Effect of initial deposition behavior on properties of electroless Ni–P coating on ZK60 and ME20 magnesium alloys

The composition of magnesium alloys is greatly associated with initial deposition behavior of electroless Ni–P coatings. Thus, the initial deposition behavior of electroless Ni–P coatings on ZK60 and ME20 alloys was investigated. The results indicated that differences in the alloy compositions significantly influenced the initial deposition process and the adhesive strength, corrosion resistance, and crystal structure. The initial deposition of coatings on ZK60 and ME20 alloys preferentially occurred on the precipitates. The precipitates in ZK60 alloy had higher chemical activity after HF activation and controlled the initial deposition rate of the coating. The initial deposition rate of the coating on ME20 alloy mainly depended on the density of the MgF₂ film formed by HF activation rather than on the precipitates. Owing to differences in the initial deposition process, the coating on ZK60 alloy had higher adhesive strength and better corrosion resistance than that on ME20 alloy. The coatings on ZK60 and ME20 alloys mainly had crystalline structures, and the coating on ME20 alloy had also a slight microcrystalline structure.     

Effect of nano Al (Scx−1Zrx) precipitates on the mechanical and corrosion behavior of Al‐2.5 Mg alloys

Microanalytical, mechanical, and corrosion studies were undertaken to investigate the effect of nano‐precipitates of Al(Sc_x−1Zr_x) on the mechanical and corrosion characteristics of Al 2.5 alloy containing 0, 0.15, 0.3, 0.6, and 0.9 wt% of Sc with 0.15 wt% Zr. Addition of 0.3% Sc significantly increased the yield strength due to small precipitates sizes (5–19 nm) and the high coherency of the nano‐particles. Largest contributor to the strength was grain boundary strengthening caused by pinning of grain boundary precipitates. The alloys showed a good resistance to corrosion in 3.5 wt% neutral chloride solution. The alloy offered a high passivation tendency because of homogeneous coherent nano Al(Sc_x−1Zr_x) precipitates. The nano precipitates interfaces and homogeneously distributed Al₃Sc precipitates offer a high degree of corrosion resistance to Al 2.5 Mg Sc alloys compared to conventional aluminum alloys, such as Al 6061 and Al6013.     

Simulation study on function mechanism of some precipitates in localized corrosion of Al alloys

The function mechanism of different types of aging precipitates in localized corrosion of Al alloys was studied. The function mechanism of the precipitates of θ (Al₂Cu) and η (MgZn₂) is validated. The precipitate of θ containing noble element Cu is cathodic to the alloy base, resulting in the anodic dissolution and corrosion of the alloy base at its adjacent periphery. The precipitate of η containing active element Mg is anodic to the alloy base, anodic dissolution and corrosion occur on its surface. Meanwhile, a localized corrosion mechanism conversion associated with the precipitate of T1 (Al₂CuLi) is advanced, which contains noble element Cu and active element Li simultaneously. The precipitate of T1 is anodic to the alloy base and corrosion occurs on its surface at the beginning. However, during its corrosion process, the preferential dissolution of Li and the enrichment of noble element Cu make its potential move to a positive direction. As a result, the corroded T1 precipitate becomes cathodic to the alloy base at a later stage, leading to the anodic dissolution and corrosion of the alloy base at its adjacent periphery.     

Localized corrosion mechanism associated with precipitates containing Mg in Al alloys

To clarify the localized corrosion mechanism associated with precipitates containing Mg in Al alloys, the simulated bulk precipitates of S and β were synthesized through melting and casting. Their electrochemical behaviors and coupling behaviors with α（Al） in NaCl solution were measured. Meanwhile, simulated Al alloys containing S and β particles were prepared and their corrosion morphologies were observed. It＇s found that there exist two kinds of corrosion mechanisms associated with precipitates containing Mg. The precipitate of β is anodic to the alloy base, resulting in its anodic dissolution and corrosion during the whole corrosion process. While, there exists a corrosion conversion mechanism associated with the S precipitate, which contains active element Mg and noble element Cu simultaneously. At an initial stage, S is anodic to the alloy matrix at its periphery and the corrosion occurs on its surface. However, during its corrosion process, Mg is preferentially dissolved and noble Cu is enriched in the remnants. This makes S become cathodic to a（Al） and leads to anodic dissolution and corrosion on the alloy base at its periphery at a later stage.     

Morphological and microchemical phenomena in the high-temperature oxidation of binary Al-Li alloys

The high-temperature oxidation behavior of binary Al-Li alloys has been characterized by scanning electron microscopy and secondary ion mass spectrometry in order to understand the mechanism of rapid oxidation in these alloys and to correlate the oxide morphology to its microchemistry. The oxide scale developed on polished specimens during short exposures in air at 530°C shows characteristic nodules that usually nucleate at grain boundaries. Examination of the alloy surface after removal of the oxide layer shows that the initial growth of the oxide nodules occurs laterally in addition to thickening normal to the oxide/alloy interface. Microchemical analysis of the oxide film with a scanning ion microprobe reveals a thick Li-oxide layer at the oxide/gas interface indicating preferential oxidation of Li at the free surface; the rest of the oxide film is composed of both Al- and Li-rich oxides, probably Li₂O and LiAlO₂ The presence of trace impurities (K, Na, F, and Cl) in the oxide scale was also detected. A microstructural model for the development of the oxide film in the Al-Li system is presented on the basis of both morphological and microanalytical data obtained in this study; this new model is compared with existing models.     

The effect of phosphorus addition on the corrosion behavior of ARC-MELTED Ni10TaP alloys in 12 M HCl

The corrosion resistance of arc-melted Ni10TaP alloys containing 0, 10 and 20 at% phosphorus in 12 M HCl solution at 30 °C was investigated. The alloys containing 0 and 10 at% phosphorus suffer severe corrosion. The addition of 20 at% phosphorus to crystalline Ni10Ta alloy results in a three-orders-of-magnitude decrease in the corrosion rate. The open circuit potentials of the Ni10Ta alloys containing 0 and 10 at% phosphorus stay almost constant in the active region of nickel, while the open circuit potential of the Ni10Ta20P alloy increases almost linearly in the initial 2 h. The Ni10Ta alloy consists of intermetallic Ni₈Ta and immersion in 12 M HCl results in faceting dissolution. Ni10Ta10P alloy is composed of major Ni₈Ta and Ni₃P phases and minor Ni₂Ta and Ni₂P phases. Immersion of Ni10Ta10P alloy leads to preferential dissolution of the Ni₈Ta phase and to continuous thickening of the corrosion product film consisting mostly of tantalum as cations. Ni 10Ta20P alloy consists of Ni₂Ta, Ni₃P, Ni₂P and NiP phases. Immersion of Ni10Ta20P alloy gives rise to initial increase in elemental phosphorus on the surface as a result of selective dissolution of nickel and selective oxidation of tantalum. The formation of elemental phosphorus with a high cathodic activity is responsible for the initial ennoblement of the open circuit potential and for the formation of the passive film in which tantalum is highly concentrated. The higher corrosion resistance of Ni10Ta20P alloy than Ni10Ta10P alloy is attributable to the formation of the Ni₂Ta phase with a higher tantalum content than the Ni₈Ta phase which is the readily corroded major intermetallic phase in the Ni10Ta10P alloy.     

Corrosion of iron–aluminium alloys in gaseous atmosphere containing hydrogen chloride and hydrogen sulphide at 600 and 700°C

Abstract

The corrosion of two binary iron–aluminium alloys was compared in gaseous CO₂–H₂–HCl–H₂S and CO₂–H₂ mixtures at 600 and 700°C. In each environment, the Fe–14Al alloy resisted corrosion due to the formation of a protective alumina scale. The Fe–4Al alloy corroded more rapidly in the CO₂–H₂–HCl–H₂S atmosphere than in the CO₂–H₂ atmosphere at both temperatures. The corrosion products comprised thick outer layers of iron oxide, porous inner layers of mixed iron–aluminium oxide and internal precipitates of aluminium oxide. Sulphur was detected near the scale/alloy interface and the increase in corrosion rate was attributed to the presence of chlorine and sulphur.     

Formation of corrosion pockets in FeNiCrAl at high temperatures investigated by 3D FIB-SEM tomography

A recently published study of high temperature nitridation of iron chromium aluminum alloys (FeCrAl) at 900°C in N₂–H₂ has redundantly shown the formation of locally confined corrosion pockets reaching several microns into the alloy. These nitrided pockets form underneath chromia islands laterally surrounded by the otherwise protective alumina scale. Chromia renders a nitrogen-permeable defect under the given conditions and the presence of aluminum in the alloy. In light of these findings on FeCrAl, a focused ion beam–scanning electron microscope tomography study has been undertaken on an equally nitrided FeNiCrAl sample to characterize its nitridation corrosion features chemically and morphologically. The alloy is strengthened by a high number of chromium carbide precipitates, which are also preferential chromia formation sites. Besides the confirmation of the complete encapsulation of the corrosion pocket from the alloy by a closed and dense aluminum nitride rim, very large voids have been found in the said pockets. Furthermore, metallic particles comprising nickel and iron are deposited on top of the outer oxide scale above such void regions.     

Effect of Y Distribution on the Oxidation Kinetics of NiCoCrAlY Bond Coat Alloys

The relation between the Y distribution in the alloy and the growth kinetics of the developing oxide scale was studied for the thermal oxidation of two Ni–20Co–19Cr–24Al–0.2Y (at.%) alloys at 1,373 K: (i) a coarse-grain cast alloy with large Ni₅Y intermetallic precipitates, and (ii) a fine-grain freestanding coating with small Ni₅Y precipitates. Using a combination of experiments and model calculations, it is shown that the average growth kinetics of a NiCoCrAlY alloy are dependent on the size and distribution of Y-rich oxide inclusions (pegs) in the α-Al₂O₃ oxide layer. Alumina scales containing a high density of small Y-oxide inclusions grow faster than α-Al₂O₃ scales containing only a few, large Y-oxide inclusions. Upon oxidation of the freestanding coating, the Y-oxide inclusions in the scale attain their maximum size after the Y in the coating is completely consumed. After this point, a decrease in the average oxidation kinetics occurs.     

Tetragonal phase stability in ZrO2 film formed on zirconium alloys and its effects on corrosion resistance

A thermodynamic model is developed to understand the origin of variation in the microstructure of ZrO₂ film formed on zirconium alloys and its effects on corrosion resistance. The correlation among the tetragonal phase fraction, the stress (macroscopic and internal one), the ZrO₂ grain size and the microstructural change of oxide film is formulized, and then analyzed. The results show that many complicated factors simultaneously govern the microstructure of oxide film. The tetragonal phase content near the oxide/metal interface, the macroscopic compressive stress near the interface, the decline gradient of macroscopic compressive stress and the internal stress induced by the transformation from the tetragonal to the monoclinic phase have very important influences on the transition from columnar grains to equiaxed grains, the crack formation and the degradation of oxidation resistance. The presence of intermetallic precipitates in oxide film may effectively relax the internal stress caused by transformation strain, stabilize the columnar-grain structure and reduce the probability of crack formation. How to reduce the transformation stress in the oxide film is a key to improve the corrosion resistance of zirconium alloys.     

An XPS Study of Native Oxide and Isothermal Oxidation Kinetics at 300 °C of AZ31 Twin Roll Cast Magnesium Alloy

Magnesium alloys are very important for lightweight applications. Industrially, these alloys cannot be used without some necessary processing to improve their corrosion properties. The most widely used methods include coating, surface treatments and cladding. In these processes, the magnesium oxide scale plays an important role in the bonding mechanism between the substrate and the coating or the cladding materials. The aim of this study is to understand the spontaneous oxide formation and the initial oxidation kinetics of the TRC AZ31 magnesium alloy. The results are important for the understanding of the subsequent surface treatment processes of that alloy. Therefore, the study comprises: first, the analysis of the native oxide which forms spontaneously after Twin Roll Casting of an AZ31 magnesium sheet, and second, the investigation of the oxidation behavior of the AZ31 magnesium alloy heated in air at 300 °C with different exposure times ranging from 1 to 180 min. The results showed that the thickness of the native oxide is 5 nm and the oxide surface mainly comprises of magnesium, oxygen, and carbon compounds. The oxide film contains magnesium oxide in the form of MgO as the main oxide compound with a very thin layer of MgCO₃ and Mg(OH)₂. The X-ray photoelectron spectroscopy results revealed two stages of oxidation kinetics during exposure to 300 °C. Rapid growth represents the first stage, which lasts for about 30 min. After that period, the oxide growth slowed, indicating a steady state character, where the oxide film growth approaches a limit value. This slow growth is due to the lack of diffusion of oxygen into a dense oxide layer possessing a low concentration of defects. The oxidation kinetics follows an inverse logarithmic law.     

Improvements in oxidation resistance by dispersed oxide addition: Al2O3-forming alloys

The improvement in oxidation resistance produced by small additions of active elements to Al ₂O₃-forming CoCrAl alloys is primarily dependent on the formation of oxide pegs which grow into the alloy around the internal oxide particles of the active element; void formation at the alloy-scale interface is also suppressed. The distribution of these pegs is critical and this paper demonstrates that an internal oxidation pretreatment can be used to convert the active element to its oxide in a controlled manner, thereby optimizing the peg distribution. Al₂O₃-forming CoCrAl containing 1% Hf or Ce is internally oxidized in a sealed quartz capsule containing a 50/50 powder mixture of CoAl-Al₂O₃; it was not possible to oxidize internally Y-containing alloys. The isothermal and cyclic oxidation resistance of these alloys is superior to that of alloys not given a prior treatment. Detailed metallographic examination indicates that the prior internal oxidation treatment produces a finer, more uniform distribution of oxide pegs penetrating into the alloy which is more efficient in combatting scale spallation. Furthermore, the lower residual hafnium content in the alloy minimizes large HfO₂ precipitates and the formation of gross Al₂O₃ intrusions, which can initiate scale failure. Thus, by internally oxidizing the alloy first, the advantages of a high alloy Hf content (1%) in producing sufficient oxide pegs, but of the right size, coupled with minimal thickening of the surface scale, can be achieved.Formerly: Department of Metallurgy and Materials Science, University of Liverpool, Liverpool, England.     

Effect of equal-channel angular pressing on pitting corrosion resistance of anodized aluminum-copper alloy

The effect of equal-channel angular pressing(ECAP) on the pitting corrosion resistance of anodized Al-Cu alloy was investigated by electrochemical techniques in a solution containing 0.2 mol/L AlCl₃ and also by surface analysis. Anodizing was conducted for 20 min at 200 and 400 A/m² in a solution containing 1.53 mol/L H₂SO₄ and 0.018 5 mol/L Al₂(SO₄)₃·16H₂O at 20 °C. Anodized Al-Cu alloy was immediately dipped in boiling water for 20 min to seal the micro pores present in anodic oxide films. The time required before initiating pitting corrosion of anodized Al-Cu alloy is longer with ECAP than without, indicating that ECAP process improves the pitting corrosion resistance of anodized Al-Cu alloy. Second phase precipitates such as Si, Al-Cu-Mg and Al-Cu-Si-Fe-Mn intermetallic compounds are present in Al-Cu alloy and the size of these precipitates is greatly decreased by application of ECAP. Al-Cu-Mg intermetallic compounds are dissolved during anodization, whereas the precipitates composed of Si and Al-Cu-Si-Fe-Mn remain in anodic oxide films due to their more noble corrosion potential than Al. FE-SEM and EPMA observation reveal that the pitting corrosion of anodized Al-Cu alloy occurs preferentially around Al-Cu-Si-Fe-Mn intermetallic compounds, since the anodic oxide films are absent at the boundary between the normal oxide films and these impurity precipitates. The improvement of pitting corrosion resistance of anodized Al-Cu alloy processed by ECAP appears to be attributed to a decrease in the size of precipitates, which act as origins of pitting corrosion.     

Hot corrosion Type II of FeCr‐based model alloys for boiler and heat exchanger applications

The hot corrosion Type II of the alloys FeCr20, FeCr20Ni10, FeCr20Ni20, and FeCr20Co10 is investigated at 700°C in air + 0.5% SO₂ with deposits consisting of Na₂SO₄ and a eutectic mixture of Na₂SO₄ and MgSO₄ for 24, 100, and 300 h. The alloying elements nickel and cobalt have a positive influence when tests are conducted using a MgSO₄‐Na₂SO₄ deposit. In this case, they reduce the metal loss and increase the time to the propagation stage. In contrast, when the alloys are exposed with a Na₂SO₄ deposit, these alloying elements increase the metal loss and allow for the transition to the propagation stage because they can form molten phases with the Na₂SO₄. During the incubation stage an oxide scale forms on the FeCr20 alloy, which is thicker than the one formed during exposure without a deposit, and iron oxides are observed, which precipitate in the deposit. The propagation stage occurs by a dissolution and precipitation mechanism forming localized pitting attack. Iron is the main species that dissolves and precipitates, while chromium remains mainly as an oxide beneath the initial surface. The additional elements are found in the pit and in the salt deposit.     

Effect of Mo on corrosion behavior of Ni20Cr–xMo alloys in air with NaCl–KCl–CaCl2 vapor at 570°C

The effect of Mo on the corrosion behavior of Ni20Cr–xMo alloys in an oxidizing chlorine-containing atmosphere using air mixed with the salt-vapor mixture of NaCl–KCl–CaCl₂ at 570°C was investigated. The results revealed that the corrosion performance of the Ni20Cr alloys in the oxidizing chlorine atmosphere was improved by Mo addition of up to 3 wt%. The Mo-free alloy formed a potassium chromate during corrosion as a result of the reaction between the Cr₂O₃ scale and KCl vapor. The chromate formation increased the chlorine potential at the scale surface and induced the breakdown of the protective Cr₂O₃ scale, resulting in internal chromium chloride precipitates and a Cr-depleted zone. In contrast, the presence of Mo resulted in the formation of a NiO scale, which did not react with the salt vapors and, therefore, prevented the formation of chromates. The beneficial effect of Mo on the high-temperature chlorination of Ni–Cr alloys in salt-vapor-containing atmospheres was ascribed to the suppression of chlorine generation due to NiO scale formation.     

Zr-XSn-1Nb-0.3Fe(X=0~1.5)合金的腐蚀行为研究

通过高压釜腐蚀实验研究了Zr-XSn-1Nb-0.3Fe合金(X=0~1.5,质量分数,%)在360℃/18.6 MPa纯水、360℃/18.6 MPa/0.01 mol·L-1 LiOH水溶液以及400℃/10.3 MPa过热蒸汽中的耐腐蚀性能。结果表明,随着Sn含量从1.5%降低至0.6%,合金试样腐蚀增重降低;进一步降低Sn含量时,合金在纯水和蒸汽中的腐蚀增重没有明显变化,但在LiOH水溶液中的腐蚀增重反而增加。采用透射电镜表征腐蚀前的显微组织发现,随着Sn含量的变化,合金中第二相的大小及类型相接近,但面密度随着Sn含量的增加而减少。采用激光拉曼光谱分析腐蚀过程中氧化膜晶体结构表明,腐蚀初期氧化膜的结构以m-ZrO2和t-ZrO2为主,随着腐蚀时间的增加,t-ZrO2转变为m-ZrO2;t-ZrO2转变越快,t-ZrO2含量越低,腐蚀速率越高。     

Effect of pH on the polarization behavior of Zr65Al7.5Ni10Cu17.5 amorphous alloy in a phosphate-buffered solution

The present study evaluates the effects of surface finishing and dissolved oxygen in phosphate buffered saline solution on the corrosion behavior of Zr₆₅Al_7.5Ni₁₀Cu_17.5 amorphous alloy for the application of the alloy to biomaterials. Non-polished and polished alloys were polarized in deaerated electrolyte, and the polished alloy was also polarized with various concentrations of dissolved oxygen. The surface of the alloy was characterized using X-ray photoelectron spectroscopy. The corrosion resistance of the alloy decreased with metallic nickel and hydroxide ion in surface oxide after polishing. The pitting corrosion resistance also decreased with the hydroxide ion after polishing. On the other hand, the pitting-corrosion resistance increased with aerating 4% O₂ because of the decrease of hydroxide ion and adsorbed phosphate ion in the surface oxide. However, oxygen above 4% O₂ prevented dissolution of nickel, causing the decrease of the pitting-corrosion resistance. When the pH was 2.2, the dissolved oxygen did not influence the pitting-corrosion resistance because of the increased solubility of the surface oxide.     

Corrosion behavior of Zr–Nb–Cr cladding alloys

Zr-Nb-Cr alloys were used to evaluate the effects of alloying elements Nb and Cr on corrosion behavior of zirconium alloys. The microstructures of both Zr substrates and oxide films formed on zirconium alloys were characterized. Corrosion tests reveal that the corro- sion resistance of ZrxNb0.1Cr （x = 0.2, 0.5, 0.8, 1.1; wt%） alloys is first improved and then decreased with the increase of the Nb content. The best corrosion resistance can be obtained when the Nb concentration in the Zr matrix is nearly at the equilibrium solution, which is closely responsible for the formation of columnar oxide grains with protective characteristics. The Cr addition degrades the corrosion resistance of the Zrl.lNb alloy, which is ascribed to Zr（Cr,Fe,Nb）2 precipitates with a much larger size than β-Nb.     

Role of chlorides in hot corrosion of a cast Fe–Cr–Ni alloy. Part I: Experimental studies

High alloy stainless steels are often used in corrosive, high temperature applications because they form a protective, adherent Cr₂O₃ scale. When the environment in such applications includes condensed molten salts, especially alkali sulfates and alkali chlorides, these alloys are likely to undergo hot corrosion, even at moderate temperatures compared to their typical maximum application temperature. The chemical (or electrochemical) reactions and transport modes for hot corrosion in a system involving a multi-component alloy and a multi-component salt are complex, but some insight can be gained with the help of a multi-component thermochemical model to identify major reactions. The present work consists of two parts: (a) experimental measurements of hot corrosion rates and characterization of corrosion products on a commercial, cast super-duplex stainless steel (HH), which result from exposure to thin deposits of a mixture of alkali sulfates and alkali chlorides, and (b) an evaluation of possible corrosion reactions by a multi-component thermochemical model. In laboratory hot corrosion tests alloy coupons experienced rapid oxidation rates, penetration of the oxide scale, scale blistering, and scale spallation (on cooling). Compared to simple air oxidation, alkali sulfate deposits increased the corrosion rate by a factor of about 200, but mixtures of alkali sulfate and alkali chloride increased the rate by about 20,000 times. A principal goal of the study was to identify the role of alkali chlorides in accelerating hot corrosion.     

Sub-Scale Depletion and Enrichment Processes During High Temperature Oxidation of the Nickel Base Alloy 625 in the Temperature Range 900�C1000?��C

Numerous chromia-forming austenitic steels and nickel-base alloys contain chromium-rich strengthening precipitates, e.g. chromium-base carbides. During high temperature exposure the formation of the chromia base oxide scale results in chromium depletion in the alloy matrix and consequently in dissolution of the strengthening phase in the sub-surface zone. The present study describes the oxidation induced phase changes in the chromium depletion layer in case of alloy 625, a nickel base alloy in which the strengthening precipitates contain hardly any or only minor amounts of chromium. Specimens of alloy 625 were subjected to oxidation up to 1000 h at 900 and 1000 °C and analyzed in respect to oxide formation and microstructural changes using light optical microscopy, scanning electron microscopy, energy and wavelength dispersive analysis, glow discharge optical emission spectroscopy, and X-ray diffraction. In spite of the fact that the alloy precipitates ??-Ni₃Nb and/or (Ni, Mo)₆C contain only minor amounts of chromium, the oxidation induced chromium depletion results in formation of a wide sub-surface zone in which the precipitate phases are depleted. However, in parallel, substantial niobium diffusion occurs towards the alloy surface resulting in formation of a thin layer of ??-Ni₃Nb phase adjacent to the alloy/oxide interface. By modeling phase equilibria and diffusion processes using Thermo-Calc and DICTRA it could be shown that the phase changes in the sub-scale zone are governed by the influence of alloy matrix chromium concentration on the thermodynamic activities of the other alloying elements, mainly niobium and carbon. The ??-phase depletion/enrichment process is caused by a decreasing niobium activity with decreasing chromium concentration whereas the (Ni,Mo)₆C dissolution finds its cause in the increasing carbon activity with decreasing chromium content.