LITERATURE SURVEY

The chromic acid anodizing process for aluminum and aluminum alloys was developed by Bengough and Stuart [28]. They carried out anodizing in electrolytic bath containing chromic acid solution or materials producing chromic acid at anode. In their process, carbon cathode was used and temperature was 40C. They were quite successful in producing corrosion resistant oxide coating for corrosion prevention of aluminum and aluminum alloys. Later on they developed another process for anodizing of aluminum and its alloys to make them corrosion resistant to sea water [29]. The degreasing of aluminum was done by washing with a solvent and then washing thoroughly with hot water. After this, the aluminum was anodized in chromic acid bath with carbon cathode and temperature was not less than 40C. The voltage across the electrolytic bath was raised to about 40 V in the course of 15 minutes and this voltage was maintained for about 35 minutes, then it was raised to 50 V in the course of 5 minutes and maintained for about 5 minutes. The anodized surface was then rinsed in distilled water and was desiccated in air. The oxide coatings produced by this method were corrosion resistant to sea water. Bengough and Sutton studied anodizing of aluminum and its alloys for the prevention of corrosion [30]. The best oxide coating on various alloys was obtained by using 3% chromic acid aqueous solution and 40C temperature. Although this method was not successful for aluminum alloys containing 5% or more copper content, because oxide film was broken down at 30 V. However this process was used to anodize aluminum silicon and aluminum zinc alloys, although Al-Si alloy containing 7.58.75 % silicon caused high current consumption. Anodic oxidation was followed by dipping in molten lanolin, a 15% solution in benzene or into a lanolin suspension, thus providing the best protection against water-line corrosion. However health and environmental problems does not allow using of hexavalent chromium due to its poisonous and carcinogenic causing effects and this process is progressively restricted even banned [40-43]. Thus the alternate of anodizing process in chromic acid is essential and vital problem in engineering areas and various problems concerning environment. 22

Bengston developed a new method for the anodizing of aluminum and its alloys [13]. He used sulphuric acid electrolytic solution for the anodizing of aluminum. This process was useful for producing anodic coloured film and the sealing of pores of oxide coating at a temperature of 80-100 C was used to increase the resistance to chemical attack. Marceau et al successfully developed anodizing process using phosphoric acid to obtain adhesively bonded Al or Al alloy parts [31]. This method was effective for increasing the environmental stability of adhesively bonded aluminum structures in service. They used this method chiefly as a pretreatment for use of organic or plated coating. Now this process is normally used to manufacture adhesively joined aluminum parts in aircraft industries and other industries [44-47]. It has also been used in printing and plating processes [48-53]. Fukuda and Fukushima studied the effect of addition of aluminum sulphate or magnesium sulphate in sulphuric acid anodizing of aluminum [54]. They found that the anodic coating surface became microscopically more even by the addition of the sulphate concentration. The porosity near the surface was also decreased. They also found that the uniformity of the film was decreased by increasing the sulphate concentration. Arowsmith and Clifford developed a method for adhesive bonding of aluminum [55]. They carried out hard anodizing using sulphuric acid electrolyte to form thick and corrosion resistant surface and this coating was accompanied by limited phosphoric acid dissolution. They also studied the surface structure and its chemical properties and found it fitting for adhesive bonding. Wong and Moji developed boric /sulphuric acid anodizing as a replacement for chromic acid anodizing [56]. They sealed the porous coating using hot dilute dichromate solution to accomplish acceptable corrosion resistance. They found that the oxide coating had properties as good as or superior to coatings applied in chromic acid anodizing Lockheed Martin introduced thin film sulphuric acid anodizing (TFSAA) process. All the parameters are the same or close to those of the (BSAA) process with the removal of boric acid [57,58]. The anodizing conditions were: 3-5% wt. sulphuric acid electrolyte solution, 25-30 C temperature, 15V and 25 minutes anodization time. The anodized aluminum was sealed in 5% wt. sodium dichromate solution at 85-95C temperature for a

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period of 20 minutes. This process required low cooling and current requirement than Type II anodizing. Both the boric/sulphuric and thin film sulphuric acid anodizing processes use environmentally caring electrolytes and relatively their treatment and disposal is cheap. These processes were planned to make thin oxide coating on Al to increase corrosion resistance and paint adhesion with low fatigue loss. The oxide film mass was in the range from 200 to 700 mg/ft2, and it was about 1 to 3 microns thickness. Various researches have revealed that boric/sulphuric acid anodizing the military and aircraft industry requirements and specifications[59-64]. Griffen and Askins studied surface preparations without chromium for aluminum adhesive bonding [65]. They evaluated the chrome free surfaces for their ability to impart both stability and acceptable property requirement to bonded aluminum joints. They also conducted various property checking tests with coated and bonded samples. They found that coated surfaces without chromium were equivalent to phosphoric acid anodizing process. Ikegaya investigated post treatment of anodic oxide film [66]. This involved dipping the aluminum anodic oxide film in a water bath (having a specific resistance > 3000 cm and pH = 6-8 and heated to 40-60 C) for 3-30 minutes. This method was used to apply a coating to prevent water adsorption to the film and to decrease the acid content in the film. They found that the cracking of the coating material in high temperature baking was prevented. Surganov et al. examined the dissolution of anodic oxide coating at the initial stage of anodization of aluminum in aqueous solution of organic acids with different dissociation constants; oxalic, malonic acid citric acids [67]. They found that practically right after applying the anodic potential Ea to the studied sample. Panitz et al. studied the formation of barrier anodic film on 6061-T6 Al alloy in electrolytes containing different ethanol to water ratios [68]. They prepared by dissolving five mixture compositions of ammonium tartarate in water and diluted with different amounts of ethanol .The effect of electrolyte temperatures within the range of 18-38C was investigated. They found that the best dielectric coatings and the shortest processing the dissolved aluminum content appeared in significant amounts (0.04 0.1 g/cm2) and thin film sulphuric acid anodizing processes generate the anodic coatings suitable and fitting for

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time occurred for the 100% water ammonium tartarate electrolyte ,while the second best coating and the processing time occurred for the 98% ethanol, 2% water plus ammonium tartarate electrolyte composition. Danford investigated the corrosion resistance of aluminum alloy 6061-T6 by different anodizing processes [69]. The anodized aluminum was obtained by both impregnated anodized coating and hard anodized coating (sealed in water and sealed in dichromate). He investigated the corrosion protection at both pH 5.5 and pH 9.5 with 28 days exposure period in 3.5% NaCl solution (25 C) for each sample. He found that corrosion resistance for all samples was superior at both pH. He found that hard anodized, hydrothermally sealed coating at pH 9.5 provided the best corrosion protection. Kim et al. investigated the growth and structural properties of the aluminum oxide thin coating grown on aluminum substrates by anodizing using phosphoric acid at 35-75 V (D.C)[70]. They investigated the surface and depth profiles of anodized thin films of alumina by scanning electron microscope (SEM), Auger electron spectroscopy (AES) and secondary ion mass spectroscopy (SIMS). The pits were formed on the anodized film surface upon increasing the anodization time. They also found that the surface was restored to its mirror like surface as revealed by SEM. Shular et al. investigated the location and estimation of air emissions from sources of chromium [71]. They updated the technical information and presented a new emission data upon which emission factors were based for hexavalent chromium emissions from cooling towers and chromium electroplating operations. They also included process descriptions for 5 kinds of plating/anodizing operations, emission control techniques for reduction of chromic acid missed from plating operations, updated information about the distribution of industrial process cooling towers that use Cr-based water treatment chemicals, new information about comfort cooling towers, emission reduction techniques for chromium emissions from cooling towers equipped with low and high-efficiency drift eliminators. Adachi et al. developed a method for the manufacturing of aluminum foil electrode for electrolytic capacitor [72]. They impregnated an etched aluminum foil with hot pure water, anodized in aqueous citric acid, depolarized by aqueous NH3, heated, re-

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anodized in aqueous phosphoric acid, heated, re-anodized again and washed to give a formed foil showing large electrostatic capacitance. Adachi et al. devised another method for the manufacture of aluminum foil electrode for electrolytic capacitor by a different method [73]. They impregnated an etched aluminum foil with hot pure water, anodized in aqueous citric acid, depolarized by aqueous ammonia, heated, re-anodized in aqueous adipic acid, heated, re-anodized again and washed to give a formed foil showing large electrostatic capacitance. Adachi et al. developed another method for the manufacture of Al foil electrode for electrolytic capacitor [74]. They impregnated an etched aluminum foil with hot pure water, anodized in an aqueous mixture of citric acid and boric acid, depolarized by aqueous ammonia, heated, reanodized in the aqueous mixture and washed to give a formed foil showing large electrostatic capacitance. Okubo et al. studied the microstructure of anodic oxide films on aluminum by pulse current technique with negative component [75]. They used electron microscopic study to provide a better understanding of cells and pores in aluminum anodic oxide films. They carried out anodizing process in 15 wt. % sulphuric acid (20 C, 2 A/dm2, 5 minutes), 5 wt. % oxalic acid (30C, 2 A/dm2, 5 minutes), 8 or 10 wt. % chromic acid (50C, constant 60 V, 30 minutes) bath using 13.3 Hz rectangular a.c. with various duty factor (ratio of post. component in one cycle). The rear surface (boundary between oxide layer and aluminum metal) of film stripped in a HgCl2 solution were shadow-cast with Au-Pd ion sputtering technique, and were observed by SEM. TEM images of pore structure were given of cross section 40 nm (in thickness) of perpendicular to film surface using ultramicrotome. They concluded that the cell size, pore diameter and pore branching has increased with increase in duty factor in oxalic acid and chromic acid bath. Albort developed electrochemical method for control of the anodization process [76]. The method evaluated the quality of the anodic coating of aluminum anodization. The anodization was conducted with an 8.5 wt % solution of chromic acid, c.d. 0.15-0.3 A/dm2 and temperature 35C. The coefficient of corrosion of the sample in millimeters per year was determined. Hoshino et al. determined chromium contents in anodic oxide coatings formed on Al in chromic acid [77]. They analyzed the chromium content in 9 conventional oxide

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films formed in chromic acid bath by instrumental activation analysis. The anodic oxidation conditions used were as follows: chromic acid electrolyte 30-90 g/L, bath temperature 40-50C, bath voltage 20-60 V and overall current 1.5-4.0 C/cm2. They found that the chromium content in the films was 0.010-0.020% and discussed relations between the chromium content and electrolytic parameters. Liu and Yang carried out high finishing hard anodizing of aluminum alloys to obtain a thick and hard alumina layer [78]. They have described the operational conditions (different sulphuric acid concentrations, temperature, c.d, oxidation time and electric potential) for high-finishing hard anodizing of hard aluminum, ultra-hard aluminum and wrought aluminum and properties of anodic films. This process had some drawbacks like poor brightness and high fragility of the oxide layer, easy peeling of the layer and electrochemical corrosion during oxidation. Anon developed a method for anodizing of aluminum using alkaline bath (hydrazine fluoride bath) containing amino acids [79]. He found that in the absence of amino acids (glycine or taurine) , uneven oxide films were formed and thickness of the film was only ~ 9 m. In the presence of aminoacids in the electrolytic bath, 15-16 m thick uniform oxide films were obtained in 30 minutes electrolysis. He also determined scratch hardness as 14.8 and 27.4 when taurine and glycine, respectively were present in the bath. Fenzl developed a method for improving the corrosion resistance of anodically produced oxide layers on aluminum alloy materials [80]. He carried out a two step sealing process after anodization of aluminum. The metal part was dipped in a potassium dichromate or sodium dichromate bath and, after an intermediate rinse, subjected to a hot water bath. Sergeev developed a new electrolyte for anodizing articles of aluminum and its alloys [81]. He added dimethyl sulphate and an antistatic agent to an electrolyte containing sulphuric acid, oxalic acid and a fluoroplast suspension for anodizing of aluminum articles which were used especially for vibrational support of diamonds. He also found an improvement in the sliding properties of aluminum. Belousova investigated anodization finishing of aluminum alloy articles in alkaline bath [82]. He found that thermo-mechanical strength was increased when the

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aluminum or aluminum-alloy articles were anodized for 30-40 minutes at the c.d. 1.5 1.7 times that of the oxide film formation, followed by the principal anodization in alkaline bath at electric arc potential, decreasing the c.d. at 150-170 m A/dm2-min and then heat treatment for 1 hour at 200 C. Xu studied the effect of pore enlargement treatment on the structure and other characteristics of aluminum coating [83]. He used transmission electron microscopy (TEM), microhardness meter and SRV friction machine to study the microscopic porous structure of oxide coating formed on aluminum using oxalic acid electrolyte. He also studied the change of oxide film porous structure after the pores in the oxide film were enlarged and its effect on the mechanical performance. Surganov et al. investigated the growth and dissolution of oxide coating of aluminum using oxalic acid electrolyte [84]. They determined dependence of the anodic potential, thickness of the anodized metal layer, and content of dissolved aluminum by using atomic emission plasma spectrometry. They resolved three characteristic stages which were inherent to the dependencies. They found that anodic oxide dissolution occurred at the beginning of the anodic process. Yashimura et al. carried out anodizing of aluminum in organic alkaline bath using ethylene-diamine alkaline bath containing ammonium fluoride and ammonium carbonate [85]. They found that the optimal concentrations were ammonium fluoride 0.25, ammonium carbonate 0.1 and ethylenediamine 0.1 mol/L. They also tried five polyhydric alcohols for studying their effects on anodizing of aluminium, and found that propylene glycol addition increased the thickness of anodic film by ~ 2 m. Also the hardness of anodic oxide film was better than that obtained from fluoride bath, but the scratch hardness was inferior to that obtained from sulphuric acid bath. Schnyder and Koetz investigated spectroscopic ellipsometry and XPS of oxide coating formation aluminum in sulphuric acid [86]. They monitored the growth and oxide layers dissolution on aluminum electrodes in 3M H2SO4 by using ex-situ spectroscopic ellipsometry and ex-situ XPS. The XPS results indicated that the porous oxide, as well the barrier oxide, grown in tartaric acid could be described as -Al2O3 containing no major amount of water. Coatings grown in 3M H2SO4 hold ~ 1.5% anions. Spectroscopic ellipsometry revealed the growth of a porous layer on top of a dense interphase layer.

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They also found that the film thickness was directly proportional to the anodizing time and applied current density. Surganov and Poznyak studied the kinetics of aluminum dissolution during electrochemical anodization in a tartaric acid electrolyte [87]. They found that the dissolution of aluminum occurred from the amount of application of an anodic potential on the sample. They explained the nature and interrelation of the kinetic dependencies of the anodic potential and the mass of the dissolved aluminum on the base of the concept of ejection of Al+3 ions from the surface of barrier oxide film into the electrolyte and by the electrochemical dissolution of the oxide. Floyd and Maddock developed an alternate finishing method of aluminum by resin-seal anodizing and provided a source of contributing corrosion protection to the aluminum without causing environmental problems [88]. They employed traditional sulphuric acid anodizing, but modified the final hydrothermal sealing step by using a resin containing bath in place of steam, water or water solution generally used. The resin particles filled the porous structure of the oxide coating. This resin-sealed surface acted successfully as a primed surface and could be used without paint or top coated. They found that the process was environmentally friendly and the finished product was weight and cost savings by this method. They used successfully resin-sealed anodizing on the C5 cargo aircraft and this process has been accepted for use in selected C-130 aircraft applications. Le and OBrien developed a new anodizing process for producing a high emittance coating on aluminum and its alloys [89]. They performed anodizing of aluminum or aluminum alloy substrate surface in an aqueous M2SO4 solution at elevated temperature (30 C) and by a step wise c-d-procedure, followed by sealing the resulting anodized surface in water at 200 F and then air dried. They found that the resulting coating has a high IR emissivity and solar absorptivity and a relatively thick anodic coating. Wolf et al. developed a process for sealing of aluminum anodic coating obtained from a chromic acid bath [90]. They performed the sealing of the oxide layer formed by chromic acid electrolyte by using a bath composition of de-mineralized water, potassium or sodium dichromate 8-12g/L, pH adjusted to 4.5 to 6.5 by NaOH addition, bath

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temperature 75-85C, and immersion time sufficient to make sure coating hydration rate of 8-15% for simultaneously obtaining good corrosion resistance and paint adherence. Danford carried out the study for comparison of chromic acid and sulphuric acid anodizing [91]. Because of federal and state restrictions on the use of hexavalent chromium, he compared the corrosion protection of 2219-T87 aluminum alloy by both Type I chromic acid and Type II sulphuric acid anodizing. Corrosion measurements were made on large, flat aluminum alloy sheet material with an area of 1 cm2 exposed to a corrosive medium of 3.5% sodium chloride at pH 5.5. He carried out both a.c electrochemical impedance spectroscopy and the d.c. polarization resistance techniques. He found that the corrosion protection obtained by Type II sulphuric acid anodizing was superior and no problems would result by substituting Type II sulphuric acid anodizing for Type I chromic acid anodizing. Golab et al. examined the anodic coating formed on aluminum alloy AlMg2 [92]. They obtained anodic coating at 1-3 A/dm2 and 5-20C temperature in oxalic acid baths. The tribolic parameters of the oxide layers were determined and compared with those of PTFE. To obtain an optimal sliding behaviour, the layer thickness must be 80-100 m, the microhardness > 4200 MPa, combined with a low roughness. They found that the optimal tribolic parameters were obtained at 1 A/dm2, 5C and 6 hours oxidation time. Zhou developed an improvement of corrosion resistance of anodized aluminium by chromic acid anodizing process [93]. He carried out anodization in a bath containing 30-60 g/L chromic acid solution and the temperature, voltage and time used were 3537C, 18-22 V and 30-40 minutes respectively. The anodic oxide film obtained was 37.756.0 mg/dm2. He found that no corrosion was observed after 5% NaCl solution was sprayed continuously for 336 hours and the adherence was also good. The chromium concentration of chromium containing waste water was reduced, so the energy used for treating waste water was decreased by using this method. Dima and Anicai studied the physical (mechanical, thermal) and electrical properties of aluminum anodic films obtained by continuously anodization of aluminum wires and aluminum sheets using an electrolyte based on boric acid, oxalic acid ,citric acid and isopropyl alcohol [94]. They found that the thickness of aluminum anodic oxide layers was 5 1, 10 1, for aluminum sheet, respectively and 5 1, 10 1, 15

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1 for aluminum wire. Aluminum oxide films ensured a breakdown voltage of minimum 200 volts, for coils having a curvature radius > 12.5 mm and operating temperature up to 500C. Gaskin et al. carried out investigation of sulphuric/boric acid anodizing as a replacement for chromic acid anodizing [95]. This research was under-taken to find the effectiveness of sulphuric /boric acid anodizing process on 2044-T3 aluminum adhesive bond durability. They analyzed three processes in this study: a phosphoric acid process and two sulphuric-boric acid processes (the patented process that was developed at Boeing and a process that was developed at Rohr). They found that the sulphuric-boric acid anodize process developed by Rohr gave results that were comparable to the phosphoric acid anodize process. Xu and Zhang developed a method for rapid anodizing of aluminum [96]. They obtained optimization of rapid anodizing of aluminum in sulphuric acid solution by using a bath containing a composite corrosion inhibitor comprising organic acids, alcohols, inorganic salts and a small amount of surfactants. They also studied the effect of the corrosion inhibitor on current density, anodization time, temperature and impurity content and tested the properties of the oxide film. Zeng developed alternating current anodization of aluminum and its alloy in sulphuric acid solution [97]. He introduced the characteristics and recent development of a.c. electrochemical oxidation in sulphuric acid. He emphasized on the mechanism of a.c. electrochemical reduction and its technology and comprehensive comparison was made between a.c. and d.c. electrochemical oxidations. Ishmuratova et al. used an electrolyte containing sulphuric acid to improve the corrosion resistance and increasing the breakdown voltage of an anodic coating on aluminum and its alloys [98]. The electrolyte used additionally contained cerium sulphate in the following proportions: sulphuric acid 180-200 g/L, cerium sulphate 0.5 10.0 g/L. Kallenborn and Emmons developed thin-film sulphuric acid anodizing as a replacement for chromic acid anodizing [99]. They studied a more dilute (5% by wt.) sulphuric acid anodizing process which produced a thinner coating than Type II or III with nickel acetate as a sealant. They evaluated this process in regard to corrosion

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resistance, throwing power, fatigue life and processing variable sensitivity and found it promising as a replacement for the chromic acid process. Noguchi and Yoshimura studied the result of organic acid salts on the anodizing of aluminum in organic alkaline baths (benzylamine-fluoride base) [100]. They conducted investigations to determine optimum bath compositions for the anodizing of aluminum in organic alkaline baths (benzylamine-fluoride base) involving ammonium fluoride and different organic acid salts (ammonium formate, ammonium acetate, ammonium oxalate, ammonium citrate). They found that uniform films were formed during anodizing in baths containing organic acid salts but non-uniform films were formed in baths without these additives. They also observed that the anodic oxide coating produced in 0.1 mol/L benzyl amine bath containing 0.1 mol/L ammonium citrate and 0.1 mol/L ammonium fluoride showed the highest corrosion resistance. Minch developed a new method with epoxy adhesives and coatings with basic bulk properties providing dissimilar metal separation and necessary corrosion protection to produce an oxide surface receptive to the formation of strong and durable bonds for anodizing of aluminum [101]. This innovation provided a two steps electrolytic process which included, phosphoric acid solution anodizing the aluminum firstly and then later on further anodizing with a boric/sulphuric acid electrolyte solution. He obtained a product with two anodized regions. The phosphoric acid produced primary outer region was characterized by open pores particularly suited for bonding with adhesives & sepoxy primers. The next base regions formed by boric/sulphuric acid solution provided a thick, hard, corrosion resistance section. Fang studied anodizing of aluminum in sulphuric/oxalic acid system and properties of anodized film of aluminum [102]. His results showed that the oxide film became thicker than that in pure sulphuric acid electrolyte. He observed that the film thickness was affected by the electrolyte concentration, current density and oxidation time. The conditions of aluminum anodizing in sulphuric acid-oxalic acid system were: electrolyte concentration 15% sulphuric acid + 1% oxalic acid, current density 1.0 A/dm2 and oxidation time 60 minutes. The results obtained helped to understand the aluminum anodizing process mechanism and showed an improvement in the properties of the anodic coating of aluminum.

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Bopp investigated boric/sulphuric acid anodizing on 2219 aluminum alloy to provide sufficient coating thickness due to alloys high copper content 5.8-6.8%[103]. The coating thickness and weight were crucial to ensure sufficient corrosion protection. He carried out the testing on a small section of this alloy to prove that the proper coating thickness and weight were achievable and met a minimum coating weight of 21.5 mg/dm2. Boeing Company used this process for anodizing of the Air Force KC-135 CFM-56 engine leading edge cowling which was being corroded in high salt environment. Fujino et al. developed anodization of aluminum in barium hydroxide alkaline bath and absorption of carbon dioxide from air was prevented by setting carbon fluoride membrane on the surface [104]. They compared the properties of the anodized film with those produced in other alkaline baths such as sodium carbonate and sodium hydrate baths and in sulphuric acid baths. Further more sodium aluminate and sodium tetraborate were added to barium hydroxide bath in order to improve hardness and abrasion resistance of the soft film produced in the alkali and the effects were examined. They found that the films obtained in barium hydroxide baths were superior to those with the same thickness (8m) obtained in sodium hydrate and sodium carbonate baths in the hardness and the resistance to alkali corrosion. The film obtained in sodium tetra borate added to barium hydroxide bath was found to have the highest hardness and greatest alkali resistance. They attributed these properties to the formation of cell structure from SEM observation of the film surface and were thought to be related to the composition ratio of aluminum & oxygen and film depth. Surganov and Poznyak studied the aluminum dissolution in the initial stages of anodization in a boric acid solution [105]. They investigated the influence of the anodic voltage scanning rate on dissolution of aluminum during its potentiodynamic anodization in 0.1 M boric acid solution. Gonzalez et al investigated the effect of triethanolamine addition on sealing time [106]. They carried out anodizing of aluminum sheets in sulphuric acid solution stirred with pressurized air and sealed the anodic layers in deionized water containing no additive or acetate ion or TEA. They also analyzed the efficiency of triethanolamine (TEA) and sodium acetate additions in accelerating sealing without detracting from its

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quality. They found that immersion for 1 minute in the presence of TEA ensured compliance with current standards, as measured by the dye spot and acid dissolution tests. This could result in substantial energy and space savings, because a single sealing bath could be used to process the output of two or more anodizing baths. Shino and Hoguchi investigated the anodic oxidation of aluminum in fluoride free baths containing amino alcohols and organic acid salts [107]. They also studied general characteristics of oxide coatings. Xu et al. investigated the structure & composition of anodic coatings of aluminum (AOF Al) formed in oxalic acid (I) and sulphuric acid (II) solutions by TEM, IR and TGA [108]. They found that the porous anodic oxide films consisted of a large number of hexagonal cells having an irregularly round pore in the center of each cell which penetrated vertically from surface to bottom, while a barrier layer under the film directly remained in contact with an aluminum substrate in scallop shape. Shawaqfeh and Baltus investigated the growth kinetics of porous aluminum films formed in phosphoric acid under galvanostatic conditions [109]. They used scanning electron measurements (SEM), Faradays law and oxide film mass measurements to analyze the growth kinetics and obtained film growth rates, pore diameter and porosity. Current efficiency was also determined from these measurements. They also examined the effect of c.d. and solution temperature on the oxide film growth rate and morphology. Mansfeld et al. developed the sealing of boric/sulphuric acid anodized (BSAA) aluminum alloys in yttrium or cerium salts at high temperature [110]. Dilute chromate solution, a cold nickel fluoride solution and boiling water sealing was also carried out to compare the results. They evaluated sealed BSAA aluminum alloy Al 2024, Al 6061, and Al 7075 for corrosion resistance by recording of impedance spectra while exposing in 0.5 N. NaCl for 7 days. Depending on the corrosion resistance, different time intervals for exposing were used for samples prepared by different sealing processes. They found that corrosion protection similar to chromate sealed BSAA aluminum alloys was obtained by sealing in cerium nitrate and yttrium sulphate solutions. Gong et al. studied the outcome of chromic acid quantity on the formation process of anodic porous alumina film [111]. They found that the c.d. of film formation increased, the time of film formation decreased and the thickness of oxide coating

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decreased with the increasing of chromic acid concentration. They pointed out that the formation of surface pores was, presumably, due to stress concentration developed during the formation of the film. Skoneczny investigated the oxide coating development mechanism on aluminum in ternary electrolyte [112]. He found that the surface of aluminum and its alloys can be improved by application of hard anodization using an aqueous ternary electrolyte (SAS). The SAS electrolyte consisted of among other things, sulphuric acid, adipic acid and oxalic acid. The electrolyte temperature during oxidation was within the 293-313K range and anodic current density (c.d) was within the 2-4 A/dm2 range. He also explained the structural patterns of the oxide coating on aluminum obtained in SAS electrolyte. Pakes et al. studied the growth of anodic films on aluminum in disodium tetraborate, so called alkaline anodizing by using transmission electron microscope (TEM) [113]. They observed that early coating growth proceeded at relatively greater efficiency under galvanostatic anodizing conditions and porous anodic film was formed during the following constant voltage period. The penetration of electrolyte species into the aluminum oxide film established conditions for field assisted dissolution, probably thermally enhanced and giving a porous anodic film. They described that the cell walls adjacent to the pores had a feathered appearance which was due to mechanical disruption of coating composition at pore base under the high filed. Domingues et al. carried out anodizing of aluminum alloy 2024-T3 using tailored sulphuric/boric acid electrolyte as an alternative to the anodizing process in chromic acid [114]. They obtained results showing that the addition of molybdate was necessary to this bath for satisfactory corrosion results. They used the technique of electrochemical impendence spectroscopy (EIS) to assess the anodic film properties. Thompson et al. investigated the effect of boric acid additions to sulphuric acid for the anodizing of Al 2024-T3 and Al 7075-T6 alloys at constant voltage [115]. They carried out anodizing after pretreatment by electropolishing, by sodium dichromate (Na2Cr2O7/H2SO4) etching or by alkaline etching. In their study, the current-time responses revealed that the concentration of boric acid in 50 g/L sulphuric acid had insignificant effect. They observed that there was negligible influence of boric acid on the coating weight, structure of the anodic coating, the thickening rate of the film, or

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corrosion resistance provided by the film of Al 7075-T6 alloy. They found that sealed anodic films in deionized water or preferably in chromate solution gave improved corrosion resistance, although not matching the far superior performance provided by chromic acid anodizing. Kurita studied the anodizing of aluminum alloys in electrolytic solutions containing sulphuric acid and oxalic acid or citric acid without decrease of surface hardness [116]. The aluminum alloys are useful for cylinders of internal combustion engines etc. He found that the anodized films obtained by this method had good abrasion resistance. Lopez et al. obtained anodic coatings in oxalic acid and sulphuric acid baths and compared their effectiveness to sealing quality control tests [117]. They found that the coating without sealing obtained in oxalic acid remained virtually unaffected in humid atmosphere in contrast to coating without sealing obtained in sulphuric acid which are autosealed. On the other hand, both types of coating aged in a qualitative identical way after sealing. The TEM study exposed a complex structure of hexagonal cells, consisting of three distinct zones in the coatings formed in oxalic acid and pores were five times larger in diameter as compared to films formed in sulphuric acid. They also found that the alteration of the film morphology, under the electron beam was slower in films obtained in oxalic acid bath. Cao et al. studied the anodizing of ZL102 Al cast alloys in boric acid/ tartaric acid mixture (weak acid anodizing) and obtained a compact, uniform anodic film with violet colour [118]. They found that the coating development rate increased by increasing the current density but coating growth was inhibited by increasing the bath temperature, while corrosion resistance of the film was also decreased with the increasing of bath temperature. Li et al. developed a method for the preparation of porous anodized film and studied its corrosion resistance [119]. They carried out anodizing of aluminum foil in sulphuric acid solution , sulphuric-acetic acid solution, sulphuric-oxalic acid solution and sulphuric-phosphoric acid solution, respectively, at 18C and 20 V for 3 hours and the anodized films were stripped from substrates by reverse voltage method. They determined the thickness of the anodized films and studied coating corrosion protection

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in media of sodium chloride, sodium carbonate, oxalic acid, hydrochloric acid and sodium hydroxide. They found that the film prepared in sulphuric acid was the thickest one and anodic films were stable in neutral media and their corrosion resistance decreased at pH < 1 or pH > 12. Wang et al. investigated the influence of concentration of phosphoric acid on formation of barrier layer of anodic porous alumina film [120]. They found that by increasing the concentration of phosphoric acid, the time needed to form barrier layer was shortened and the barrier layer became thinner also. They interpreted this phenomenon reasonably by the stress concentration that developed in barrier layer. Wang and Hu carried out anodizing of aluminum alloy (LF2) in a solution containing sulphuric acid (d = 1.84) 150-200, CK-LY additive 20-35 and Al+3 0.5-20g/L at 15-35C and c.d 1.5A/dm2 for 20 minutes time [121]. The CK-LY additive contained organic acid and a conducting salt. They found that this composition widened the temperature range of anodization process. The results of this process were also compared with that of conventional sulphuric process and their process was found better. Mansour et al. studied anodizing of aluminum and some of its alloys in organic and inorganic acids [122]. They carried out anodizing of Al, Al-Mn alloys and Al-Mg alloys in acetic acid, butyric acid, citric acid, propionic acid, oxalic acid, maleic acid, tartaric acid, phosphoric acid and sulphuric acid at 1.0 A/dm2 and 30 0.1C temperature. They found that the anodization of Al, Al-Mn and Al-Mg alloys for 0.5 hour in citric acid and tartaric acid at c.d. 1.0 A/dm2 resulted an increase in the weight of each specimen by 0.13-0.0156 g/20 cm2, while the weight increased by (0.6-9.0) x 10-3 g/20 cm2 in the other acids. Lee et al. examined the effect of additives on formation of porous oxide coating by anodizing in sulphuric acid [123]. They prepared porous alumina membrane from aluminum metal (99.9%) using d.c. power supply of constant current mode in an aqueous solution of sulphuric acid. Different additives like aluminum sulphate, aluminum phosphate and aluminum nitrate were added to aqueous sulphuric acid electrolyte to prevent the chemical dissolution of alumina membrane by providing Al+3 ions. They evaluated the effects of these additives on the formation of porous alumina membrane under various electrolyte concentration (5-20 wt %) and current densities (10-50 m

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A/cm2). They used various techniques like inductively coupled plasma atomic emission spectrometry, SEM, TEM and electrochemical impedance spectroscopy. They found that the membrane surfaces were damaged with all the additives except aluminum sulphate and a uniform surface of porous alumina was obtained with aluminum sulphate additive. Konno et al. developed a two step anodizing of aluminum to improve the physical and chemical characteristics of oxide film [124]. This process gave hard and corrosion resistant oxide coating on aluminum. The process consisted of two steps; the formation of chromate/phosphate treated layer was followed by sulphuric acid anodizing. This process gave anodic oxide coating containing Cr (III) and phosphate species mostly in the outer part of the porous layer. They found that the coating obtained by this process gave a better corrosion protection to the substrate aluminum from pitting in a chloride medium than the films formed by conventional anodizing. Serebrennikova et al investigated the characteristics of porous oxide coating by silver electrodeposition [125]. They compared the characteristics of different porous aluminum oxide coating in terms of their electrochemical responses during silver electro-deposition. The cyclic voltametric and current-time responses during silver deposition showed an increased rate in the following sequence; sulphuric acid grown films (smallest pores), phosphoric acid grown films (large pores) and barrier oxide films (no pores), under the same applied voltages. They found that thicker porous oxide coating formed after longer times of anodizing showed lower deposition currents, while coating formed at higher voltages (expected to yield larger diameter pores) resulted in higher silver deposition currents. Kumar et al. studied white anodizing for space applications using mixture of sulphuric acid, glycerol, lactic acid and sodium molybdate electrolyte system [126]. They investigated the effect of anodic film thickness and various operating parameters viz. electrolyte formulation, operating temperature, applied current density, on the optical properties of the coating, for the optimization of this process. Atomic absorption spectroscopic analysis, thickness and micro hardness evaluation were used to characterize the oxide coatings. They evaluated the space worthiness of the coating by humidity, thermal cycling, thermo-vacuum performance tests and optical properties measurement and found it appropriate in space environment for heat control applications.

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Kim et al. investigated the structural characteristics of electrochemically designed porous oxide films on AlMg1 [127]. They changed anodizing conditions in a broad range (electrolyte: sulphuric acid, phosphoric acid and mixture from these, concentration: 0.32.0 M, voltage: 5-10V, time 30-90 seconds, temperature 25-50C) and characterized the oxide layers via spectroscopic interference measurements to find the coating thickness. They also observed the layer morphology by atomic force microscopy (AFM) and characterized structural parameters of the anodic coating by electrochemical impedance spectroscopy (EIS). Shih and Tzou studied the characteristics of anodized films on aluminum using a pulsed current in mixed electrolytes of nitric acid-sulphuric acid or boric acid-sulphuric acid [128]. They proved in film dissolution tests that the anodic film contained two layers, and the composition of the film was also changed by the anodizing electrolytes. These results could also be obtained from energy dispersive spectroscopy analysis, when nitric acid or boric acid was added to an electrolyte of 10% wt. sulphuric acid. They found that the film thickness and microhardness could increase greatly by addition of a modifier. Zhang and Wang investigated the anodizing process and corrosion protection of 7050 T7451 aluminum alloy, which hardly formed the anodic coating in traditional chromic acid method [129]. They studied the effects of the anodizing voltage to find a suitable anodizing method. They found that the suitable voltage was greater than 30 V for this alloy anodized in chromic acid, and deoxidization worsened the corrosion resistance of the alloy. Chi et al. studied antibacterial activity of anodized aluminum by depositing silver [130]. Aluminum samples were anodized in a sulphuric acid bath, followed by silver electrodeposition into pores of the coated sample by using a.c.current. They tested the coated aluminum with deposited silver for its antibacterial activity. They found that the antibacterial rates of the samples with deposited silver were above 95% against the growth of different bacteria. Transmission electron microscope(TEM) was used to characterize the morphology of the silver in pores of anodized aluminum. Silver was assembled in the form of nanowires with the diameter of 10 or 25 nm. as shown by micrographs.

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Ono and Masuko determined the pore diameter of anodic film formed on aluminum in four major electrolytes by pore filling technique [131]. They found that the porosity of anodic film decreased with increasing voltage and at an identical voltage, it increased in the order of the oxide coating obtained in oxalic acid, sulphuric acid, chromic acid and phosphoric acid solution. Zuo et al. studied the influence on the corrosion behaviour of three anodized aluminum alloys, 1070, 2024 and 7075, in sodium chloride solutions by different sealing methods [132]. They sealed the anodic films by boiling water, stearic acid, potassium dichromate and nickel fluoride methods and studied the passivation and pitting behaviour obtained by these sealing methods using the potentiodynamic polarization tests and surface morphology by using SEM technique. They revealed that good corrosion protection was provided in acidic solution by the boiling water and potassium dichromate sealed films, while nickel fluoride sealed film was better in basic solution , while stearic acid sealed film offered good corrosion protection both in acidic and in basic solutions. Djozan and Zehni investigated an anodizing method for the inner surface of long and small bore aluminum tubes and investigated parameters affecting thickness, shape, porosity and stability of the oxide layer formed[133]. They determined optimum conditions for electrolyte solution, temperature, applied voltage and anodizing time. Anodizing was performed both in dynamic and static modes. Chemical characteristics of anodic film were studied by adsorbed amount of fuchsin and physical characteristics of anodic film were studied by SEM. They found in their results that the quality of aluminum oxide layer formed in dynamic mode was better. Li et al. developed an environmentally friendly coating method (modified anodizing) by using aqueous sodium bicarbonate electrolyte and studied corrosion protection characteristics of oxide coatings on an Al-Si alloy [38]. They deposited oxide coating on Al-Si alloy samples to form hard and corrosion protective coating using three different techniques: hard anodizing (HA), anodizing (A) and modified anodizing (MA). The corrosion resistance of the coatings was determined by potentiodynamic polarization tests. The coating microstructure and chemical composition was studied by SEM and EDX studies before and after the corrosion test. They concluded that the modified

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anodizing is an environmentally friendly coating method which gives a hard oxide coating having good corrosion protection. Wang and Wang carried out analysis of porous aluminum oxide coating formed in mixed electrolyte of phosphoric acid, oxalic acid and cerium salt [134]. They investigated growth, morphology and chemical composition of the film by using SEM, EDAX and XPS techniques. Their results indicated that the formation of porous layers in this solution undergo three stages during anodizing, as in other conventional solution, while the whole growth rate was non-linear. They also observed that this electrolyte was sensitive to anodizing temperature, which affected current density to a greater degree. They found that the corrosion section of film has two distinct layers; outer layer was of uniform structure and the inner one was about 8 m which bounded the substrate compactly. Kaplanoglou et al. studied the effect of different alloys on the anodizing process of aluminum [135]. They used specimens of AA 5083 and AA 6111 (unheat and heattreated) for their investigation in comparison with the pure aluminum during anodizing in sulphuric acid bath by using electrochemical techniques, SEM/EDX and XRF. They found that alloy type affected the kinetics of anodizing but the basic aspects and certain qualitative characteristics of the anodizing mechanism were similar. Garcia-Vergara et al. investigated the effect of copper on the morphology of porous anodic alumina [136]. They used sputtering deposited Al-Cu alloy layers and an Al-Cu/Al bi-layer to study the influence of copper on the structure of porous anodic alumina films formed galvano-statically in either sulphuric or phosphoric acid. They revealed in their results that the development of an irregular morphology of pores during anodizing of the alloy layers, contrasting with the linear porosity of films formed on aluminum. Further, the rates of film growth and alloy consumption were relatively low, since oxygen was generated following enrichment of copper in the alloy and incorporation of copper species into the anodic film. They also found that the linear morphology was re-established following depletion of the copper in the bi-layer and at the same time, film growth was accelerated as oxygen evolution diminished. They considered that the irregular pore morphology was due to the stress-driven pore development influenced by effects of oxygen bubbles.

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Bensalah et al. carried out the optimization of anodic layer properties on aluminum in mixed oxalic/sulphuric acid bath using statistical experimental methods [137]. They obtained a four variables Doehlert design (bath temperature, anodic current density, sulphuric acid and oxalic acid concentrations). They conducted a multicriteria optimization using desirability function in order to maximize the growth rate and the microhardness of the anodic oxide layer and to minimize in the same time their chemical and abrasion resistances. They used dissolution rate of the oxide in phosphochromic acid solution (ASTM B 680-80) to express the chemical resistance of films. They attributed the higher abrasion and chemical resistance of the optimum layer with its structure. Aerts et al. investigated the temperature effect on the porosity and the mechanical properties of the oxide coating [138]. They evaluated the microhardness and fretting wear resistance of anodic oxide layers, produced on commercially pure aluminum by potentiostatic anodizing in sulphuric acid under conditions of controlled convection and heat transfer in a reactor with a wall-jet configuration, as a function of the electrolyte temperatures in a wide range from 5C up to 55C. The microstructure information of the anodic films was obtained by FE-SEM analyses, whereas image analysis of highresolution surface images provided quantitative information on the evolution of the surface porosity as a function of the electrolyte temperatures. They found that increased mechanical characteristics were directly related to the microstructure. They also measured local temperatures at the backside of the working electrode (WE) by five thermocouples (type T), embedded in the sample holder at 5 different radial positions, these being 15 mm, 10 mm, 0 mm, 5 mm and +15 mm from the centre of the anode respectively. They pointed out that anodized electrodes had displayed a regular anodizing behaviour without occurring of local phenomena. Sulka and Parkola studied the temperature effect on well-ordered nanopore structures grown by anodization of aluminum in 20% wt sulphuric acid at various cell potentials and temperatures [139]. They performed quantitative analyses of defects and Fourier transforms (FFT) from SEM images showing that regularity of nano pores arrangement could be improved by increasing anodizing potential, independently of the anodizing temperature. They found that the best result in controlled anodization of aluminum could be obtained at 25 V and the temperature of 1C.

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Bartolome et al. investigated the corrosion behaviour of different bare and anodized aluminum alloys using exposure tests in natural atmospheres with three different coating thicknesses [140]. They evaluated these coatings for two years exposure in two natural atmospheres of very different corrosivities, one urban and the other marine. Shanges in the specimens during exposure were evaluated by several techniques but direct attention was focused to the direct measurement of corrosion by gravimetry and its indirect estimation by the comparatively much more sensitive electrochemical independence spectroscopy (EIS) technique. The results showed that if no demands were placed on the conservation of its appearance, aluminum may be used without protection even in an atmosphere of medium or higher corrosivities. Harscoet and Froelich studied the use of life cycle assessment (LCA) methodology to asses the environmental benefits of substituting chromic acid anodizing (CAA) [141]. They carried out a precise literature review to evaluate bath atmospheric emissions. The results of the performed assessment confirmed that the only way to efficiently deal with hexavalent chromium compounds is to substitute the electrolyte used in the bath as the most hxavalent chromium emissions are caused by other stages than the main. Other specific issues, such as water and energy consumptions have, nevertheless, to be studied throughout the whole life cycle of the chemical substitute to monitor performance against chromic acid anodizing. Zhang et al. studied the bonding strength and corrosion protection of aluminum alloy by phosphoric acid modified boric acid/sulphuric acid anodizing bath [142]. They examined the microstructure and topography of the anodic films by using SEM and AFM techniques and also studied the adhesive strength and corrosion behaviour with lap-shear test, wedge test and electrochemical technology. Their results revealed that a thicker film with high porosity and big pores could be produced by this anodizing method. They found that the porous film was beneficial to improve the durability and lap-shear strength of the bonding joints and the thicker film provided better corrosion protection. Gonzalez et al. studied that atmospheric corrosion of bare and anodized aluminum in a wide range of environmental conditions [143]. They obtained the oxide coating in a sulphuric acid bath and sealed for 60 minutes in boiling deionized water and characterized before and after different exposure times by means of visual inspection;

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observation with a magnifying glass; and using classic gravimetric techniques. They also compared behaviour of aluminum in the bare condition and when protected with anodic films of approximately 7, 17 and 28 m thickness for 42 months of exposure in 11 atmosphere of very different aggressivities, with salinity values ranging between 2.1 and 684 mg Cl- m-2 d-1. They concluded that anodizing and sealing prevented the danger of pitting corrosion even in the most aggressive atmospheres. Aluminum is a most multipurpose metal. It can be finished in a variety of ways. It can be made to resemble other metals, or can be finished to have a colourful as well as a hard, durable finish unique unto itself. Only the imagination limits the finish and colours possible with anodized aluminum [25]. It is widely used in aircraft industry, aerospace, construction industries, transport, packaging, ship building and other fields [144-146]. Pretreatment of aluminum provides not only strong tensile strength and durability but also good corrosion protection. Chromic acid anodizing process with a potassium dichromate/ sulphuric acid etching procedure was one of the most widely used pretreatment for structural bonding due to good properties of the films incorporating some Cr (VI) and Cr (III) [42]. However the use of hexavalent chromium is not allowed from a health and environmental concerns due to its poinous and carcinogenic effects. This process is gradually limited even banned [40-43]. Alternate of chromic acid anodizing process has been vital and critical subject in industrial sectors and environmental studies. In Europe, there was interest in boric acid anodizing [36], while in the U.S.A. Boeing developed phosphoric acid anodizing process [31]. A ferric sulphate/sulphuric acid treatment was used as alternate of dichromate/sulphuric acid etching procedure prior to phosphoric acid anodizing [147]. Besides phosphoric acid anodizing, a mixed sulphuric acid/boric acid process, carried at out lower temperature, has been patented [56]. Thin film sulphuric acid anodizing [57, 58, 99] has also been developed to replace chromic acid anodizing. The modified boric acid anodizing or boric/ sulphuric acids anodizing processes have been studied by some scientists [148-150]. Zhang et al [142] have developed a process of phosphoric acid modified boric/sulphuric acid anodizing to improve bonding properties and corrosion resistance.

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Earlier work [20, 151-153] has described the influence of anodizing conditions (voltage, temperature, composition and acid concentration of the bath) on the anodizing current density, the porosity and the diameter of the pores of the anodic oxide in sulphuric acid electrolyte as follows. 1. Both the current density and the coating porosity increase by increasing the temperature at a given anodizing voltage due to thermal enhanced field assisted dissolution. The dissolution of the outer oxide surface is also increased. 2. At a given anodizing voltage the current density increases by increasing the sulphuric acid concentration due to higher solubility of the oxide film. This higher film dissolution is also responsible for the increase of the pore diameter and the coating porosity. 3. At a given temperature, the current density, the barrier layer thickness and the diameter of the pores increase by increasing the anodizing voltage, while the coating porosity decreases.

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2.1

Plan of Work
Aluminum metal and its alloys are widely used in aviation, aerospace, and other

fields and it is anodized to resist harsh environmental conditions in its service life. The anodizing of aluminum and aluminum alloys provides not only strong tensile strength and durability but also good corrosion resistance. Chromic acid anodizing was one of the most widely used pretreatment of aluminum and aluminum alloys. However the use of hexavalent chromium is not allowed from a health and environmental concerns due to its poinous and carcinogenic effects. This process is gradually limited even banned. Alternate of chromic acid anodizing process has been an essential and critical subject in industrial sectors and environment studies: 1. In the present work, different electrolyte compositions including acetic acid, oxalic acid, citric acid, tartaric acid, boric acid and sulphuric acid being environmentaly safe were prepared to carry out the anodizing of aluminum samples at different conditions. 2. 3. The anodized aluminum samples were evaluated using different techniques for its thickness and morphological studies. Corrosion study of the anodized aluminum samples was carried out using Potentiostat PG30 to find the effectiveness of anodic oxide coating against corrosion.

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