Studies of the morphology of the Al-Rich interfacial layer formed during the hot dip galvanizing of steel sheet

A small addition of Al in the liquid Zn bath inhibits the Fe/Zn reactions during hot dip galvanizing of steel sheets. Although it is well known that Al and Fe are tied up in an layer located at the interface between Fe and Zn, the effect of the galvanizing parameters on the formation of this Al-rich interfacial layer is not. This study has been carried out to determine the effect of the galvanizing parameters on the formation of this Al-rich layer. Five zinc baths containing 0.10, 0.12, 0.13, 0.16, and 0.18 wt pct Al were used to produce galvanized coatings of commercial ultra-low-carbon (ULC) steel substrate. Full inhibition of the Fe/Zn reactions was achieved in baths with Al content above 0.15 wt pct. The Al-rich layer is isomorphous to Fe₂Al₅ crystals and the Fe/Al ratio is close to Fe₂Al₅ with large amounts of Zn present (22 to 28 wt pct). The morphology of the Al-rich layer is strongly related to the Al content of the bath. Indeed, bath contents above 0.15 wt pct are associated with two sublayers of Fe₂Al₅ crystals, making up colonies of grains of similar crystallographic orientation and directly associated to the crystallographic orientation of the steel grains. In baths with contents below 0.15 wt pct, the Al-rich layer has only one sublayer of crystals and shows colonies of grains with similar orientation. Finally, the Fe₂Al₅ crystals have a strong crystallographic texture. X-ray diffraction (XRD) reveals that the (200) planes are parallel to the surface of the substrate.     

The effect of iron oxide as an inhibition layer on iron-zinc reactions during Hot-Dip galvanizing

A study was conducted on the effect of a uniform oxide layer on the galvanizing reaction in 0.20 wt pct Al-Zn and pure Zn baths at 450 °C. In the 0.20 wt pct Al-Zn bath, poor wettability of the oxide layer was observed. No significant liquid Zn penetration of the oxide occurred and, therefore, attack of the steel substrate to form localized Fe-Zn growth did not occur. It was found that the iron oxide acted as a physical barrier or inhibition layer in the pure Zn bath, similar to the Fe₂Al₅ inhibition layer that forms at the steel interface in Al-Zn baths. The inhibition effect of the oxide in the pure Zn bath was temporary, since cracks and other macrodefects in the oxide acted as fast diffusion paths for Zn. Localized Fe-Zn growth (outbursts) formed at the steel/coating interface, and the number of outbursts was generally inversely proportional to the oxide layer thickness at constant immersion times. Increased immersion time for a constant oxide layer thickness led to an increase in the number of outbursts. These results simulate the diffusion short circuit mechanisms for Fe₂Al₅ inhibition layer breakdown in Al-containing Zn baths.     

Effect of substrate grain size on iron-zinc reaction kinetics during hot-dip galvanizing

In the galvanizing process, it has been proposed that the grain size of the substrate steel influences the Fe-Zn alloy phase reaction kinetics and growth rate during immersion in the liquid Zn bath. Two grain sizes (nominally 15 and 85 μm) were developed in a decarburized low-carbon (0.005) steel and hot-dipped galvanized in 0.00 wt pct Al-Zn and 0.20 wt pct Al-Zn baths to study the effect of substrate grain size on Fe-Zn phase formation. Uniform attack of the substrate steel occurred in the 0.00 wt pct Al-Zn bath, since an Fe₂Al₅ inhibition layer did not form. No barrier to nucleation of the Fe-Zn phases exists in this Zn bath, and therefore, the substrate steel grain size had no significant effect on the kinetics of phase growth for the gamma, delta, and zeta phase layers. In the 0.20 wt pct Al-Zn bath, discontinuous Fe-Zn phase growth (outburst formation) occurred due to the initial formation of the Fe-Al inhibition layer. The nucleation of the Fe-Zn phases was significantly retarded in this bath for the large (85 μm) substrate grain size. Whereas outbursts were found in the 15-μm grain size substrate after 10 seconds of immersion time, it required 1200 seconds to nucleate just a few outbursts in the 85-μm substrate. These results support the mechanism that Fe-Al inhibition layer breakdown occurs along fast diffusion paths for Zn in the inhibition layer that correspond to the location of substrate steel grain boundaries where reaction with Fe can occur.     

Effect of phosphorous surface segregation on iron-zinc reaction kinetics during hot-dip galvanizing

Phosphorous was ion implanted on one surface of a large grain (10 to 20 mm) low-carbon steel sheet in order to study the effect of surface segregation on the formation of Fe-Zn phases during galvanizing. Both an Al-free and a 0.20 wt pct Al-Zn bath at 450 °C were used in this investigation. It was found that P surface segregation did not affect the kinetics of Fe-Zn phase growth for the total alloy layer or the individual Fe-Zn gamma, delta, and zeta phase alloy layers in the 0.00 wt pct Al-Zn baths. In the 0.20 wt pct Al-Zn bath, the Fe₂Al₅ inhibition layer formed with kinetics, showing linear growth on both the P-ion implanted and non-P-ion implanted surfaces. Fe-Zn phase growth only occurred after extended reaction times on both surfaces and was found to directly correspond to the location of substrate grain boundary sites. These results indicate that P surface segregation does not affect the growth of Fe-Zn phases or the Fe₂Al₅ inhibition layer. It was shown that in the 0.20 wt pct Al-Zn bath, substrate grain boundaries are the dominant steel substrate structural feature that controls the kinetics of Fe-Zn alloy phase growth.     

The effects of silicon on the reaction between solid iron and liquid 55 wt pct Al−Zn baths

The effect of various silicon levels on the reaction between iron panels and Al-Zn-Si liquid baths during hot dipping at 610°C was studied. Five different baths were used: 55Al−0.7Si−Zn, 55Al−1.7Si−Zn, 55Al−3.0Si−Zn, 55Al−5.0Si−Zn, and 55Al−6.88Si−Zn (in wt pct). The phases which formed as a result of this reaction were identified as Fe₂Al5 and FeAl3 (binary Fe−Al phases with less than 2 wt pct Si and Zn in solution),T1, T2, T4, T8, andT _5H (ternary Fe−Al−Si phases), andT _5C (a quaternary Fe−Al−Si−Zn phase). Compositional variations through the reaction zone were determined. The phase sequence in the reaction zone of the panel dipped for 3600 seconds in the 1.7 wt pct Si bath was iron panel/(Fe₂Al₅+T ₁)/FeAl₃/(T _5H+T _5C)/overlay. In the panel dipped for 1800 seconds in the 3.0 wt pct Si bath the reaction zone consisted of iron panel/Fe₂Al₅/(Fe₂Al₅+T ₁)/T ₁/FeAl₃/(FeAl₃+T ₂)/T _5H/overlay. In the panel dipped for 3600 seconds in the 6.88 wt pct Si bath the phase sequence was iron panel/Fe₂Al₅/(Fe₂Al₅+T1)/(T1+FeAl3)/(T1+T2)/T2/T8/T4/overlay. The growth kinetics of the reaction zone were also studied. A minimum growth rate for the reaction zone which formed from a reaction between the iron panel and molten Al−Zn−Si bath was found in the 3.0 wt pct Si bath. The growth kinetics of the reaction layers were found to be diffusion controlled in the 0.7, 1.7, and 6.88 wt pct Si baths, and interface controlled in the 3.0 and 5.0 wt pct Si baths. The presence of the interface between theT2/T5H, Fe2Al5/T ₁, orT ₁/FeAl₃ phases is believed responsible for the interface controlled growth kinetics exhibited in the 3.0 and 5.0 wt pct Si baths.     

Liquid metal corrosion of 316L,Fe<Subscript>3</Subscript>Al,and FeCrSi in molten Zn-Al baths

Corrosion tests of 316L and two intermetallic compounds Fe₃Al and FeCrSi in industrial Galvanizing (Zn-0.18Al), GALFAN (Zn-5Al), GALVALUME (Zn-55Al), and Aluminizing (Al-8Si) baths and lab-scale static baths were conducted. In on-line tests in industrial hot-dip baths, 316L steel shows better corrosion resistance than Fe₃Al in Galvanizing, GALFAN, and GALVALUME baths. The corrosion resistance of 316L and Fe₃Al is similar in Aluminizing bath. In static tests, FeCrSi shows the best corrosion resistance in pure Zn, Zn-55Al, and Al-8Si baths. The corrosion resistance of 316L is better than that of Fe₃Al. In Zn-5Al bath, 316L shows no thickness loss after the test. For the same bath composition, the corrosion rates of the alloys in industrial baths are higher than those in static baths. Bath temperature and chemical composition play important roles in corrosion and intermetallic layer formation. Increasing bath temperature accelerates the corrosion process and changes the nature of intermetallic layers. A small amount of aluminum reduces the corrosion process by reducing the activity of Zn and forming inhibition layer. However, after aluminum content reaches the critical point, the dominant corrosion process changes from Zn-Fe reaction to Al-Fe reaction, and, consequently, the corrosion process accelerates by increasing aluminum content in the bath.     

Influence of Gas Atmosphere Dew Point on the Selective Oxidation and the Reactive Wetting During Hot Dip Galvanizing of CMnSi TRIP Steel

The selective oxidation and reactive wetting of intercritically annealed Si-bearing CMnSi transformation-induced plasticity steels were investigated by high-resolution transmission electron microscopy. In a N₂ + 10 pct H₂ gas atmosphere with a dew point (DP) ranging from 213 K to 278 K (?60 °C to 5 °C), a continuous layer of selective oxides was formed on the surface. Annealing in a higher DP gas atmosphere resulted in a thinner layer of external oxidation and a greater depth of internal oxidation. The hot dipping was carried out in a Zn bath containing 0.22 mass pct Al, and the bath temperature was 733 K (460 °C). Coarse and discontinuous Fe₂Al_5?x Zn _x grains and Fe-Zn intermetallics (?? and ??) were observed at the steel/coating interface after the hot dip galvanizing (HDG) of panels were annealed in a low DP atmosphere 213 K (?60 °C). The Fe-Zn intermetallics were formed both in areas where the Fe₂Al_5?x Zn _x inhibition layer had not been formed and on top of non-stoichiometric Fe-Al-Zn crystals. Poor wetting was observed on panels annealed in a low DP atmosphere because of the formation of thick film-type oxides on the surface. After annealing in higher DP gas atmospheres, i.e., 263 K and 278 K (?10 °C and 5 °C), a continuous and fine-grained Fe₂Al_5?x Zn _x layer was formed. No Fe-Zn intermetallics were formed. The small grain size of the inhibition layer was attributed to the nucleation of the Fe₂Al_5?x Zn _x grains on small ferrite sub-surface grains and the presence of granular surface oxides. A high DP atmosphere can therefore significantly contribute to the decrease of Zn-coating defects on CMnSi TRIP steels processed in HDG lines.     

Influence of Gas Atmosphere Dew Point on the Galvannealing of CMnSi TRIP Steel

The Fe-Zn reaction occurring during the galvannealing of a Si-bearing transformation-induced plasticity (TRIP) steel was investigated by field-emission electron probe microanalysis and field-emission transmission electron microscopy. The galvannealing was simulated after hot dipping in a Zn bath containing 0.13 mass pct Al at 733 K (460 °C). The galvannealing temperature was in the range of 813 K to 843 K (540 °C to 570 °C). The kinetics and mechanism of the galvannealing reaction were strongly influenced by the gas atmosphere dew point (DP). After the galvannealing of a panel annealed in a N₂+10 pct H₂ gas atmosphere with low DPs [213 K and 243 K (?60 °C and ?30 °C)], the coating layer consisted of δ (FeZn₁₀) and η (Zn) phase crystals. The Mn-Si compound oxides formed during intercritical annealing were present mostly at the steel/coating interface after the galvannealing. Galvannealing of a panel annealed in higher DP [263 K and 273 K, and 278 K (?10 °C, 0 °C, and +5 °C)] gas atmospheres resulted in a coating layer consisting of δ and Г (Fe₃Zn₁₀) phase crystals, and a thin layer of Г ₁ (Fe₁₁Zn₄₀) phase crystals at the steel/coating interface. The Mn-Si oxides were distributed homogeneously throughout the galvannealed (GA) coating layer. When the surface oxide layer thickness on panels annealed in a high DP gas atmosphere was reduced, the Fe content at the GA coating surface increased. Annealing in a higher DP gas atmosphere improved the coating quality of the GA panels because a thinner layer of oxides was formed. A high DP atmosphere can therefore significantly contribute to the suppression of Zn-alloy coating defects on CMnSi TRIP steel processed in hot dip galvanizing lines.     

On the nature of the Fe-bearing particles influencing hard anodizing behavior of AA 7075 extrusion products

The deleterious effects of Fe-bearing constituent particles on the fracture toughness of wrought Al alloys have been known. Recent studies have shown that the presence of Fe-bearing constituent particles is also detrimental to the nature and growth of the hard anodic oxide coating formed on such materials. The present study, using a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron probe microanalysis (EPMA), was made to examine the influence of the nature of the Fe-bearing particles on the hard anodizing behavior of AA 7075 extrusion products containing varying amounts of Si, Mn, and Fe impurities. It was found that, in the alloy containing 0.25 wt pct Si, 0.27 wt pct Mn, and 0.25 wt pct Fe, the Fe-bearing constituent particles are based on the Al₁₂(FeMn)₃Si phase (bcc with a=1.260 nm). These particles survive the hard anodizing treatment, add resistance to the electrical path, causing a rapid rise in the bath voltage with time, and cause a nonuniform growth of the anodic oxide film. In the materials containing 0.05 wt pct Si, 0.04 wt pct Mn, and 0.18 wt pct Fe, on the other hand, the formation of the Al₁₂(FeMn)₃Si-based phase is suppressed, and two different Fe-bearing phases, based on Al-Fe-Cu-Mn (simple cubic with a=1.265 nm) and Al₇Cu₂Fe, respectively, form. Neither the Al-Fe-Cu-Mn-based phase nor the Al₇Cu₂Fe-based phase survive the hard anodizing treatment, and this results in a steady rise in the bath voltage with time and a relatively uniform growth of the anodic oxide film. Consideration of the size of the Fe-bearing particles reveals that the smaller the particle, the more uniform the growth of the anodic oxide film.     

Microstructural Evolution of the 55 Wt Pct Al-Zn Coating During Press Hardening

Press hardening is increasingly being used to produce ultra-high strength steel parts for passenger cars. Al-Si, Zn, and Zn-alloy coatings have been used to provide corrosion protection to press hardening steel grades. The use of coatings has drawbacks such as coating delamination or liquid metal-induced embrittlement. In the present work, the microstructural evolution of Al-Zn coating during press hardening was studied. The 55 wt pct Al-Zn coating can in principle provide both Al barrier protection and Zn cathodic protection to press hardened steel. During the heat treatment associated with the press hardening, the 55 wt pct Al-Zn alloy coating is converted to an intermetallic surface layer of Fe₂Al₅ and a FeAl intermetallic diffusion layer. The Zn is separated from both intermetallic compounds and accumulates at grain boundaries and at the surface. This Zn separation process is beneficial in terms of providing cathodic protection to Al-Zn coated press hardening steel.     

The reaction between solid iron and liquid Al-Zn baths

The reaction which occurred between iron panels and Al-Zn baths during hot dipping was investigated. Three baths were studied: 45Al-55Zn, 55Al-45Zn, and 75Al-25Zn (in wt pct) in the temperature range of 570 to 655 °C. The reaction between the iron panel and the Al-Zn bath was very severe and in all cases the iron panel was totally consumed by the bath in less than two minutes. The rapid attack of the iron panels by the Al-Zn baths was attributed to two separate causes depending on growth conditions. First, in some panels the intermediate layer which formed between the iron panel and the molten bath was nonadherent. This resulted in the direct contact of the molten bath with the iron panel at a nonequilibrium interface, which presented a large driving force and little inhibition for the reaction. Second, in panels containing an adherent alloy layer, the layer had channels of liquid Zn which extended from the molten bath to the iron panel. These channels allowed rapid transport of Zn and Al to the iron panel which resulted in a very high reaction rate. The controlling step in the reaction between the iron panel and molten Al-Zn bath was the diffusion rate of Al in the molten bath to the surface of the iron panel. The diffusion coefficient of Al in the molten bath was found to be in the range of 1 × 10^-5 to 5 × 10^-5 cm²/s. Microstructural, electron microprobe, and X-ray diffraction data are presented to support the above-mentioned mechanisms and conclusions.     

Microstructure and Thickness of 55 pct Al-Zn-1.6 pct Si-0.2 pct RE Hot-Dip Coatings: Experiment, Thermodynamic, and First-Principles Study

The microstructure and thickness of 55 pct A1-Zn-1.6 pct Si-0.2 pct RE coatings during continuous hot-dip on Q235 steel were investigated in this work. The experimental results revealed that the intermetallic layer was composed of the Fe₂Al₅, FeAl₃, and α-FeAlSi phases. The results of thermodynamic calculations with Pandat software package (CompuTherm, LLC, Madison, WI) indicated that FeAl₃ and α(β)-FeAlSi phase precipitated during the period of temperature cooling, which was consistent with experimental result. Then, the thickness of intermetallic layer was characterized. It was shown that the thickness of intermetallic layer decreased after 0.2 wt pct RE was added. Finally, a first-principles calculation was performed to interpret the effect mechanism of RE on the thickness of intermetallic layer. The results indicated that La substitution in Fe₂Al₅ and FeAl₃ phases could grab electronic charges from Al atoms and weaken the formation of Fe-Al compounds.     

Structural evolution in mechanically alloyed Al-Fe powders

The structural evolution in mechanically alloyed binary aluminum-iron powder mixtures containing 1, 4, 7.3, 10.7, and 25 at. pct Fe was investigated using X-ray diffraction (XRD) and electron microscopic techniques. The constitution (number and identity of phases present), microstructure (crystal size, particle size), and transformation behavior of the powders on annealing were studied. The solid solubility of Fe in Al has been extended up to at least 4.5 at. pct, which is close to that observed using rapid solidification (RS) (4.4 at. pct), compared with the equilibrium value of 0.025 at. pct Fe at room temperature. Nanometer-sized grains were observed in as-milled crystalline powders in all compositions. Increasing the ball-to-powder weight ratio (BPR) resulted in a faster rate of decrease of crystal size. A fully amorphous phase was obtained in the Al-25 at. pct Fe composition, and a mixed amorphous phase plus solid solution of Fe in Al was developed in the Al-10.7 at. pct Fe alloy, agreeing well with the predictions made using the semiempirical Miedema model. Heat treatment of the mechanically alloyed powders containing the supersaturated solid solution or the amorphous phase resulted in the formation of the Al₃Fe intermetallic in all but the Al-25 at. pct Fe powders. In the Al-25 at. pct Fe powder, formation of nanocrystalline Al₅Fe₂ was observed directly by milling. Electron microscope studies of the shock-consolidated mechanically alloyed Al-10.7 and 25 at. pct Fe powders indicated that nanometer-sized grains were retained after compaction.     

Structural stability of the rod-like iron-iron sulfide eutectic at elevated temperatures

A study has been made of the thermal stability of microstructures within unidirectionally solidified ingots of the rod-like Fe?Fe_1-xS eutectic. The ingots were heat treated at temperatures of up to 98.7 pct of the eutectic’s melting point for times of up to 500 hr. At the higher temperatures the iron rods broke-up and spheroidized; these processes were accompanied by diffusion and precipitation of iron at surfaces and grain boundaries of specimens. The greater termalinstability of the Fe?Fe_1-xS eutectic compared with that of the Al?CuAl₂ and Al?Al₃Ni eutectics was attributed to the higher interfacial energy of the former system, the absence of preferred crystallographic orientations and the higher temperatures of heat treatment.     

Orientation domains and texture in hot-dipped galvanized coatings

The crystallographic orientation of galvanized coatings (Zn-0.2Al-0.15Sb in wt pct) has been characterized by Electron-Backscattered Diffraction (EBSD) and optical microscopy. While 80 pct of the nucleation spots in the coating give rise to single-crystal Zn grains, it has been found that about 20 pct of them give rise to two or more orientation domains, each having a specific crystallographic orientation. For such “polycrystalline Zn grains,” the orientations of the domains are crystallographically related: they have a dense crystallographic direction (〈1010〉, 〈1120〉, or 〈0001〉) in common. Moreover, the crystallographic relationships are similar to those observed in snowflakes and can be partially explained by the concept of a coincidence-site lattice (CSL). The EBSD measurements were also used in order to measure quantitatively the crystallographic texture. In particular, it has been evidenced that the (0001) texture of galvanized coatings is the result of two contributions: (1) the nuclei are preferentially oriented with the basal plane parallel to the coating plane (33 pct of the grains have an angle between the basal plane and the coating plane smaller than 22.5 deg), and (2) the grains having the basal plane parallel to the coating plane grow faster (these grains represent 43 pct of the coating surface). This reinforcement of the texture during growth is in agreement with that predicted by growth models, which take into account the effect of the interfaces.     

Reaction mechanisms for the coatings formed during the hot dipping of iron in 0 to 10 Pct Al-Zn baths at 450° to 700°C

The reaction mechanisms and the structures of the phases formed during the hot dipping of iron in 0 to 10 pct Al-Zn alloy baths at temperatures of 450° to 700°C were studied by X-ray diffraction and electron microprobe analysis techniques. A new mechanism for the inhibition reaction between iron and zinc is proposed. At bath temperatures below 600°C, a thin layer of an Fe-Al-Zn ternary compound forms on the iron surface and inhibits the growth of Fe-Zn phases. Breakdown of inhibition occurs during the dipping process when the ternary compound becomes rich in aluminum and transforms to a more stable structure which is isomorphous with Fe₂Al₅. While this breakdown is occurring, the zinc atoms react with iron and form the conventional Fe-Zn phases. In 1 to 10 pct Al-Zn baths at temperatures≥600°C a very violent, highly exothermic reaction occurs during hot dipping. This type of process is due to the electronic bond rearrangements which occur during the formation of the intermetallic Fe₂(AlZn)₅. This intermetallic forms from the reaction of aluminum-bearing FeZn₇ with the Zn-Al alloy bath.     

Intermetallic phases formed during hot dipping of

The formation and growth of intermetallic phases during hot dipping of low carbon steel in a Galfan bath (5 wt pct Al-Zn plus 0.05 pct mischmetal) at 450 °C have been studied by using scanning electron microscopy, X-ray diffraction, and energy dispersive spectroscopy (EDS). The first intermetallic phase to appear was in the form of local outbursts at the substrate/melt interface; intermetallic phases subsequently developed a breakaway morphology. Both the inter- metallic outbursts and the breakaway were found to be mixtures of Fe₂Al₅-Zn_x and FeAl₃-Zn_x, the latter being in each case further away from the intermetallic/substrate interface. The initial outbursts were determined to be mainly Fe₂Al₅-Zn_x; this phase grew into the substrate with a (001) preferred growth direction. The breakaway was mainly FeAl₃-Zn_x with Fe₂Al₅-Zn_x found only close to the interface. Both intermetallic growth morphologies can be characterized by a reaction path of Fe (substrate)/Fe₂Al₅-Zn_x/FeAl₃-Zn_x/galfan (melt).     

On the nature of the Fe-bearing particles influencing hard anodizing behavior of AA 7075 extrusion products

The deleterious effects of Fe-bearing constituent particles on the fracture toughness of wrought A1 alloys have been known. Recent studies have shown that the presence of Fe-bearing, constituent particles is also determental to the nature and growth of the hard anodic oxide coating formed on such materials. The present study, using a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron probe microanalysis (EPMA), was made to examine the influence of the nature of the Fe-bearing particles on the hard anodizing behavior of AA 7075 extrusion products containing varying amounts of Si, Mn, and Fe impurities. It was found that, in the alloy containing 0.25 wt pct Si, 0.27 wt pct Mn, and 0.25 wt pct Fe, the Fe-bearing constituent particles are based on the Al₁₂(FeMn)₃Si phase (bcc with α=1.260 nm). These particles survive the hard anodizing treatment, add resistance to the electrical path, causing a rapid rise in the bath voltage with time, and cause a nonuniform growth of the anodic oxide film. In the materials containing 0.05 wt pct Si, 0.04 wt pct Mn, and 0.18 wt pct Fe, on the other hand, the formation of the Al₁₂(FeMn)₃Si-based phase is suppressed, and two different Fe-bearing phases, based on Al−Fe−Cu−Mn-based (simple cubic with a=1.265 nm) and Al₇Cu₂Fe, respectively form. Neither the Al−Fe−Cu−Mn-based phase nor the Al₇Cu₂Fe-based phase survive the hard anodizing treatment, and this results in a steady rise in the bath voltage with time and a relatively uniform growth of the anodic oxide film. Consideration of the size of the Fe-bearing, particles reveals that the smaller the particle, the more uniform the growth of the anodic oxide film.     

Experimental study of phase equilibria in the Al-Fe-Zn-O system in air

The phase equilibria in the Al-Fe-Zn-O system in the range 1250 °C to 1695 °C in air have been experimentally studied using equilibration and quenching techniques followed by electron probe X-ray microanalysis. The phase diagram of the binary Al₂O₃-ZnO system and isothermal sections of the Al₂O₃-“Fe₂O₃”-ZnO system at 1250 °C, 1400 °C, and 1550 °C have been constructed and reported for the first time. The extents of solid solutions in the corundum (Al,Fe)₂O₃, hematite (Fe,Al)₂O₃, Al₂O₃*Fe₂O₃ phase (Al,Fe)₂O₃, spinel (Al,Fe,Zn)O₄, and zincite (Al,Zn,Fe)O primary phase fields have been measured. Corundum, hematite, and Al₂O₃*Fe₂O₃ phases dissolve less than 1 mol pct zinc oxide. The limiting compositions of Al₂O₃*Fe₂O₃ phase measured in this study at 1400 °C are slightly nonstoichiometric, containing more Al₂O₃ then previously reported. Spinel forms an extensive solid solution in the Al₂O₃-“Fe₂O₃”-ZnO system in air with increasing temperature. Zincite was found to dissolve up to 7 mole pct of aluminum in the presence of iron at 1550 °C in air. A meta-stable Al₂O₃-rich phase of the approximate composition Al₈FeZnO_14+x was observed at all of the conditions investigated. Aluminum dissolved in the zincite in the presence of iron appears to suppress the transformation from a round to platelike morphology.