The corrosion behavior of Fe-based shape memory alloys

Fe-30Mn-6Si, Fe-30Mn-6Si-5Cr and Fe-13Mn-5Si-12Cr-5Ni shape memory alloys were prepared by a VIM technique. The various corrosion tests were conducted to investigate the corrosion behaviors of these alloys. Experimental results show that in 3.5% NaCl solution, the Fe-13Mn-5Si-12Cr-5Ni alloy had the best chemical corrosion resistance, whereas the Fe-30Mn-6Si-5Cr alloy was locally attacked, forming many corrosion pits after immersion test. In addition, the detachment of the corrosion product covering the Fe-30Mn-6Si alloy caused an abrupt increase in the weight loss. After 2 h of heat treatment at 1000 °C, the corrosion potential of the Fe-30Mn-6Si alloy increased due to the formation of α-ferrite, while the Fe-30Mn-6Si-5Cr alloy became more active. In the stress-corrosion cracking test, the Fe-13Mn-5Si-12Cr-5Ni alloy, having the highest fracture stress in the atmosphere among these alloys, exhibited the largest decrease in fracture stress in the saturated H₂S solution due to the existence of α-martensite.     

含有Nb、Ce的形状记忆合金FeMnSiCrNi在3.5%NaCl溶液中的空蚀行为

利用超声波振动仪研究形状记忆合金Fe-14Mn-6Si-9Cr-5Ni-Nb-Ce在3.5%NaCl溶液中的空蚀行为,并探讨合金在3.5%NaCl溶液中处于静态和空蚀情形下的自腐蚀电位和极化曲线.结果表明,Fe-14Mn-6Si-9Cr-5Ni-Nb-Ce合金在3.5%NaCl溶液中呈现优异的抗空蚀性能,空蚀率为0.37 mg/h.空化能使Fe-14Mn-6Si-9Cr-5Ni-Nb-Ce合金的自腐蚀电位变负,变化量为-65 mV.在静态和空化两种条件下,Fe-14Mn-6Si-9Cr-5Ni-Nb-Ce合金在3.5%NaCl溶液中的自腐蚀电流密度都很低,因此合金具有优异的抗腐蚀性能,其纯腐蚀率和力学效应诱导的腐蚀率仅占空蚀率的2.24%.     

Inhibition mechanism of S-containing additives towards intergranular corrosion of a sensitized stainless steel

The comparison of the polarization curves recorded on both pure Fe, Cr, Ni, and Fe-18Cr-8Ni, Fe-8Cr-8Ni alloys, and Fe-10Ni, Fe-17Cr alloys in 1 N H₂SO₄ at 70°C clarifies the mechanism of inhibition of IG corrosion on sensitized AISI 304 SS by S-containing additives. These additives stimulate the anodic dissolution process of Fe-18Cr-8Ni alloy and inhibit this process on Fe-8Cr-8Ni alloy. The anodic behaviour of Fe-18Cr-8Ni is similar to that of pure chromium, while the behaviour of Fe-8Cr-8Ni is similar to that of pure iron.     

Electrochemical kinetics of the high entropy alloys in aqueous environments—a comparison with type 304 stainless steel

A high entropy alloy (HEA) is a multi-component alloy containing several major alloying elements, which has a high degree of atomic disorder that leads to various unique magnetic, mechanical, and electrochemical properties. It is known that one HEA, evaluated previously, is more resistant to general corrosion than type 304 stainless steel (304s), both in H₂SO₄ and in NaCl solutions at room temperature, but pitting corrosion resistance of the HEA is less than that of 304s.The anodic polarization curves determined for the HEA in aqueous environments showed that the general corrosion resistance of both HEA and 304s decreases as the temperature increases above room temperature. The decrease in the corrosion resistance of the HEA with an increase in temperature is less in NaCl than in H₂SO₄. The general corrosion rate for the HEA is lower than that for 304s in H₂SO₄, but higher than that for 304s in NaCl. The activation energies are: 94.06 kJ/mole for the HEA and 219.97 kJ/mole for 304s in 1 N H₂SO₄, and 310.43 kJ/mole for the HEA and 343.18 kJ/mole for 304s in 1 M NaCl. In addition, it was observed that concentration polarization occurred in cathodic reduction processes in deaerated 1 M NaCl at various temperatures.The polarization curves for the HEA and 304s indicated there is mixed control in 1 N H₂SO₄ and anodic control in 1 M NaCl based on the assumption that the surface chemical compositions of the two alloys are similar to their bulk chemical compositions. However, the decrease in the cathodic current with time for the HEA at more negative applied potentials is attributed to the high hydrogen overvoltage. In addition, the weak endothermic reaction revealed by differential scanning calorimetry (DSC) analysis showed that only small amounts of Cu-rich phases are segregated in the interdendritic phases; and the wide range of temperatures over which the endothermic reaction occurs indicates the formation of pro-eutectoid phases.     

Evaluation of hydrogen absorption behaviour during acid etching for surface modification of commercial pure Ti, Ti-6Al-4V and Ni-Ti superelastic alloys

The hydrogen absorption behaviour during acid etching for the surface modification of commercial pure Ti, Ti-6Al-4V and Ni-Ti superelastic alloys has been investigated on the basis of the surface morphology, electrochemical behaviour and hydrogen thermal desorption analysis. To simulate the conventional acid etching for the improvement of the biocompatibility of Ti alloys, the specimens are immersed in 1 M HCl, 1 M H₂SO₄ or 0.5 M HCl + 0.5 M H₂SO₄ aqueous solution at 60 °C. Upon immersion, commercial pure Ti absorbs substantial amounts of hydrogen irrespective of the type of solution. In H₂SO₄ or HCl + H₂SO₄ solutions, the hydrogen absorption occurs for a short time (10 min). For Ti-6Al-4V alloy, no hydrogen absorption is observed in HCl solution, whereas hydrogen absorption occurs in other solutions. For Ni-Ti superelastic alloy, the amount of absorbed hydrogen is large, resulting in the pronounced degradation of the mechanical properties of the alloy even for an immersion time of 10 min, irrespective of the type of solution. The hydrogen absorption behaviour is not necessarily consistent with the morphologies of the surface subjected to corrosion and the shift of the corrosion potential. The hydrogen thermal desorption behaviour of commercial pure Ti and Ni-Ti superelastic alloy are sensitively changed by acid etching conditions. The present results suggest that the evaluation of hydrogen absorption is needed for each condition of acid etching, and that the conventional acid etching often leads to hydrogen embrittlement.     

Inhibiting effects of butyl triphenyl phosphonium bromide on corrosion of mild steel in 0.5 M sulphuric acid solution and its adsorption characteristics

Butyl triphenyl phosphonium bromide (BuTPPB) has been evaluated as a corrosion inhibitor for mild steel in 0.5 M H₂SO₄ solutions using galvanostatic polarisation and potentiostatic polarisation measurements. The study was also complemented by infra red (IR) spectroscopy, scanning electron microscopy (SEM) and quantum chemical calculations. Galvanostatic polarisation measurements showed that the presence of BuTPPB in aerated 0.5 M H₂SO₄ solutions decreases corrosion currents to a great extent and the corrosion rate decreases with increasing inhibitor concentration at a constant temperature. At 298K, inhibition efficiency was found to be 94.5% for 10⁻⁷ M BuTPPB which increased to about 99% for the BuTPPB concentration of 10⁻² M. The effect of temperature on the corrosion behaviour of mild steel was studied at five different temperatures ranging from 298 to 338K. The polarisation curves clearly indicate that BuTPPB acts as a mixed type inhibitor. Adsorption of BuTPPB on the mild steel surface follows the Langmuir isotherm.Potentiostatic polarisation measurements showed that passivation was observed only for lower BuTPPB concentrations (10⁻⁵ and 10⁻⁷ mol l⁻¹) for the mild steel in 0.5 M H₂SO₄. IR and SEM investigations also confirmed the adsorption of BuTPPB on the mild steel surface in 0.5 M H₂SO₄ solutions. The molecular parameters obtained using PM3 semi-empirical method, were correlated with the experimentally measured inhibitor efficiencies.     

The Hot Corrosion of Fe-Mn-Al–C Alloy with NaCl/Na2SO4 Coating Mixtures at 750°C

The high-temperature corrosion behavior of Fe-30.1Mn-9.7Al-0.77C alloy initially coated with 2 mg/cm² NaCl/Na₂SO₄ (100/0, 75/25, 50/50, 25/75 and 0/100 wt.%) deposits has been studied at 750°C in air. The result shows that weight-gain kinetics in simple oxidation reveals a steady-state parabolic rate law after 3 hr, while the kinetics with salt deposits all display multi-stage growth rates. The corrosion morphology of the alloy with 100% Na₂SO₄ coating is similar to that of simple oxidation. NaCl acts as the predominant corrosion species for Fe-Mn-Al-C alloy, inhibiting the formation of a protective oxide scale. For the alloy coated with over 50% NaCl in salts, NaCl induces selective oxidation of manganese and results in the formation of secondary ferrite in the alloy substrate as well as void-layers with different densities of voids layer by layer in the secondary-ferrite zone.     

Fe—Mn─Al合金的腐蚀性能与钝化膜的研究

应用阳极极化及ＡＥＳ／ＸＰＳ技术,研究了Ｆｅ－３０．８Ｍｎ－８．２Ａｌ奥氏体合金在ｐＨ值为－０．８至１５．３的水溶液中的腐蚀性能,并与Ｆｅ－３０Ｍｎ合金、低碳钢、９％Ｎｉ低温钢及１Ｃｒ１３不锈钢进行对比。在所测试的水溶液中,该合金的腐蚀抗力优于低碳钢和Ｆｅ－３０Ｍｎ合金,与９％Ｎｉ钢相当,但不及１Ｃｒ１３不锈钢。Ｆｅ－３０．８Ｍｎ－８．２Ａｌ合金在１ｍｏｌ／ＬＮａ２ＳＯ个中形成的钝化膜的最表层可能为氢氧化物,而膜的主体由Ｆｅ２Ｏ３、Ｍｎ２Ｏ３及Ａｌ２Ｏ３组成。     

Galvanic corrosion between the constituent phases in duplex stainless steel

The exclusive single-phase with the exact chemical composition of the constituent phase in 2205 duplex stainless steel (DSS) could be prepared using selective dissolution method. The respective electrochemical behavior of each constituent phase could then be measured. The experimental results showed that the two distinct peaks in the active-to-passive transition region of the polarization curve determined in 2 M H₂SO₄ + 0.5 M HCl mixed solution were actually corresponded to the respective anodic peaks of the single austenite and ferrite phases. A polarity reversion was found between austenite and ferrite phases in mixed H₂SO₄ + HCl solution and HNO₃ solution. Galvanic current measurements also revealed that austenite was anode in HNO₃ solution, but became cathode when exposed in 2 M H₂SO₄ + 0.5 M HCl mixed solution.     

A comparison between the corrosion resistances of some HVOF-sprayed metal alloy coatings

This study compares the corrosion resistance of one Co-based alloy coating, namely Co-28Mo-17Cr-3Si (similar to Tribaloy-800), four Ni-based alloy coatings, namely Ni-17Cr-4Fe-4Si-3.5B-1C (Diamalloy-2001), Ni-20Cr-10W-9Mo-4Cu-1C-1B-1Fe (Diamalloy-4006), Ni-22Cr-9Mo-4Nb-5Fe (similar to Inconel-625), Ni-32Mo-16Cr-3Si-2Co (similar to Tribaloy-700), and a (WC-12Co)-33Ni-9Cr-3.5Fe-2Si-2B-0.5C cermet-Ni alloy blend coating. They were produced by liquid-fuelled HVOF spraying onto AISI1040 steel plates. Electrolytic hard chrome (EHC) plating was characterised as a reference material, to verify whether some HVOF coatings are suitable as an EHC replacement. The microstructure of the coatings was examined by SEM and XRD. Electrochemical polarization tests and free corrosion tests were performed in 0.1 M HCl aqueous solution; the corrodkote test (ASTM B380-97R02) was also performed, to rank coatings qualitatively.The lowest corrosion current densities (I_corr) were recorded for EHC and Tribaloy-700. The latter coating contained few secondary phases and little porosity; the damage was mainly due to corrosion activation along lamellae boundaries. Diamalloy-2001 exhibited the highest I_corr and was significantly damaged after the polarization test, as its multi-phase microstructure had triggered severe galvanic corrosion. During free corrosion in 0.1 M HCl, Tribaloy-700 and Diamalloy-4006 retained rather stable polarization resistance (R_p), whereas the R_p of EHC decreased significantly. Tribaloy-700 survived 40 h of corrodkote test with no apparent damage and EHC underwent limited pitting corrosion. All other coatings had visible corrosion. The Inconel-625 coating failed to protect the substrate after 20 h of testing, due to inadequate processing conditions.     

Corrosion behavior of Cr/Cu-coated Mg alloy (AZ91D) in 0.1 M H2SO4 with different concentrations of NaCl

An electroplating process was proposed for obtaining a protective Cr/Cu deposit on the two-phase Mg alloy AZ91D. The corrosion behavior of Cu-covered and Cr/Cu-covered AZ91D specimens was studied electrochemically in 0.1 M H₂SO₄ with different NaCl concentrations. Experimental results showed that the corrosion resistance of an AZ91D specimen improved significantly after Cr/Cu electrodeposition. The corrosion resistance of Cr/Cu-covered AZ91D decreased with increasing NaCl concentration in 0.1 M H₂SO₄ solution. After immersion in a 0.1 M H₂SO₄ with a NaCl-content above 3.5 wt.%, the surface of Cr/Cu-covered AZ91D suffered a few blisters. Cracks through the Cr deposit provided active pathways for corrosion of the Cu and the AZ91D substrate. Formation of blisters on the Cr/Cu-covered AZ91D surface was confirmed based on the results of an open-circuit potential test, which detected an obvious potential drop from noble to active potentials.     

The corrosion behaviour of WC-VC-Co hardmetals in acidic media

The effect of increasing vanadium carbide (VC) content on the corrosion behaviour of tungsten carbide - 10 wt% cobalt hardmetals was investigated in 1 M hydrochloric (HCl), and sulphuric (H₂SO₄) acids solutions. Increasing VC content makes the open circuit potential (OCP) in the test solutions more negative than the base alloy. Specimens exhibited pseudo passivation in all the test solutions. Increasing VC led to decreasing corrosion current density. However, the corrosion current densities during chronoamperometric tests were lower for 0 wt% VC. XRD and Raman spectroscopy showed that hydrated WO₃ formed in the surface films of all specimens in hydrochloric acid (HCl), while hydrated vanadyl sulphate also formed for higher VC content specimens in sulphuric acid (H₂SO₄).     

Microstructure and Corrosion Behavior of Hot-Deformed and Cold-Strained High-Mn Steels

The electrochemical corrosion properties of 26Mn-3Si-3Al and 27Mn-4Si-2Al austenitic steels in two different states were studied in 0.1 M H₂SO₄ and 3.5% NaCl using potentiodynamic polarization tests. The effect of cold deformation on the microstructure and corrosion behavior of steels was analyzed. In acid solution, both steels exhibited lower corrosion resistance than in chloride solution independently on the steel state (hot-rolled, cold-worked). Cold deformation decreases the corrosion resistance, though this effect is smaller than the effect of chemical composition related to the combined Al + Si addition. All steels showed the evidence of pitting corrosion. The intensive dissolution of Fe and Mn takes place in the acid medium.     

Corrosion behaviour of an alloy formed by inductive melting of a cobalt-based alloy and AISI 4140 steel

A bimetal of Co-based alloy/AISI 4140 steel was fabricated by induction melting. The microstructure of the Co-based alloy was examined and the influence of on the alloy of acid solutions, the temperature of these solutions, and the immersion time was investigated. The results show that the microstructure of Co-based alloy consisted of a Co-rich phase, a Cr-rich phase, and W₃CoB₃. In a solution of 20% HCl and 6% FeCl₃, the Co-rich phase was attacked to form porous channels but transformed to a Si-rich passivation film to prevent further attack in the solution of 72% H₂SO₄. Therefore, the relative corrosion resistance of Co-based alloy to acid solution is 72% H₂SO₄ > 20% HCl > 6% FeCl₃.     

Electrochemical corrosion behaviour of microcrystalline aluminium in acidic solutions

The electrochemical corrosion behaviour of microcrystalline pure aluminium coating, fabricated by a magnetron sputtering technique, has been investigated in both 0.5 mol/l NaCl and 0.5 mol/l Na₂SO₄ acidic (pH = 2) aqueous solutions. The corrosion resistance of the microcrystalline Al coating has deteriorated more compared with that of the cast pure Al in Na₂SO₄ acidic solution. However, its oxide film has a higher pitting resistance in the NaCl acidic solution. Chloride ions play a big role in the formation of the oxide film on the microcrystalline Al coating. The higher pitting resistance was attributed to the more acidic isoelectric point which the oxide film achieved.     

Corrosion behaviour of die-cast AZ91D magnesium alloy in aqueous sulphate solutions

The corrosion behaviour of die-cast AZ91D magnesium alloys in sulphate solutions was investigated by SEM, FTIR and polarization measurements. For immersion times less than 48 h, no pitting corrosion occurred and only generalized corrosion was apparent. According to the polarization curves, the corrosion rate order of the die-cast AZ91D Mg alloy in three aqueous solutions was: NaCl > MgSO₄ > Na₂SO₄. The main corrosion products were Mg(OH)₂ and MgAl₂(SO₄)₄·22H₂O in the sulphate solutions and the product film was compact. Precipitation of MgAl₂(SO₄)₄·22H₂O required a threshold immersion time.     

The effect of microstructure on the shape recovery of a Fe–Mn–Si–Cr–Ni stainless steel shape memory alloy

In this work the effect of varying the microstructure on the shape memory properties of a Fe-15Mn-7Si-9Cr-5Ni (wt.%) stainless steel shape memory alloy was evaluated using a simple bend test. The best shape recovery was obtained for a single-phase austenite microstructure and for a two-phase microstructure composed of an austenite matrix and Fe₅Ni₃Si₂ type intermetallic grain boundary phase. The maximum shape recovery was achieved at the reversion temperature of 600 °C and when the pre-stain was less than 2%.     

The effect of processing gas on corrosion performance of electroless Ni-W-P coatings treated by laser

An investigation of the microstructural and corrosion characteristics of electroless Ni-5.5 W-6.5P coatings on steel substrates after laser treatment in argon and air is presented. The microstructural characteristics of the coatings, in terms of crystallisation, grain size, microstrain, porosity as well as surface chemistry, were examined using quantitative X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Electrochemical tests, using potentiodynamic polarisation in 0.5 M H₂SO₄ solution and electrochemical impedances spectroscopy (EIS) in 3.5% NaCl solution, were undertaken to evaluate the corrosion behaviour of the coatings. The results indicated that the laser-treated coatings consisted of nanocrystalline Ni and Ni₃P phases, along with retained amorphous phase; further, the dimensions of the Ni crystallites were larger than those of Ni₃P. The laser-treated coating in argon revealed the presence of submicron scale porosity, while no porosity was evident in the coating surface treated by laser in air. The uniform corrosion revealed in 0.5 M H₂SO₄ solution is mainly determined by the microstructural characteristics of the coating. Pitting corrosion in 3.5% NaCl solution depended on the amount of porosity on the surface. The laser-treated coating in air exhibited better corrosion resistance in both acidic and chloride environments than that laser-treated in argon.     

Corrosion behaviour of vacuum induction-melted Ni-based alloy in sulphuric acid

A vacuum induction-melted (VIM) Ni-based alloy was immersed in 60% H₂SO₄ solution to investigate its corrosion behaviour and resistance. The results indicate that the microstructure contains a γ-Ni solid solution + Ni₃Si particles, dendrite Ni₃Si, Ni₃B, Cr₇C₃, and CrB. The corrosion started at the zones of the γ-Ni solid solution + Ni₃Si particles and dendrite Ni₃Si. These zones transformed to oxide films and protected the alloy from significant attack. However, the pitting corrosion created paths for acid solution and/or to further attack. Therefore, the corrosion rate decreased and then stabilised at a high value as the immersion time increased.     

Semiconductor properties and protective role of passive films of iron base alloys

Semiconductor properties of passive films formed on the Fe-18Cr alloy in a borate buffer solution (pH = 8.4) and 0.1 M H₂SO₄ solution were examined using a photoelectrochemical spectroscopy and an electrochemical impedance spectroscopy. Photo current reveals two photo action spectra that derived from outer hydroxide and inner oxide layers. A typical n-type semiconductor behaviour is observed by both photo current and impedance for the passive films formed in the borate buffer solution. On the other hand, a negative photo current generated, the absolute value of which decreased as applied potential increased in the sulfuric acid solution. This indicates that the passive film behaves as a p-type semiconductor. However, Mott-Schottky plot revealed the typical n-type semiconductor property. It is concluded that the passive film on the Fe-18Cr alloy formed in the borate buffer solution is composed of both n-type outer hydroxide and inner oxide layers. On the other hand, the passive film of the Fe-18Cr alloy in the sulphuric acid consists of p-type oxide and n-type hydroxide layers. The behaviour of passive film growth and corrosion was discussed in terms of the electronic structure in the passive film.