TERM PAPER, 2012 On

Aluminizing

Submitted By Atanu Kumar Khan (08MT3012) Manoj Kumar Singh (08MT1030)

1 LITERATURE SURVEY 1.1 What is Aluminizing? Aluminizing is a process in which the surface of a metallic component is coated with a layer of aluminium. Steels and nickel-based alloys are the most common metals that are aluminized for commercial applications. Aluminium coating on steel or other materials increases their resistance to oxidation at high temperatures (500-800C). It may also increase the corrosion-resistance of steel in hydrocarbons and sulphurous atmospheres. 1.2 Aluminizing Methods Various methods can be employed to obtain an aluminium coat on the surface of metals. In some cases the surface may only be enriched with aluminium by impregnation to enhance its resistance to oxidation at elevated temperatures. The various methods commercially employed for aluminizing are as follows. 1) Pack Aluminizing 2) Spray Aluminizing (Metallizing) 3) Vacuum Aluminizing 4) Gas Aluminizing 5) Cladding 6) Electrolytic Coating 7) Hot Dip Aluminizing Pack Aluminizing is carried out at fairly high temperatures (900-1080C). The surface to be aluminized is first cleaned of the scale and dirt and then packed in air-tight retorts with aluminizing mixture, which consists of aluminium or ferro-aluminium dust or powder. The retorts are then heated to the aluminizing temperature for up to 30 hrs. This method is expensive and time-consuming and is only recommended for articles of intricate shapes. Typical applications of pack-aluminizing are nickel-based alloys used in gas turbines, although steels can also be pack-aluminized to improve its high temperature oxidation resistance. Spray Aluminizing (Metallizing). In this method an aluminium coating of a precise thickness is sprayed on pre-cleaned surface . The process includes melting and spraying the metal with a jet of compressed air (at 25-60 psi pressure) with special metallizes. The bond thus obtained is of low strength, although the adherence can be improved by roughing the surface of the substrate. Annealing at 850-1250C for long time is done to increase the bond strength. Vacuum Aluminizing. In this process an aluminizing coating is applied by vaporizing the aluminium and condensing it on the substrate. The coating thickness in this case is of the order of 0.1 micron . Vacuum chamber with a pressure of 10-3 - 10-5 mm of Hg is required. Electron beam devices are used to melt the aluminium and raise its temperature up to 1400C. Substrate also has to be heated up to 175-370C. This process gives a good coating adherence. Gas Aluminizing. In the gas-aluminizing method, the steel substrate is impregnated with aluminium by means of gaseous phase of aluminium chloride . The process is carried out in a retort which contains the mixture of following composition 45% pure aluminium 45% Al2O3

10% AlCl3 This mixture in the retort is heated to 600C. The substrate to be aluminized is placed at the opposite end of the retort and is heated there at 900-1000C. Impregnation of steel takes place according to the following reaction: AlCl3 + Fe FeCl3 + Al Due to the complexity of the process and a considerable consumption of energy, this method is rarely used in industry. Cladding is accomplished by cold-rolling together the sheets of steel and aluminium. During the rolling process metallic bond is formed between aluminium and steel. In this way bimetallic strip or sheets are also formed . Electrolytic Coating. In electrolytic coatings either fused electrolytes composed of a mixture of fused salts of aluminium chloride or aluminium in ethyl bromide and benzene are used. Before coating the substrate is thoroughly cleaned, degreased and pickled in HCl solution [1]. The deposition-rate of aluminium metal onto the substrate in this process is very slow; typically a coating thickness of 0.01 mm may be obtained in around 30 minutes. 1.3 Hot Dip Aluminizing In this method of aluminizing the steel substrate is dipped after cleaning the surface into molten aluminium or an alloy of aluminium at 700-800C for a certain length of time. The process is essentially a thermo-chemical treatment similar to galvanizing or zinc-coating. During the holding of substrate in molten aluminium a reaction takes place between solid iron and liquid aluminium producing one or more inter-metallic compounds of FenAlm type between the outer aluminium layer and the substrate steel [1]. The thickness of the interlayer depends on holding time and temperature. The quality of aluminizing is markedly affected by the cleanliness of the surface of substrate. The process was developed after 1st world war in Russia, U.S.A. and Japan. 1.3.1 Continuous HDA of Mill Products Aluminium hot dip coating of steel strip and wire is performed by a number of patented processes, using continuous anneal-in-line equipment similar to that used for galvanizing. The process consists essentially of three operations: surface preparation, pre-heating of the steel base, Aluminium coating.

Surface preparation is a two-phase operation. First, all soil is removed from the surface by oxidizing at elevated temperature or by chemical cleaning. Then, the surface oxides are reduced in a suitable atmosphere to prepare the strip for coating [1]. Because the reaction between aluminium and steel is extremely rapid, the immersion time, the temperature of the molten aluminium, and the temperature of the strip before and after coating must all be controlled to prevent the formation of an excess of iron aluminium interfacial alloy. Unless a void layer separates the alloyed coating from the base metal, the amount of iron in the alloyed coating increases with time as the aluminium continues to diffuse into the base metal. The amount of brittle interfacial alloy layer can be controlled also by the addition of silicon to the coating bath [1]. This increases the apparent ductility of the coating, enabling more severe

fabrication of the sheet without peeling of the coating. The thickness of the interfacial layer decreases rapidly as the silicon content increases to about 2.5%. A smaller decrease occurs as the silicon content is further increased. 1.3.1.1 Equipment Equipment for a continuous line of hot dip aluminium coating consists of a feeding section, a furnace section, and a delivery section. In the feeding section, equipment uncoils incoming strip and feeds it into the coating line at a designated constant speed under specified tension. The furnace section contains the preheating or oxidizing furnace, the annealing furnace, the cooling furnace, and the coating pot. If chemical cleaning is used, alkaline cleaner and water rinse tanks are substituted for the preheating furnace [1]. The cooling furnace is connected directly with the annealing furnace and extends to the coating bath with its end sealed by means of a snout extending into the molten aluminium bath. A dry reducing atmosphere of hydrogen and nitrogen is maintained within the annealing and cooling furnaces. The delivery section is equipped to provide rapid cooling and sufficient time for setting the coating before the strip contacts the support roll over the coating bath. Drive rolls and equipment for looping roller levelling, coiling and shearing, and stretch levelling and surface conditioning are all contained in the delivery section. The Process line is shown in Figure 1.1.

Figure 1.1. Process diagram of continuous hot dip aluminizing of steel strip and wire [2].

1.3.1.2 Effect of Coating on Strength and Fabricability For different reasons, aluminium-coated steel strip and wire decreases measurably in strength. The strength of strip decreases because it is normally annealed prior to coating in order to improve its fabricability. Wire strength decreases as a result of the high temperature, above 650C, of the hot dip coating bath [1]. An example is aluminium conductor steel reinforced ACSR wire, which is either aluminium coated or galvanized. Its tensile strengths range from 1140 to 1450 MPa (165 to 210 ksi) depending on the type and class of coating specified. Steel sheet coated with aluminium silicon alloy withstands moderate forming, drawing and spinning operations without flaking or peeling of the coating. Steel sheet coated with commercially pure aluminium withstands moderate brake and roll forming operations and can be spun or embossed, but is not suitable for drawing [1]. Sheet with either type of coating can be given a 180 bend around a diameter equal to twice the thickness of the material; however, in any forming operation, it is advisable to allow liberal radii to prevent crazing of the coating. Because sheared edges are susceptible to corrosion, the use of aluminium coated sheet for fabricated assemblies may be limited for appearance considerations. Corrosion protection is not impaired, because there is no undercutting of the coating.

Coated sheet should be fabricated before the coating is diffused. Diffusion converts the coating to an iron-aluminium compound, which is very brittle [1]. The alloy arises from interaction of molten, commercially pure aluminium with the steel surface and is the agent that bonds the total coating to the substrate [2]. The alloy is an essential part of the coating protection system, supplementing the aluminium layer and providing a second line of defence to ensure long term durability. Control of the alloy layer thickness and thickness uniformity assures the degree of coating formability. Aluminium spontaneously forms an aluminium oxide passive film, as it is a characteristic of aluminium. This film imparts its usual resistance to major environmental factors influencing corrosion behaviour in water and soils [2]. Corrosion due to dissolved gases and carbon dioxide and erosion corrosion due to high velocity water are the common influential factors in a pipe waterside environment. The passive film imparts high resistance to all of these factors. Figure 1.2 shows the typical microstructure of a HDA steel sheet.

Figure 1.2: Microstructure of a hot-dip-aluminized steel sheet showing; surface Al-coating, Al-alloy interlayer, and the steel substrate [2].

1.3.1.3 Typical Applications A wide variety of industrial, farm, and consumer products are fabricated from steel sheet aluminium coated at the mill. The following products require resistance to oxidation and corrosion at temperatures from 95 to 680C: combustion chamber and outer casings, agricultural crop dryers, automotive mufflers, space heaters, furnace flues, oven interiors, barbecue grills, and wrappers for water heater elements. Fabrication of these parts requires moderate drawing, forming, punching and spot welding [1]. 1.3.2 Batch Hot Dip Coating of Parts Steel parts to be aluminized are first cleaned by hot-alkaline dipping and water rinsing. Steel parts are then de-scaled by abrasive blasting or acid pickling, rinsed and dried [1]. Gray or malleable iron parts are given an additional cleaning in molten salt to remove carbon smut. For coating parts by the fused-salt fluxing method, an electrically heated fluxing furnace is used in conjunction with a coating furnace. The fluxing furnace is lined with a porous refractory brick, such as mullite, and insulated with porous silica brick surrounded by a steel shell. The brick

lining must be compatible with both aluminium and halide salts of sodium and potassium, at temperatures up to 790C. The fluxing furnace contains aluminium for maintenance of the salt bath. The coating furnace is preferably a low-frequency induction furnace with a mono-cast or rammed lining. To prevent oxidation, a layer of molten salt 25 to 75 mm thick floats above the molten aluminium [1]. A cast iron pot can be used for the coating furnace, but the pot must be coated with a wash of iron oxide and titanium dioxide in a silicate binder to prevent attack by the molten aluminium. 1.3.2.1 Procedures and Control An example of an automatic conveyorized line for high-production batch hot dip coating of small parts such as fasteners is shown in Figure 1.3. The procedure consists of cleaning, preheating, fluxing, and coating [1].

Figure 1.3. Flow sheet diagram showing batch hot-dip-aluminizing process for steel parts [1].

In this cleaning process, about 100 kg load of parts is put into a basket and immersed in reducing salt at a temperature of 540C for 20 to 25 min. The parts are dip rinsed in cold water and then pickled for 15-20 minutes in 8-10% H2S04 at 70C. The parts are dipped and sprayed with cold water, and dried in circulating hot air. For the preheating and fluxing processes, a basket is loaded with 10-20 kg (20 to 40 lb) of cleaned parts. The parts are dipped in salt (40% NaCl, 40% KCI, 10% AlF3, and 10% Na3AlF6) for 8 to 15 min at 705C [1]. The basket is in constant motion during the preheating, fluxing and coating processes to remove any trapped air and to flux all surfaces of the part thoroughly. The basket of parts proceeds to the coating process where the parts move through the molten aluminium alloy at 700C for 1 to 2.5 min. Excess aluminium is removed from parts by centrifuging, air blasting or shaking. After the basket is unloaded, the parts are quenched in water at 70 to 80C. Then, they are air dried and inspected. In another coating process, the pickling and fluxing operations are eliminated. Parts are abrasive grit blasted and then immersed directly into molten aluminium. The bath surface is skimmed before parts are immersed and before they are removed. Unless it is carefully controlled, this procedure has the disadvantages of (a) heating parts to coating temperatures in the molten aluminium, producing a heavier alloy layer, and (b) dissolving additional iron into the bath. An iron content in excess of 2%; may produce rough coatings. The iron content of the coating bath can be controlled to some extent by reducing bath temperature. At lower temperatures, aluminium high in iron becomes mushy and concentrates along the sides and corners of the pot from which it can be removed rapidly [1]. Another method of reducing the iron content is to remove part of the bath and add iron-free aluminium.

Temperature control of the molten aluminium is important. Higher temperature increases the thickness of the intermetallic layer and decreases the thickness of the pure aluminium overlay. A wider range of temperatures can be tolerated when the aluminium contains 5% silicon. Immersion time must he controlled closely. The thickness of the intermetallic layer increases with immersion time. The pure aluminium overlay, is not affected, because its thickness depends upon the viscosity of the aluminium and on the speed with which the part is withdrawn from the bath [1]. 1.3.2.2 Limitations Small parts with fine threads are considered impractical to coat by dip methods. Washers and cup shaped parts that may nest offer some difficulty in batch processing. Continuous uniform coatings are difficult to produce on items with complicated configurations involving blind holes and reentrant angles, in which air can be entrapped [1]. Long slender parts of thin cross section may warp at coating temperatures 660 to 720C. Such parts must be well supported or immersed in the vertical position to minimize warping; however, some deformation still may occur as a result of the stress-relieving effect of the bath temperature. The use of the lower temperature aluminium-silicon alloy may help to minimize distortion. The strength of coated parts, especially those made of cold worked material, may be reduced by the coating operation. In certain instances, this condition can be alleviated by the use of higher strength material. One producer of aluminium-coated bolts made of 4140 steel states that a tensile strength of 760 to 790 MPa is the maximum practical strength that can be obtained after coating without resorting to high-alloy steels. The composition of the steel does not limit the batch hot dip coating process. The choice of steel depends on the strength and service requirements. Aluminium coatings applied by hot dipping are more costly than hot dip coatings of other metals. This is because the basis metal- requires more thorough cleaning, more heat is needed for coating at about 700C, and electricity must be used for heating the ceramic pot [1]. Fuel costs may be decreased by the use of iron pots fired by gas or oil, but ceramic pots are preferred for this process. 1.3.3 Coating of High Production Parts Automotive poppet valves, blades and nozzle vanes for gas turbine engines, and fasteners used in connection with pole line hardware and aluminium assemblies are examples of high production parts that are coated with aluminium [1]. 1.3.3.1 Corner Castings In contrast to the complexity of the high-production line for fasteners and complicated small parts is the procedure for coating large corner castings used on aluminium fabricated cargo containers. These castings, each weighing about 14 kg (30 lb), are made of medium-carbon steel. The procedure for aluminium coating a production run of 12,000 of these castings is as follows: Inspection: incoming castings are inspected visually for flaws. If cavities are present, a fixture is used to check their size. Because the finished product must mate with another steel fixture, the size of part and build-up of excess aluminium are critical. Cleaning: castings are oven-baked in batches at 200C for 5 h to remove gases and grease contamination, and then blasted with clean steel grit, 25 to 40 mesh. Racking: castings are handled with clean cotton gloves to prevent surface contamination during racking. Castings must be racked so that air pockets do not develop during immersion in molten aluminium. An air pocket causes oxidation of the ferrous metal surface and interferes with coating.

Immersion: each rack containing 30 pieces is dipped into molten aluminium, 99.5%, at 720C for 12 min. The iron and silicon contents of the bath are determined weekly. When the sum of the two exceeds 3% uncontaminated aluminium is added to reduce the concentration, or the bath is scrapped and recharged. Cleaning: immediately on removal from the molten aluminium, the rack is shaken and the castings are air blasted to remove excess aluminium. Inspection: each piece is inspected to ensure fit [1].

1.3.3.2 Turbine Blades and Vanes These parts, usually made of super-alloys for use at 700 to 1100C, can be coated satisfactorily or impregnated with aluminium by the slurry method, by pack diffusion, or by hot dipping and diffusion treatments [1]. The earliest work used a hot dip process that recognized the importance of a thin alloy surface layer for optimum resistance to thermal shock and corrosion. The following are basic steps in the processing of turbine blades or turbine vane segments by the hot-dip-and-diffuse method. Surface preparation: o Immerse in molten caustic, oxidizing at 500C for 15 min o Rinse in water at 80C for 2to 3 min o Wet blast with 240-mesh grit at gage pressure of 690 kPa Aluminium coating: o Immerse in molten salt flux: 35 to 37% KCl, 35 to 45% NaCI and 0.5 to 12% AlF, 8 to 20%, Na3AlF6 at 720C for 3 to 5 min. This flux should be maintained above the molten aluminium for the purpose of activation. o Immerse in aluminium bath at 700oC for 3 to 10 s. o Rinse in molten flux, then air blast or centrifuge and wash in water. o Dip in 25% HNO3 solution at 21oC to brighten and clean the surface. o Leach in 10 to 12% HCl solution at 65 to 75C when necessary to remove aluminium. o Wash in water at 100C and dry Heat treating for diffusion: o Load in furnace at temperature o Diffuse at 1090 to 1150C for 2 h at temperature in air, argon, helium or endothermic generator gas. o Cool slowly in furnace to below 760C Final cleaning of the diffusion heat treated blades is necessary if an accurate dye penetrant or fluorescent oil penetrant inspection is required [1]. Wet blasting is suitable for removing the oxide prior to such inspection. 1.3.3.3 Automotive Poppet Valves The most advanced method of coating poppet valves consists of these operations: ng and grinding aluminium onto preheated surfaces. Spray gun should be at a fixed position from the preheating station. Valves are rotated to obtain uniform mechanically bonded coating. lve progresses to an induction heating station, where the coating is heated to bond it metallurgically to the substrate metal by diffusion to a depth of about 25 m (1 mil).

This method results in minor discoloration of the valve head and a slight roughening of the aluminium coating. Subsequent surface conditioning is unnecessary, and even undesirable, because the full thickness of heat resistant surface alloy is an advantage during service. The slightly roughened surface, consisting of undiffused aluminium, becomes smooth in the first few

seconds of engine operation [1]. Most aluminium-coated valves are made by this method, which is the most economical and the most effective for developing soundness, uniformity and durability. Valves may be coated also by the hot-dip-and-diffuse method or by spraying and subsequently diffusing in a salt bath, but the cost of either of these procedures is greater than for the method described above. 1.4 Fe-Al Binary Phase Diagram 1.4.1 The Range 0-54 At. % Al The liquid and solidus curve of the phase in the Figure 1.4 was plotted using the highest liquidus temperature and the smallest solidification intervals reported [4-7]. The vertex of the loop has been reported as about 1.2 wt % (2.4 at. %) Al [6], and about 1.0 wt % (2.0 at. % ) Al [8]; see data points in the insets of Figure 1.4. The /( + ) and /( + ) boundaries calculated by [9] extended to about 1.2 at. % (0.6 wt %) and about 2.0 at. % (1.0 wt %) Al, respectively, at about 1150C. Because of the lack of reliable experimental data, the location of the high-Fe boundary of the + and + field is uncertain. In addition, information related to the probable connection of the latter phase boundary with the disorder order transformation 2 = FeAl is still missing. The /( + ) boundary is merely based on the thermal results of Gwyer and Phillips [7]; its extension to lower temperature is tentative. Both [6] and [10] found that solubility of Al in -Fe decreased with fall in temperature. It is not known whether the composition FeAl lies inside or outside the heterogeneous field.

Figure1.4. Iron-Aluminum binary phase diagram [3].

Table 1.1. Description of phases formed at different wt% Al [3].

1.4.1.1 The Order-Disorder and Magnetic Transformation. First indication of the occurrence of transformation in the solid solution was the detection of an ordered b.c.c. structure of the CsCl (B2) type [11]. The existence of two super lattices based on the ideal composition Fe3Al = 1 and FeAl = 2 was established by Bradley and Jay [12,13]. Alloys with 0-51 at. % Al were (a) quenched from 700 and 600C and (b) slowly cooled from 750C. Upto about 18.5 at. % Al the atomic distribution in the b.c.c. lattice of -Fe was random, independent upon heat-treatment. In the range 18.5-25 at. % Al the atomic arrangement was random after quenching from 600C or higher, but ordered after slow-cooling to room temperature, with the degree of ordering increasing to 92% at 25 at. % Al. The super-lattice Fe3Al gradually emerging from the random arrangement is of the BiF3 (DO3) type, and the lattice constant twice that of the phase. Between 25 and 34 at. % Al the structure was of the Fe 3Al type (gradually changing to FeAl type) after slow cooling and of the FeAl (B2) type after quenching from 600C or higher temperature. Above 34 at. % the structure was solely of the FeAl type, after both slow cooling and quenching from 600 and 700C. These finding indicate that the Fe3Al superlattice is formed below 600C whereas the FeAl superlattice is stable upto 700C; however, the formation of the latter superlattice might not be suppressed by quenching. With the heat treatments used in these studies, no regions containing both and Fe 3Al structures and both Fe3Al and FeAl structures could be found. Bradley and Jay [12,13] therefore claimed that the transition of one type of structure to the other was continuous. Additional studies using clearly defined long-time anneals, is necessary to prove whether this is true. Some workers [14-17] studied the order-disorder transformations in the Fe3Al range by means of thermal [15], specific-heat [15,17], dilatometric [15], resistivity [14,16,17], and magnetic [15,17] methods. The transition temperatures reported by these workers are shown in Figure 1.5, which also contains the curves of the curie points of the disordered -phase and the ordered Fe3Al structure based on the fairly closely agreeing results of [15,16,18,19]. Curie temperatures were also determined by [6,20,17]. As shown in Figure 1.5, Saito [17] found the transition temperatures in the range 10-24 atomic % Al which were claimed to belong to short-range ordered superstructure of Fe13Al3 (18.75 atomic % Al). This type of structure was found to coexist with the Fe 3Al superstructure in alloys

containing more than 21.4 at. % Al. A new phase diagram was proposed for the range 10-30 atomic % Al. Although considerable information on order-disorder and magnetic transformations is available, more work is needed. As a consequence, the transformation curves and dashed structure boundaries in Figure 1.4, proposed in principle by Bradley and Taylor [21], are to be regarded as tentative. Transition temperatures of the order-disorder transformation FeAl (2) have not been determined as yet. For more complete information of the transformation in the range 0-50 at. % Al, the papers [12-27] should be consulted.

Figure 1.5 Fe-rich-end of the Fe-Al phase diagram showing different ordering and disordering transformations [28].

1.4.2 The Range 54-77 At. % Al The solidification equilibria suggested by [4-7] are greatly at variance. The various findings have been summarized by Hansen [28]. In contrast to [5, 6], who found only one phase of variable composition between 68 and 76 at. % Al, some workers [7, 29, 30] gave evidence of the existence of two phases in this region, Fe2Al5 = and FeAl3 = . In addition to the phase which forms peritectically at 1230C [5], 1207C [6], 1232C [7] or 1210C [29] and decomposes eutectoidally at about 1100 [5], 1080 [6,29] or 1103C, another phase between 65 and 70 at. % Al was detected by Gwyer and Phillips [7]. This phase, , was shown to be formed by the peritectoid reaction + at 1158oC i.e., only about 7oC below the + eutectic [7]. Because of the incompleteness of this reaction on relatively rapid cooling and insufficient annealing, no singlephase alloy

could be obtained in this range. Gwyer and Phillips [7,31] assumed this phase to contain about 65 at. % Al; however, Hansen [28] suggested it to be somewhat richer in Al and correspond to the composition FeAl2. The phase relationships shown in Figure 1.4 are based mainly on the work of Gwyer and Phillips [7]. However instead of a liquidus maximum (1161C) at FeAl3, and a eutectic FeAl2-FeAl5 at 1159C and about 74 at. % (54 wt %) Al, Ageew and Vher [10] suggested the peritectic reaction: melt + Fe2Al5. The thermal data of [5] and the microstructure of the alloys with 72.8 at. % Al [10] and 72.7 at. % Al [7], showing peritectic rather than eutectic structures, are in favor of this generally accepted version. The intermediate phase richest in Al has been widely accepted to correspond to the composition FeAl3 [4,6,7,29]. Bradley and Taylor [30] claimed to have found strong X-ray evidence that FeAl3 = decomposed at some temperature below 600C to give a mixture of Fe 2Al5 and Fe2Al7 (77.8 at. % Al), the latter being stable between about 77.5 and 78.6 at. % (62.5 and 64 wt %) Al. The powder pattern of Fe2Al7 was reported to differ only slightly from that of FeAl 3, the difference being clearly defined as second-order effects [30]. According to Bradley and Taylor [21] no indication of thermal effect was found on cooling curves, however, these results could not be reproduced by recent careful X-ray studies [32]. There were no differences in the powder patterns of specimens (including a single crystal) containing 76.4-76.8 at. % Al, quenched from 900C or subjected to a long-time anneal at 470C. The conclusion that FeAl3 does not decompose was also drawn by [33]. On the other hand, there is some indication that the composition of the intermediate phase coexisting with the aluminium rich solid solution is lower in iron than previously assumed: [34], who analysed primary crystals extracted from alloys, found the compositions to be close to Fe2Al7. Additional work is needed to verify these and other findings [35,36] which indicate that the phase FeAl 3 is actually richer in aluminium, or to conclude that it has a wider homogeneity range. Until then, the formula FeAl 3 should be retained for convenient reference. The boundaries of Fe2Al5 ( phase) given by various workers [7, 29, 30, 37] differ somewhat ranging from 53-55.5 wt % Al on the Fe-side to 55.5-57 wt % Al on the Alside. As a compromise, 53-56 wt % (70-72.5 at. %) Al was accepted in Figure 1.4. 1.4.3 The Range 77-100 At. % Al The liquidus curve is based on the closely agreeing thermal data of [5,7,38]. The eutectic temperature was given as 646-649C [4], 648C [39,7], 652C [5], 650C [40], 655C [41], 653C [7] and 654oC [39,42] and the eutectic composition in wt % Fe as 2.0 [39] 2.5 [40] about 1.7 [41] about 2.2 [43] 1.9 [7], and 2.0 [38]. There appears to be a little doubt that these differences are mainly caused by the use of aluminium of different purities. Also, the tendency of the melt to under cool might have affected the results. The most reliable data indicate the eutectic point to be located at 1.8 0.1 wt % (0.9 0.05 at. %) iron and 654-655C. Results as to the solid solubility of iron in aluminium were chiefly reported by [41,44,45]. Those of Edgar [45], based on lattice-spacing measurements, are most reliable and complete; 0.052 wt % Fe at 655C, 0.025% at. 600C, 0.006% at. 500C, and practically zero at 400-450C. With extremely high cooling rates during solidification, supersaturated solutions containing as much as 0.17 wt. % Fe can be obtained [46]. 1.4.3.1 Crystal structures Lattice parameter of alloy in the range 0-50 at. % Al were reported by [47,29,13] in which those of Bradley and Jay [13] being most reliable. The structural changes connected with the disorder order transformation Fe3Al (= 1) and FeAl (= 2) were elucidated by [12,13]. The Fe3Al structure is of the BiF3 (DO3) type, with a lattice constant twice that of the phase, and the

FeAl structure is isotypic with the CsCl (B2) structure. The phase was suggested to be b.c.c. with 16 atoms per unit cell and phase (FeAl 2) to be rhombohedral with 18 atoms per unit cell [29,48]. The structure of the later phase was claimed to be more complicated [30]. The phase Fe2Al5 first believed to be monoclinic with 56 atoms per unit cell [28], was reported to be orthorhombic, with a=7.675, b = 6.403, c=4.203 for 72.0 5 at. % Al [49]. The phase (FeAl3) was previously believed to be orthorhombic [29,48,50,51]. A complete structure analysis, using specimens with about 76.5 at. % Al revealed the structure to be monoclinic with 100 atoms per unit cell and a = 15.489, b = 8.083, c = 12.476, = 107 o43 1 [52]. The existence of an unstable phase Fe2Al claimed to be present in a complex Fe-Ni-Cr Alloy was reported by [53]. It was stated to be isotopic with MgZn2. 1.5 Mechanism of Hot-Dip-Aluminizing Hot-dip-aluminizing (HDA) involves essentially a reaction between solid Fe at steel surface and liquid Aluminium. The steel substrate to be aluminized is immersed in a bath of molten aluminium or its alloy. The coating process occurs by wetting, dissolution, inter-diffusion, and then the formation of intermetallic. It must be appreciated that in hot dip aluminizing it is difficult to join the aluminium with steel without the formation of intermetallic layer at the face of the solid because of their limited mutual solubility. A clean surface of the substrate ensures good wetting and authenticates better aluminizing. Aluminium has good affinity with oxygen. The presence of iron oxide in the melt further becomes the problem for hot-dip-aluminizing process. The intermetallic layer is brittle in nature. This layer grows and dissolves concurrently into the molten aluminium alloy, which is directly associated with the loss of the steel substrate. The growth and the dissolution rates of the intermetallic layer determine thickness of the layer. The rates are closely related with temperature of the molten aluminium alloy and dipping time of the steel [54,55,56-58]. The thickness of the layer also varies depending on chemical composition of the molten alloy [59] and of the steel substrate. 1.6 Role of Intermetallic Hot-dip-aluminized steels have got very good resistance against oxidation and corrosion at room and elevated temperature and it depends upon the physical and mechanical properties of the alloy, chemical bond between the aluminium and steel [60]. Any pitting in the aluminium layer will be arrested at the thick alloy layer. At the alloy layer, pits grow in width rather than in depth. The aluminium layer may exhibit abrasion losses in high velocity rainfall run-of carrying bed load but the alloy layer provides enhanced resistance to mildto-moderate abrasion [2]. The alloy layer also resists erosion corrosion by water and soil, thus providing effective long term protection. As a consequence of its combined coating properties, aluminized steel achieves a superior service life over the full range of normal exposure conditions common to drainage pipe environment. Exceptions include service abrasive conditions and service corrosive conditions such as exist in seawater, acid mine-water and sanitary sewage [2]. The very slow rate of pit growth observed in the field survey of 30 years old pipes (Figure 1.6) is due to the galvanic protection mechanism of aluminized steels. The electro-chemical factors provide effective long term substrate protection throughout the entire pipe service life [2].

Figure 1.6. Coating Pit on 30-years old pipe demonstrating arrested pipe penetration [2].

The mechanical properties of the coating largely depend upon the thickness of intermetallic compound layer. Aluminium coatings that contain 5 to 11% Si minimize the thickness of the iron aluminium alloy bond and improve formability [60]. Above 480C further alloying occurs between the aluminium coating and the steel substrate. Because the rate of alloying is dependent upon time and temperature, all the coating converts into aluminium-iron-silicon alloy with sufficient time and temperature. The refractory intermetallic alloy formed is extremely heat resistant and resistant to spalling upto 680C [60]. Spalling at service temperature above 680C can be minimized by the use of heat resistant aluminized steel that contains sufficient Titanium. Compared with stainless steel, aluminized carbon steels offer greater resistance to attack by hydrogen sulphide and this resistance is about 100 times more than 18-8 stainless steel at 595C [60]. 1.7 Studies on Intermetallic Layer According to Wang Deqing, Shi Ziyuan and Zou Longjiang [61] the thickness of the pure aluminium layer on the steel substrate is reduced with the increase in temperature and time in the initial hot dipping stage, and the thickness of the aluminium layer does not increase with time at given temperature when identical temperature and complete wetting occur between liquid aluminium and the substrate surface. The thickness of the FeAl intermetallic layer on the steel base is increased with the increase in hot dipping temperature and time. The top portion of the coated steel substrate is composed of a thin layer of -Al2O3, followed by a thinner layer of FeAl3, and then a much thicker one of Fe2Al5 on the steel base side. Shigeaki Kobayashi and Takao Yakou [62] showed that the coating layers of hot dip aluminized steel consist mainly of aluminium and Fe2Al5. The thickness of the coating layer increases with increasing immersion temperature. In the diffusion-treatment process of specimens immersed in molten aluminium, an Fe2Al5 layer preferentially grows and the coating layer consists of a single phase of Fe2Al5 at temperatures lower than 1273K, while the intermetallic compounds of FeAl and Fe3Al produce at temperatures higher than 1273K. The hardness values of the FeAl and Fe3Al layers are HV600 and HV320, respectively. These values are lower than the hardness of Fe2Al5 (HV1000) produced at the normal aluminizing temperature. The fracture resistance of FeAl and Fe3Al are higher than that of Fe2Al5. The activation energies for the growth of the FeAl and Fe3Al layers are 180 and 260 kJ/mol, respectively. According to Sung-Ha Hwang et al [63] the dissolution rate of substrate decreases as the carbon concentration of the steel specimen increases. An intermetallic layer forms on the steel substrate as a result of a reaction between the molten aluminium alloy and the steel substrate. The thickness x of the intermetallic layer increases with dipping time t following the relationship: x = kt0.5,

where k is a growth rate constant. The thickness decreases as the carbon content of the steel substrate increases. The interface between the intermetallic layer and the steel substrate also becomes smoother with the increase of the carbon content. They [63] also suggested a diffusion mechanism controlling the dissolution of the steel substrate that the carbon atoms in the intermetallic layer reduce the diffusion rate of iron and aluminium through the layer. Li Yajiang, Wang Juan, Zhang Yonglan and X Holly [64] observed that the FeAl alloy layer is composed of -Fe (Al) solid solution, Fe3Al (13.87% Al), FeAl (32.57% Al), Fe2Al5 (54.71% Al) with different proportions. There is no brittle phase containing higher aluminium content such as FeAl3 (59.18% Al) and Fe2Al7 (62.93% Al). Chaur-Jeng Wang and Shih-Ming Chen [65] investigated the high-temperature oxidation behavior of low carbon steel with hot-dip aluminizing coating in the temperature range from 750 to 950C in air for various durations of time. They found the following results: (a) The thickness of aluminised layer remained almost the same for all durations of test. However, the Fe2Al5+FeAl2 dominated aluminide layer transformed to FeAl gradually with increasing time owing to the aluminium dilution. (b) The accumulation of voids at the interface between the aluminised layer and the steel substrate might produce cracks and result in the degradation of the aluminide layer. Therefore, protrusion of iron oxide nodules on the surface of coated specimen occurred after oxidation at 850C for 24 hrs, (c) Severe cracking and internal oxidation occur in the coated specimen after high-temperature oxidation. Thus, these limitations degraded the use of aluminized coatings in high-temperature oxidation environments. H.R. Shahverdi, M.R. Ghomashchi, S. Shabestari and J. Hejazi [66] examined the microstructure of solid iron and molten aluminium couple at the interface to identify the phases as Fe 2A15 and FeA13. The former grows faster and is the major phase while the latter is easily detectable at the later stages of reaction and dissolves partially within molten aluminium. This is in contradiction with thermodynamic principles, where FeA13 is expected to form before Fe2A15, which may suggest the importance of kinetics in this system. It was further shown that it is possible to miss FeA13 detection due to the following reasons: a) Small quantity of FeA13 due to faster growth rate of Fe2A15, which is directly related to its defects crystallography. b) Similarity of XRD spectra of both FeA13 and Fe2A15. c) Spalling, subsequent re-melting and dissolution of FeA13 into molten aluminium with time. d) As reaction proceeds, FeA13 patches join together to form a continuous layer over the Fe 2A15 phase and even after 3000s, its thickness does not exceed more than 10 m. 1.8 Control of Intermetallic at interface According to Sung-Ha Hwang et al [63] when steel is in contact with a molten aluminium alloy, the intermetallic layer grows and dissolves concurrently into the molten aluminium alloy, which is directly associated with the loss of the steel substrate. The growth and the dissolution rates of the intermetallic layer determine thickness of the layer. The rates are closely related with temperature of the molten aluminium alloy and dipping time of the steel [54,55,56-58]. The thickness of the layer also varies depending on chemical composition of the molten alloy [59]. A typical alloying element that is known to alter the thickness significantly is silicon. It is well known that the thickness of the intermetallic layer decreases with the increase of the silicon content in the melt [54,67,56,59]. During the HDA process, silicon is normally added into the melt to reduce the thickness of the brittle intermetallic layer as well as to increase surface hardness of the steel sheet. However, a limit of silicon concentration in the melt is reported; the layer thickness hardly decreases with addition of silicon over around 10 wt. % [54,68]. Moreover,

the growth rate of the intermetallic compound layers decreases with increasing carbon content in the steel substrate [69], and is inhibited by silicon atoms [70,71]. 1.8.1 Effect of aluminizing temperature Shigeaki Kobayashi and Takao Yakou [62] investigated the effect of temperature on the growth of intemetallic layer between steel substrate and surface aluminum coat. They hot dip aluminized steel samples at 973K, 1023K, 1073K, 1123K and 1173K for 300 s. Figures 1.7 (a-e) show micrographs of cross sections of the coating layers of steel substrates for these samples. They [62] showed that all the coating layers consist of two phases. The dark layer at the interface between the layers shown in Figure 1.7(a) was a shadow from the step in the coating produced by the mechanical polishing process. Their XRD results showed that the surface and lower layers were aluminum and Fe2Al5, respectively. These results are consistent with the literature [37,7275]. Moreover, in the case of specimens immersed at temperatures higher than 1073K, the columnar grains grew from the Fe2Al5 layer towards the surface aluminum layer. These columnar grains coarsened and increased with increasing immersion temperature. It has been suggested that the columnar grains are FeAl3 [37,72-75]. They [62] also showed that the thickness of the coating layer increased with increasing immersion temperature. With regard to the thickness of the two formed layers, the thickness of the surface aluminum layer gradually increased from 100 to 200 mm. On the other hand, the Fe2Al5 layer grows rapidly with increasing immersion temperature at temperatures ranging from 973K to 1073K and the growth was saturated at temperatures higher than 1073K. The interface between the Fe2Al5 layer and steel substrate [62] was irregular due to the tonguelike morphology of the Fe2Al5 layer. The irregularity of the thickness of the Fe 2Al5 layer increases with increasing immersion temperature. Conversely, the interface between the surface aluminum and Fe2Al5 layers was flat regardless of immersion temperature.

Figure 1.7 (a-e) Cross section micrographs of specimens immersed into molten aluminum for 300 seconds at (a) 973K, (b) 1023K, (c) 1073K, (d) 1123K and (e) 1173K [62].

1.8.2 Effect of Diffusion Treatment Shigeaki Kobayashi and Takao Yakou [62] also discussed the effect of diffusion treatment on the growth of intemetallic layer between steel substrate and surface aluminium coat. They diffusion treated five steel samples (HDA at 973K, 1023K, 1073K, 1123K and 1173K for 300 s) at 873K (0.48 TmFe, where TmFe is the homologous temperature of the melting point of Fe), 1073K (0.59 TmFe), 1273K (0.70 TmFe) and 1323K(0.73 TmFe) for 1.2 ks after immersion and then in another diffusion treatment for longer time 3.6 ks at the same temperatures. Figure 1.8 shows micrographs of the cross section of the coating when diffusion-treated for 1.2 ks after immersion. Figure 1.9 shows the micrographs in the case of a longer treatment time of 3.6 ks. The intermetallic compound layers in the surface upper layer are denoted by A, B and C. The black area in the coating layers formed at 1073-1323K are likely to be oxides formed from the specimen surface by high temperature oxidation. Figures 1.10 (a), (b) and (c) show the results of XRD measurements for layers A, B and C, respectively. Layer A exhibited an intense peak attributable to (002) Fe2Al5. The individual tongue-like grains of Fe2Al5 were single crystals and grew in a unidirectional manner perpendicular to the surface of the specimen. Layers B and C showed peaks of FeAl and Fe3Al, respectively. These intermetallic layers only grew at relatively higher temperatures than 1273K (0.70 TmFe). It was shown [62] that in the case of the diffusion-treatment at temperatures lower than the melting point of aluminum, the morphology and thickness of the coating layers hardly changed from that of the initial coating layers after immersion shown in Figure 1.7 even though the samples were diffusion-treated for 3.6 ks. In specimens diffusion-treated at temperatures higher than 1073K (0.50 T mFe), the Fe2Al5 layer (layer A) preferentially grew towards the aluminum layer. In specimens with a thin aluminum layer formed by immersion at temperatures ranging from 973 to 1023K, the aluminum layer disappeared completely, and the coating layer changed into a layer consisting of a single phase of Fe2Al5 as shown in Figure 1.8. Aluminum layers disappeared completely after 3.6 ks of heattreatment at these temperatures, even in specimens initially coated with a thick aluminum layer as shown in Figure 1.9. Although the growth of FeAl3-columnar grains was simultaneous with the growth of the Fe2Al5 layer, the coating layer developed into a single phase of Fe 2Al5 due to the preferential growth of the Fe2Al5 layer. Moreover, in specimens diffusion-treated at temperatures greater than 1273K, FeAl (layer B) and Fe3Al (layer C) layers were newly formed at the interface between the steel substrate and the Fe2Al5 layer. FeAl and Fe3Al layers grew with increasing temperature and time of diffusion treatment. These layers initially exhibited an irregular shape that reflected the tongue like structure of Fe2Al5 layer in the pre-diffusion treated specimen, before developing a flat interface with increasing heating time. As mentioned above, it was found [62] that Fe-Al intermetallic compound layers formed by hot dip coating and subsequent diffusion treatment transform from layers with a higher iron composition into layers with a lower iron composition towards the surface of the specimen. No FeAl2 layers were formed under the conditions examined in this study, although an FeAl2 phase was formed in chemical compositions ranging from 66 to 67 at. % Al [3]. In the case of diffusion-treatment in air at temperatures higher than the melting point of aluminum, high temperature oxidation occurred on the surface of the specimen. Particularly, in pre-diffusion treated specimens with a thin coating layer, the coating layer peeled away from the FeAl/Fe3Al interface (B/C interface) due to the presence of oxides at the interface. While oxides preferentially exist in the surface Fe2Al5 layer (layer A) and the FeAl/Fe3Al interface (B/C interface), the inner FeAl and Fe3Al layers have sound structures without oxidation.

Figure1.8. Cross section micrographs of specimens diffusion-treated for 1.2 ks at 873K, 1073K, 1273K and 1323K [62].

Figure 1.9. Cross section micrographs of specimens diffusion-treated for 3.6 ks at 873K, 1073K, 1273K and 1323K [62].

Figure 1.10. XRD patterns taken from intermetallic compound layers after the diffusion treatment [62].

1.8.3 Effect of the Carbon Contents of steel substrate Sung-Ha Hwang, Jin-Hwa Song and Yong-Suk Kim [63] investigated the effect of carbon contents of the steel substrate on the control of interlayer between steel substrate and surface aluminum coat. They selected three different steel compositions with C = 0.202, 0.456 and 1.103 % and then hot dip aluminized in molten Al9.08 wt.% Si 0.98 wt.% Fe alloy at 660C for 10 min under a rotating condition with two different speeds of revolution, 16 and 26 rpm. Figure 1.11 shows variation of the dissolved amount (weight loss) as a function of carbon concentration of these steel specimens. The dissolved amount decreases with the increase of the carbon concentration at both revolution speeds. Specimens tested at the higher rotation speed experienced more rapid dissolution.

Figure 1.11. Weight loss per unit area vs. carbon concentration of specimens hot-dipped in the molten AlSiFe alloy at 660C for 10 min. Specimens were rotated in the melt with two different speeds of revolution [63].

They [63] also measured the weight loss of the specimens as a function of dipping time, and the result is displayed in Figure 1.12. The dissolved amount per unit exposed area of all specimen increases linearly with time. The specimen with C = 0.202% has the lowest carbon content lost the largest amount, and showed the highest dissolution rate (Figure 1.12). The gradient of plots in Figure 1.12, which represents the dissolution rate, decreases as the carbon content increases. Calculated gradients of the plots for the specimens with C = 0.202, 0.456 and 1.103 %, in Figure 1.12 are 1.90 107, 1.17 107, and 1.04 107 g/mm2, respectively. Figures 1.11 and 1.12 demonstrate that the carbon content of steel directly influences the dissolution of the steel into the molten aluminum alloy. As the carbon content of steel increases, less amount of the steel was dissolved into the molten aluminum alloy with the decrease of the dissolution rate. 0.2 wt% C 0.45 wt% C 1.10 wt% C

Figure 1.12. Weight loss per unit area vs. dipping time for steel specimens with varying carbon contents, hotdipped in the molten AlSiFe alloy at 660C [63].

Sung-Ha Hwang, Jin-Hwa Song and Yong-Suk Kim [63] also studied the cross sections of the aluminized steel specimens which revealed intermetallic layers formed between the top aluminum alloy coat and the steel substrate. Figure 1.14 shows variation of intermetallic layer thickness of specimens with different carbon content as a function of dipping time [63]. The thickness increases with dipping time for all specimens. The intermetallic layer of the specimen with C = 0.202% grew much faster than those of the other specimens. The thickness versus time plots in Figure 1.14 look very similar to the weight loss versus time plots in Figure 1.12. Both of the intermetallic layer thickness and the dissolved amount increased with dipping time, and both decreased with the increase of carbon content of the steel substrate.

Figure 1.14. Intermetallic layer thickness vs. dipping time for steel specimens with varying carbon content, hotdipped in the molten AlSiFe alloy at 660C. Specimens were rotated in the melt with the rotation speed of 16 rpm [63].

1.8.4 Role of Silicon It is well known [59,37,78,79], that after hot dip aluminizing of steel the coating obtained is of a duplex nature. It contains a brittle layer of intermetallic compounds adjacent to the steel substrate, which is called the alloy layer. On this a layer of the melt material is superimposed, which gives good corrosion resistance. As has been discussed in the literature [59,78], thick alloy layers grow under normal operating conditions in pure and iron containing aluminum melts. These cannot withstand bending and forming operations without peeling and flaking. It was pointed out by Gittings et al. [59], that silicon as an addition to the aluminum melt reduces the thickness of the alloy layer. 1.8.5 Role of alloying elements M. V. Akdeniz and A. O. Mekhrabov [85] calculated the pairwise inter-atomic potential and ordering energies to predict the effect of various alloying additions on the activity co-efficient of Al-atoms in -Fe0.95(Al1-nXn)0.05 alloys where X =Si, Ti, Ge, Sb, Mg, Cu, Ca, Ag, Cd, Cr, Co, Zn, Mn, Ni, Pb or Bi considered upto 1 at%. The results of calculations showed that the impurity elements with regard to their effect on the activity co-efficient of Al-atoms may be classified into two groups; I-group impurity elements, X1 = Si, Ti, Ge, Sb, Mg, Cu, Ca, Ag, Cd and Cr which decrease the activity co-efficient of Al-atoms, reduce the thickness of Fe-Al intermetallic diffusion layer and II-group impurity elements XII = Co, Zn, Mn, Ni, Pb and Bi, which increase the activity co-efficient of Al-atoms tend to increase the thickness of diffusion layer at the Fe-Al interface H. Glasbrenner and E. Nold, Z. Voss [86] doped the Al-melt with one of the elements Mo, W or Nb with a nominal composition of about 1 wt% during HDA. They studied the influence of these elements on the coating formed and on the following oxidation process Hot dip aluminizing was carried out at 800C for 5 min under dry Ar atmosphere. The oxidation experiments were performed at 950C for 24 h in air. Compared to the HDA processes with pure A1, the addition of the alloying elements leads to a thinner intermetallic layer.