack detection e.g. in forgings. The orange/red electrolyte oozes from cracks after anodizing and colours the dry coating.

(b)

Sulphuric Acid Anodizing

It is used for all aluminum alloys except those containing insoluble constituents.

Anodizing in sulphuric acid produces semi-transparent colourless films in thickness upto about 35m [13, 26]. When properly processed and sealed these coatings are suitable for both decorative and corrosion resistant applications. The appearance of the coatings is considerably influenced by the original outside finish of aluminum. The bright anodizing is achieved by sealing aluminum alloys of high purity (99.7%+) aluminum or alloys based on it, followed by a brightening process and then anodizing in sulphuric acid.

The sulphuric acid process gives very hard coatings (known as hard anodizing) at low temperatures e.g. -5C to 5C, and is widely employed in the engineering industry.

(c)

Oxalic Acid Anodizing

Oxalic acid anodizing tends to produce translucent hard yellowish films that have

been used for architectural applications and also, in Japan, for cook ware [27]. The anodized layer formed by oxalic acid has abrasion resistance almost double that of a conventional sulphuric acid process coating. This process is one of the earliest integral colour processes to achieve universal recognition.

(d)

Phosphoric acid anodizing

The anodic coatings obtained in phosphoric acid have larger pore size than in

usual sulphuric acid films [31]. This greater pore size provides a better conducting path and phosphoric acid films have been used for pre-treating aluminum before electroplating due to this reason. It has also been adopted to prepare aluminum for adhesive bonding for aircraft components.

(e)

Integral Colour Anodizing Electrolytes

This term includes a wide range of organic acid solutions, usually containing

small additions of sulphuric acid. The oxide films produced have double abrasion resistant as compared to that of sulphuric acid films and can be produced in a range of colours from pale gold / beige through bronze to black. These processes have been widely used for architectural work such as windows, shop fronts and curtain walling. The hardness of the film has also resulted in its use for other industrial purposes as an alternative to hard anodizing and has recommended itself for building components exposed to the sandy atmosphere of the Middle East. The integral colours are exceptionally lightfast and can confidently be specified for prolonged exposure outdoors. (f) Non-Solvent Electrolytes The acid solutions mentioned above have a solvent effect on the oxide film and the resultant porosity enables relatively thick films to be built up. The non-solvent electrolytes e.g. boric acid or ammonium tartarate offer thin impermeable barrier layer films with electrical properties fitting for use in capacitors [25, 32]. This type of process is generally carried out on continuous strip and has a very important field of application.

1.4

Equipment for Anodizing

Generally the equipment for anodizing comprises a source of electric current (i.e.

rectifier) and a series of tanks for holding various solutions [33, 34]. These tanks include units for cleaning, water rinsing, electrolytic oxidation and sealing.

1.4.1 Anodizing Current Supply

Most anodizing processes operate with direct current (DC) which is usually supplied by a rectifier.The current supply to the anodizing tank in small manually operated plants is often operated by a manual control, but even in small installations, and certainly in large ones, some form of automatic control is desirable in order to standardize the process conditions.

1.4.2 Tank Construction

Some of the materials now commonly specified for tank construction [25, 34] are listed in Table 1.1. Table 1.1 Materials for tank construction for anodizing process. Solution Trichloroethylene Hot sulphuric acid cleaner Caustic soda Etches containing HF Brytal Phosphoric acid base electro-polishing preferably with solutions. Phosphoric/sulphuric acid-based steel chemical polishing solutions. Phosphoric acid/nitric-base chemical Galvanized required) Tank Material iron (special construction

Chemical lead-lined steel Mild steel Plastics-lined mild steel or lead lining (in the absence of nitric acid) Mild steel. Separate mild steel cathodes Antimonial lead-lined steel,

glass shields on ends and bottom. Separate lead or stainless-steel cathodes. Chemical lead-(not antimonial) lined

Molybdenum-bearing stainless steel for

polishing solutions and rinses Sulphuric acid anodizing

tanks and steam heating coil, stainless or silica-sheathed immersion heaters. Polythene or PVC linings, acid-resisting rubber or lead-lined steel or acid-resisting bricks (lead or lead-covered steel coils). Lead or aluminum cathodes. Mild steel with stainless-steel cathodes. Hard rubber or PVC-lined mild steel PVC or butyl rubber lined mild steel, stainless steel or glazed earthenware. Reinforced concrete; lead, rubber, plasticslined mild steel, galvanized mild steel (not suitable for acid rinses), wood, acid-resistant brick, PVC or fiberglass. Stainless steel, chemical lead-lined steel Stainless steel, rubber or lead-lined steel Stainless steel or aluminum. Rubber-lined or lead-lined steel; stainless steel. Stainless steel, Rubber-lined steel or wood may be used where bath is kept for one dye only.

Chromic acid anodizing Oxalic acid anodizing Nitric acid (cold) Water rinses

Aqueous sealing and fixing solutions Nickel and cobalt acetate Potassium permanganate Ferric ammonium oxalate Organic dyes

Chrome/phosphoric stripping or desmutting Stainless steel

The tanks themselves are designed so as to avoid undue distortion when filled with liquid, e.g. in a 10-meter-long tank the total deflection at the centre should not exceed 5 cm. Tanks that require frequent cleaning out e.g. water rinse tanks should have a drain valve at the bottom, while tanks containing strongly alkaline or acid solutions are safer if no bottom valve is fitted. They can be emptied using hoses and a suitable portable pump. The heating coils are usually fitted along the bottom of the tank, except when appreciable amounts of sludge are likely to accumulate. 9

1.4.3 Water Purification Plant

Water must be analyzed before anodizing process as certain natural impurities in water can render it unsuitable for making up some of the processing solutions. For example chloride can upset the operation of anodizing solutions while excessive phosphate and silicate will prevent effective hot-water sealing. A high total dissolved solids content will cause water staining during the final drying off process of aluminum.

1.5

Chemical Treatment Processes before Anodizing

Different chemical treatment processes are carried out before the anodizing of

aluminum [24, 35-36].

1.5.1 Removal of Heavy oil and Grease

Some parts become heavily coated with lubricant during fabrication. In order to avoid imposing too heavy a load on the wet cleaning processes it may be advisable to remove most of the oil in a vapour liquor apparatus using trichloroethylene or similar solvent.

1.5.2 Chemical Cleaning

The purpose of chemical cleaning is to remove polishing composition, oil, grease and general dirt from the aluminum so as to leave a clean surface ready for the following process. Most of these cleaners are widely alkaline and formulated so as to produce either a slight etching action or none at all. Alkaline cleaners incorporating silicates as inhibitors are not favoured in view of the possibility of silicate being carried through to the sealing solutions. A useful general cleaner that will remove thin films of oxide (formed during heat treatment), polishing composition and grease is a 10% by volume solution of sulphuric acid at 90 C.

1.5.3 Alkaline Etching

The 5% caustic soda solution is the cheapest and most widely used materials for producing a clean whitish etch on aluminum. The operating temperature is 40-50 C. The rate of chemical attack increases rapidly with temperature. Thermostatic control of the temperature assists in the production of a uniform rate of etching. The reaction between

10

aluminum and caustic soda is exothermic so that heavily loaded solutions may need a cooling coil or panel to prevent a rise in temperature. The alkaline etching solutions do not dissolve all the constituents found in aluminum alloys, and the un-dissolved materials form a smut on the metal surface. Copper containing alloys such as 2011 give a black smut while high silicon alloys (e.g. 4047A) produce a slate grey smut that does not dissolve in nitric acid. It can be cleared in a mixture of nitric and hydrofluoric acid. It is advisable to de-smut the etched surface using either 10-30% by volume nitric acid at room temperature or proprietary solutions based on ferric sulphate solution and nitric acid. Aluminum sample should not be left in the alkali rinse solutions where it is liable to corrode.

1.5.4 Acid Etching

Acid etching solutions are needed for some special applications. The production of a matte surface for lithographic plates and also capacitor foil involves electrolytic etching in a solution based mainly on hydrochloric acid. Solutions containing upto 10% hydrofluoric acid or a mixture of the acid and 2% nitric acid are useful for etching alloys containing 5% or more silicon. A very mild acid etch suitable for removing heat treatment scale contains 10% sulphuric acid and 2% sodium fluoride. All acid etches operate at room temperature.

1.5.5 Electrolytic Polishing

This process includes electrobrightening which also increases the surface reflectivity but removes less metal than electropolishing. The effect of both types of process is to bring about a micro-smoothing of the surface by preferential attack on the high spots while depressions are protected from electrolytic dissolution by the temporary formation of a viscous layer that impedes the flow of current. The electrolytic polishing processes are mainly based on phosphoric acid solutions with additions of other acids such as chromic, nitric or sulphuric acids and will smooth a wide range of materials. Good agitation, preferably mechanical, is desirable to produce uniform polishing conditions at the metal surface. Although electropolishing will produce a bright smooth finish the subsequent anodic coating will lose its specular reflection properties as the coating thickness is

11

increased, except in the case of the special alloys that have been developed for bright anodizing.

1.5.6 Chemical Brightening

Chemical brightening acts in a similar manner to electropolishing but requires no electric current. This type of process has been widely adapted as a basis for bright anodizing. The first process was invented in the U.K and it used the mixture of phosphoric acid (s.g 1.75) 60 75% by volume and sulphuric acid (s.g 1.84) 25 40% by volume. This solution was used at 95 100 C [26, 36]. The aluminum surface should be clean and well drained or dry before immersion in this solution. Hydrogen is evolved during the reaction but the highly viscous solution prevents spray emission. After about 2 to 3 minutes immersion (heavier pieces requiring extra time to attain the operating temperature), aluminum is removed and drained. White foam is formed on the metal during the draining period. The sample is then plunged into a 1% solution of chromic acid. The treated metal has a bright diffused finish and is particularly useful for removing polishing burns and thereby giving an attractive uniform finish. A more widely adopted solution is based on a mixture of phosphoric acid and nitric acid together with additions of sulphuric acid, boric acid, salts of nickel or copper, wetting agents and antifuming agents such as ammonium sulphate. In the U.K. these are marketed as the phosbrite solutions. These solutions are used at 95 105 C and emit nitrogen peroxide, especially when the work is withdrawn from the solution. These fumes must be exhausted and scrubbed before discharging to the atmosphere. An immersion of 2 minutes is the average [26,36]. The finish has a high specular reflectivity, especially when used on alloys based on 99.7% + aluminum. It is first rinsed in warm water, followed by a running water rinse and then by a dip in a de-smudging solution which may consist of either 20% by volume nitric acid (s.g. 1.42) or 1% chromic acid or a proprietary mixture based on ferric sulphate. These de-smudging solutions, all of which are at room temperature, remove the thin copper-containing film that is left on the metal during chemical polishing. After de-smudging and rinsing the surface is ready for anodizing.

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1.6

Colouring the Anodic Oxide Coating

After anodizing process, the oxide coating is porous in nature and capable of

absorbing dyestuff. While natural anodic finishes are attractive in themselves, the range of decorative applications is extended by colouring the film. The main characteristics determining suitability for colouring are the thickness of the coating, its absorptive power and its natural colour. The sulphuric acid process gives semi-transparent and colourless coating on appropriate grades of aluminum ideal for dyeing to pastel shades or full, rich tones. In order to obtain maximum fastness to light, resistance to weathering and depth of colour, a 25 m or thicker coating is essential. Where thin coatings are dyed e.g. with bright anodized aluminum for artificial jewellery, the colour fastness is reduced [25, 36]. The opaque off-white coatings formed after the chromic acid process are ideal for mellow pasted shades and have the colour fastness adequate for general interior work provided suitable dyestuffs are used. But this anodized layer is inadequate for external exposure. The anodized layer formed after the oxalic acid process, effects may be obtained similar to those obtained with sulphuric acid, but the shade is modified if the original oxalic acid film has a golden colour [25, 36]. Aluminum alloys containing silicon, the anodized layer obtained after the usual anodizing processes give a grey or purplish grey film which can be very attractive and is permanently colour fast, but it modifies the shade of dyed colours to a marketed extent. Other tints due to alloying elements will also affect the final result. The anodized films with the maximum retention of colouring matter are obtained by anodizing at the higher limits of temperature, time and acid concentration in all the anodizing processes. Other properties required in the anodic film, however, often modify these conditions. The anodic film must be of even thickness and can be produced in conditions avoiding local variations in temperature or acid concentration for achieving uniformity of colour [25, 36]. Different organic dyestuffs and some inorganic pigments are used to colour anodic coatings of metal.

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1.7

Sealing the Anodic Oxide Coating

The anodic coating after dyeing or without dyeing is like hard brittle blotting

paper. It is essential to prevent the adventitious absorption of substances that may be unwanted or deleterious. These preventative methods are known as sealing processes and fall into two categories, physical sealing and chemical sealing, which may be either by hydration or by reaction with metal salts, which itself may include partial or complete hydration[25].

1.7.1 Physical Sealing

The anodic coatings produced in chromic acid were painted afterwards or coated with a solution of anhydrous lanolin in a mixture of solvent naphtha and white spirit. These substances provided a physical blocking of the coating pores and for this reason this process is called physical sealing. A wide range of organic materials have since been used for physical sealing [25]. They have some advantages in special applications. For example, sealing in lubricating oil or graphite/oil suspensions provides a lubricating surface that has been used for pistons, polytetrafluoroethylene/resin mixtures will form a non-stick layer having low coefficient of friction, silicon coatings have also been specified for curtain railing. Physical sealing does not decrease the surface hardness or wear resistance of the coating which is important in hard anodizing applications. However some physical sealing materials can be removed by solvents or prolonged weathering, leaving an imperfectly sealed coating with properties inferior to those intended. There are practical difficulties in applying some of the physical sealing agents on a large scale and chemical sealing can be used in such cases [36].

1.7.2 Chemical sealing

Chemical sealing can be carried out by using boiling water, steam or some chemical additives. 1.7.2.1 Hydration Sealing This type of sealing is the most widely used commercially. Originally the process consisted of treating the well-rinsed anodic coating in saturated steam at atmospheric pressure or in boiling water. Although the exact mechanism of the process is not completely understood it is known with certainty that the following processes occur [25, 36].

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1.

Some of the absorbed or loosely combined electrolyte with the oxide coating is dissolved away but is not completely removed. The residual sulphate (as SO4) in a sealed sulphuric acid coating is typically about 13% , the precise amount depends upon the coating thickness and the anodizing conditions.

2.

The original unsealed coating is almost anhydrous, 0.5% water content is usually quoted. During sealing this water content increases rapidly at first and later more slowly. A conventional water sealed sulphuric acid coating contains about 8-13% water, but sealing in steam at atmospheric pressure provides less hydration.

3. 4. 5. 6. 7.

The absorption of water leads to an increase in weight of the coating but a decrease in the apparent density from 2.6 to 2.4 g/cm3. The clearly defined porous structure becomes less distinct as the pores become blocked, starting at the outer surface. The original aluminum oxide is partly transformed into a hydrated oxide resembling Bhmite Al2O3.H2O. The outer layers of the film are reduced in hardness and are more easily abraded. A thin powdery deposit known as sealing bloom forms on the surface. The effect of hot water or steam sealing is to reduce or eliminate the ability of the

coating to absorb dyes and the blocking of the pores increases the corrosion resistance of the coating. The electrical insulation is increased and current carrying ability is decreased [36]. 1.7.2.1.1 The Practice of Hot Water Sealing This is the most widely used sealing process, but its apparent simplicity is deceptive [25]. The factors that must be taken into account in order to obtain the best results are as follows: 1. Temperature Ideally the water free from impurities should be simmering at 99-100 C but a temperature range of 96-99 C is acceptable. It is difficult to maintain a uniform temperature in large volumes of water and specialized thermostat systems are needed to impose this close temperature range.

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2.

pH of the Water The pH of the sealing water is important. At pH value below 5.4 the quality of

sealing decreases and at pH value in the alkaline range i.e. above 7.0, there is danger of chemical attack on the coating. In commercial practice a pH in the range of 5.6 6.6 0.1 is used. The control of pH presents serious technical difficulties because residual acid electrolyte in the anodic coating tends to bring about a continuous reduction of the pH value. This effect can be corrected by the addition of an alkali such as caustic soda or ammonia. In addition the drag in of acid in the coating can be minimized by soaking the anodized sample in warm water before sealing. If the pH rises beyond the chosen upper limit, it can be corrected by adding sulphuric acid or preferably acetic acid. 3. Quality of Sealing Water If the water has a high temporary hardness, a continuous precipitation of calcium carbonate (and sulphate) is produced in the sealing bath, which in turn deposits a limescum on the anodized sample. This difficulty is overcome by the addition of acetic acid to the sealing bath before it is heated up, thus keeping some of the calcium in solution as calcium acetate. Ion-exchange resin can also be used to remove all anionic or cationic impurities. 4. The Time of Sealing The basis of sealing times varies in different countries. In the U.K. a time of 2 minutes per micron of coating thickness has given satisfactory results. Elsewhere, times of 3 or even 4 minutes per micron have been specified which ever time is chosen it is essential that the sealed coating should pass the well-established acceptance tests. 5. The Sealing Bloom Hot-water sealing, whether in main supply water or demineralized water, causes the formation of a bloom on the oxide coating. In small-scale operations this can be removed by wiping or lightly buffing, but on a large scale this would be too labour intensive. Two methods of dealing with this problem are in common use. 1. 2. The removal of bloom in an acid dip, usually nitric acid, followed by rinsing and drying. The use of special additives to the sealing bath to minimize or prevent bloom formation [25, 36].

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1.7.2.2 Sealing with Chemical Additives This type of sealing of the anodic coating is immersed in solutions of chemicals that react with the aluminum oxide in such a way as to improve its resistance to corrosion and general chemical attack. 1.7.2.2.1 Metal Salt Sealing (i) The Practice of Nickel Acetate Sealing The earliest examples of sealing salts were based on nickel acetate, cobalt acetate or mixture of the two. A solution that has stood the time of test is nickel acetate 8-10g/L, pH 5.6 5.8 and temperature 80 C [14-15]. The addition of boric acid as a buffer should be avoided as it reduces the performance of the coating when tested by Kape method. During use, nickel is precipitated in the coating as nickel hydroxide. This inhibits staining by dyestuffs, increases the resistance of the coating to alkaline attack and if the coating has been dyed, increases the light fastness of most colours. The nickel acetate treatment is essential to achieve the maximum light fastness for some dye colours. The time of immersion in nickel acetate is usually 2 to 3 minutes, after which the anodized sample is rinsed and finally sealed in hot water. It is found that dyes are prevented from bleeding out at the hot water stages. It is a sure sign that the fixing process has been successful. Nickel sealing produces a smut on the surface of the anodized sample which adds to the bloom arising from the subsequent hot water sealing. This smut can be removed by hand wiping, mechanical polishing with a swansdown mop or barrel polishing (in case of small items) [25]. (ii) The Practice of Dichromate Sealing The corrosion resistance of anodized aluminum, particularly in a marine environment, can be improved by sealing in a solution of a chromate or dichromate [17]. The sodium salt is usually chosen as it is cheaper than the potassium or ammonium salt. These formulations are based on work originally carried out in the U.S.A and the U.S.S.R. The sealing solution usually contains sodium dichromate 70 100 g , sodium carbonate 18 g (or sodium hydroxide 13 g ) dissolved in 1dm3 water and pH of this solution is 6.3 7.4.The temperature of solution should not be less than 96 C. The immersion time is 5 to10 minutes for this solution which is insufficient to bring about full

17

hydration sealing but an appreciable quantity of chromate is absorbed by the oxide coating giving a distinct yellow colour. The intensity of yellow colouring increases with coating thickness. Sometimes the sealing solution contains sodium dichromate 40 60 g dissolved per litre water and pH is 5.6 6.0 .The temperature of the solution should not be less than 96 C. With this formulation the time of immersion is about the same as the time for anodizing. This results in a fair degree of hydration but not necessarily complete sealing. The acid attack sealing tests are not applied to items sealed by either of the above methods for this reason. (iii) Room Temperature (Cold) Sealing Sealing of anodized aluminum was modified by the advance of room temperature sealing (7090 F) [25]. Unlike the high temperature and mid-temperature sealing which depend on hydration process, the cold seals depend on a chemical reaction between the aluminum oxide and the nickel fluoride present in a sealing solution. Unfortunately this reaction is slow at ordinary temperatures and the sealing process can continue up to 24 hours. However it has been found that a warm water rinse (160 F) after the cold seal immersion will speed up the sealing process. Organically dyed parts can be sealed in cold seals are found to have advantage. Light stability testing (fade resistance) has revealed that parts sealed by cold seals achieve additional light fastness.

1.8
1.8.1

Anodic Film Evaluation

Film thickness by Gravimetric Method (Stripping off Method) The weight of anodic film per unit area is a direct measure of processing

uniformity, and represents a closer approach to a substitute quantitative index of quality, at least from one lot to another processed under similar anodizing conditions. Film weight/mass was determined by stripping off a sample of known area, free from grease in a solution containing 20 g chromic acid and 35 ml (85% d = 1.75) phosphoric acid per litre (with distilled water) held at boiling point (99C) [24, 37]. The oxide coating was dissolved rapidly after 5 minutes immersion time. Sometimes a whitish appearance on withdrawing sample was formed which indicated the incomplete oxide film removal. The process was continued until a clean metallic surface was revealed and the sample attained

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a constant weight. This stripping solution is completely inhibited against attacking metallic aluminum. The specimen was weighed before and after coating removal. The loss in weight divided by the area provided a value for the mass of the coating per unit area (Film thickness). Film thickness (mg/ft2) =
Loss in weight (mass of oxide coating in mg ) Area ( ft 2 )

The coating weights of less than 1 mg/sq inch are unlikely to meet salt spray test requirements but even much thicker coatings must be properly formed and sealed to be adequately protective. The density of the coating is about 2.4 for unsealed coatings and 2.6 for coatings sealed by hydration. For convenience these values have been universally adopted. From the weight loss measured above the coating thickness can be calculated from the formula.

T
Where T W a d

=
= = = =

1000 W ad
Coating thickness in micron Mass of coating in milligrams Surface area of the coating in square millimeters Density of the coating.

1.8.2 Corrosion Resistance Measurement

It has always been difficult to devise accelerated corrosion tests that can be correlated with long term exposure. Tests for anodic oxide coatings are no exception, but following methods are mostly used [37]. a) Acetic acid Salt-Spray test This is particularly suitable for coatings up to 5 m in thickness and involves exposure in a suitable cabinet to a spray-mist derived from a solution containing 50 5 g sodium chloride per litre with the pH adjusted to 3.2 + 0.1 by the addition of glacial acetic acid. The cabinet atmosphere is maintained at 35C and an exposure time of 24 hours is usually specified. No pitting of the coating should be visible after spraying. b) Copper accelerated acetic acid salt spray test (CASS Test)

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The acetic acid salt spray is a relatively mild reagent. Where thicker films require testing a more active reagent for the spray solution is made up by dissolving sodium chloride 50 5 g and cupric chloride 0.26 0.02 g per liter water (preferably purified). The pH is adjusted to 3.2 0.1 by the addition of glacial acetic acid. The cabinet temperature is maintained at 50 1C and the standard exposure time is 8 hours. A rating system has been devised to enable a performance number to be allocated to corroded surfaces. Ratings of at least 8 for 15-25m coating and at least 6 for 5-15 m coating are acceptable [37]. c) Salt Spray tests A spray from a 5% or 10% solution of sodium chloride is still used. It may take several thousands of hours before signs of pitting become apparent on well produced films so that the test is unsuitable for production control. By comparison a good standard of nickel plus chromium plate on a steel basis metal should withstand 90 hours salt spray. For stressed components in air craft, the salt-spray test is followed by fatigue tests to ascertain the effect of any corrosion on the mechanical properties of the coated component [37]. d) Cyclic Corrosion Test The cyclic corrosion tester is competent of performing exposure testing to a number of corrosion environment types. The instrument exposes the anodized sample through a cycle between salt spray, dry heat, high humidity and ambient conditions. The corrosion environment created by repeated cycling between these conditions provides a severe test. The cabinet conditions produce a severe test. For accurate control, the cabinet is monitored by a test cycle computer. In addition to performing cyclic exposures, the cyclic corrosion tester is gifted of running to a single set of conditions [38]. e) Potentiodynamic Polarization Test A potentiostat is a control and measuring device which keeps the potential of the working electrode at a constant level with respect to the reference electrode in an electrolytic cell. It comprises of an electric circuit which controls the potential across the cell by sensing changes in its resistance, varying accordingly the current supplied to the system. A high resistance will give a decreased current, while a low resistance will give increased current, so as to keep the voltage constant.

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If corrosion resistance of anodic film is more, anodic current of the sample is decreased and corrosion potential is increased, as compared to the uncoated aluminum substrate [39].

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