Corrosion resistance and thermal stability of sputtered Fe44Al34Ti7N15 and Al61Ti11N28 thin films for prospective application in oil and gas industry

Fe-and Al-based thin-film metallic glass coatings (Fe₄₄Al₃₄Ti₇N₁₅ and Al₆₁Ti₁₁N₂₈) were fabricated using magnetron co-sputtering technique, and their corrosion performances compared against wrought 316L stainless steel. The results of GI-XRD and XPS analyses demonstrated amorphous structure and oxide layer formation on the surface of the fabricated thin films, respectively. The potentiodynamic (PD) polarization test in chloride-thiosulfate (NH₄Cl ​+ ​Na₂S₂O₃) solution revealed lower corrosion current (I_corr) (0.42 ​± ​0.02 ​μA/cm² and 0.086 ​± ​0.001 ​μA/cm² Vs. 0.76 ​± ​0.05 ​μA/cm²), lower passivation current (I_pass) (1.45 ​± ​0.03 ​μA/cm² and 1.83 ​± ​0.07 ​μA/cm² Vs. 1.98 ​± ​0.04 ​μA/cm²), and approximately six-fold higher breakdown potential (E_bd) for Fe- and Al-based coatings than those of wrought 316L stainless steel. Electrochemical Impedance Spectroscopy (EIS) of both films showed 4- and 2-fold higher charge transfer resistance (R_ct), 7- and 2.5-times higher film resistance (R_f), lower film capacitance values (Q_f) (10 ​± ​2.4 ​μS-s^acm^-2, and 5.41 ​± ​0.8 ​μS-s^acm^-2 Vs. 18 ​± ​2.21 ​μS-s^acm^-2), and lower double-layer capacitance values (Q_dl) (31.33 ​± ​4.74 ​μS-s^acm^-2, and 15.3 ​± ​0.48 ​μS-s^acm^-2 Vs. 43 ​± ​4.23 ​μS-s^acm^-2), indicating higher corrosion resistance of the thin films. Cyclic Voltammetry (CV) scan exhibited that the passive films formed on the Fe- and Al-based coatings were more stable and less prone to pitting corrosion than the wrought 316L stainless steel. The surface morphology of both films via SEM endorsed the CV scan results, showing better resistance to pitting corrosion. Furthermore, the thermal analysis via TGA and DSC revealed the excellent thermal stability of the thin films over a wide temperature range typically observed in oil-gas industries.     

Effect of Nb on the corrosion behavior of continuous bulk metallic glass-coated steel wire composites

(Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5)_100?xNb_x (at%, x=0 and 8) bulk metallic glasses (BMGs) were coated on the surface of Q195 steel wires by a continuous coating process. The potentiodynamic polarization tests of these BMGs were conducted in 3.5wt% NaCl aqueous solution. It is found that the addition of 8at% Nb into Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 alloy results in the improvement of corrosion resistance with the pitting potential of ?52 mV, the open circuit potential of ?446 mV, and the corrosion current density of 9.86×10?6 mA/cm2. This may be attributed to that Nb is beneficial to passivate and stabilize Zr and Ti.     

Electrochemical corrosion behavior of the cobalt modified aluminide coating in 3.5 wt% NaCl solutions

In this paper, we achieved the Co modified aluminide coating on nickel base superalloys by pack cementation process. The corrosion currents(i_(corr)) of coated and uncoated substrate after 1 h of immersion tested by potentiodynamic polarization in 3.5 wt% NaCl solutions are 9.73 b × 10~(-7) A/cm~2 and 1.31 × 10~(-6) A/cm~2, respectively. With the immersion time extension, the icorrof the coating decreases and the values of |Z| by EIS increase, indicating that the electrochemical reaction rate of the coating becomes slower. The coating presents good corrosion resistance due to the Al_2O_3 formed on the surface.     

Effects of crystallization on corrosion behaviours of a Ni-based bulk metallic glass

The effects of microstructure change on the corrosion behaviours of Ni₅₅Nb₂₀Ti₁₀Zr₈Co₇ bulk glass-forming alloy were investigated in 1 mol/L HCl and 0.5 mol/L H₂SO₄ solutions. Different microstructures of the Ni-based alloy were achieved by annealing the bulk glassy rod prepared by copper mould casting. The microstructure, grain size, grain distribution, and phase composition were characterized. Electrochemical behaviours of the Ni-based alloy were revealed by static immersion and anodic potentiodynamic polarization tests. It is indicated that the corrosion behaviours of the Ni-based bulk glass-forming alloy are related to its microstructures, while the fully crystallized alloy exhibits a relatively lower corrosion resistance than those of the amorphous states.     

Corrosion study of resorbable Ca60Mg15Zn25 bulk metallic glasses in physiological fluids

The corrosion activity of amorphous plates of Ca_(60)Mg_(15)Zn_(25)alloy was investigated.The biocompatible elements were selected for the alloy composition.The electrochemical corrosion and immersion tests were carried out in a multi-electrolyte fluid and Ringer's solution.Better corrosion behavior was observed for the samples tested in a multi-electrolyte fluid despite the active dissolution of Ca and Mg in Ringer's solution.The experimental results indicated that reducing concentration of NaCl from 8.6 g/dm~3for Ringer's solution to 5.75 g/dm~3caused the decrease of the corrosion rate.The volume of the hydrogen evolved after 480 min in Ringer's solution(40.1 ml/cm~2)was higher in comparison with that obtained in a multi-electrolyte fluid(24.4 ml/cm~2).The values of opencircuit potential(E_(OCP))for the Ca_(60)Mg_(15)Zn_(25)glass after 1 h incubation in Ringer's solution and a multielectrolyte fluid were determined to be-1553 and-1536 m V vs.a saturated calomel electrode(SCE).The electrochemical measurements indicated a shift of the corrosion current density(j_(corr))from 1062μA/cm~2for the sample tested in Ringer's solution to 788μA/cm~2for the specimen immersed in a multi-electrolyte fluid.The corrosion products analysis was conducted by using the X-ray photoelectron spectroscopy(XPS).The corrosion products were identified to be CaCO_3,Mg(OH)_2,CaO,MgO and Zn O.The mechanism of corrosion process was proposed and described based on the microscopic observations.The X-ray diffraction and Fourier transform infrared spectroscopy(FTIR)also indicated that Ca(OH)_2,CaCO_3,Zn(OH)_2and Ca(Zn(OH)_3)_2·2H_2O mainly formed on the surface of the studied alloy.     

Effects of chloride ion concentration and pH values on the corrosion behavior of Cr12Ni3Co12Mo4W ultra-high-strength martensitic stainless steel

The effects of Cl- ion concentration and pH values on the corrosion behavior of Cr12Ni3Co12Mo4W ultra-high-strength martensitic stainless steel (UHSMSS) were investigated by a series of electrochemical tests combined with observations by stereology microscopy and scanning electron microscopy. A critical Cl- ion concentration was found to exist (approximately 0.1wt%), above which pitting occurred. The pitting potential decreased with increasing Cl- ion concentration. A UHSMSS specimen tempered at 600°C exhibited a better pitting corrosion resistance than the one tempered at 400°C. The corrosion current density and passive current density of the UHSMSS tempered at 600°C decreased with increasing pH values of the corrosion solution. The pits developed a shallower dish geometry with increasing polarization potential. A lacy cover on the pits of the UHSMSS tempered at 400°C accelerated pitting, whereas corrosion products deposited in the pits of the UHSMSS tempered at 600°C hindered pitting.     

Conductive and corrosion behaviors of silver-doped carbon-coated stainless steel as PEMFC bipolar plates

Ni–Cr enrichment on stainless steel SS316L resulting from chemical activation enabled the deposition of carbon by spraying a stable suspension of carbon nanoparticles; trace Ag was deposited in situ to prepare a thin continuous Ag-doped carbon film on a porous carbon-coated SS316L substrate. The corrosion resistance of this film in 0.5 mol·L-1 H₂SO₄ solution containing 5 ppm F- at 80℃ was investigated using polarization tests. The results showed that the surface treatment of the SS316L strongly affected the adhesion of the carbon coating to the stainless steel. Compared to the bare SS316L, the Ag-doped carbon-coated SS316L bipolar plate was remarkably more stable in both the anode and cathode environments of proton exchange membrane fuel cell (PEMFC) and the interface contact resistance between the specimen and Toray 060 carbon paper was reduced from 333.0 mΩ·cm2 to 21.6 mΩ·cm2 at a compaction pressure of 1.2 MPa.     

Effect of Ce addition on hot corrosion behaviours of a cast γ′-strengthened Co–Al–W–Mo–Ta–B alloy at 800 ​°C

Hot corrosion behaviours of a novel Co–9Al-4.5W-4.5Mo–2Ta-0.02B alloy doped with 0.01, 0.05, 0.1 and 0.2 ?at% Ce exposed at 800 ?°C in a solution of 75%Na₂SO₄/25%NaCl were investigated. The alloys comprised a coherent γ-Co_SS/γ′-Co₃(Al, W) microstructure (0.01Ce and 0.05Ce alloys) and κ-Co₃(W, Mo) precipitates (0.1Ce and 0.2Ce alloys) at grain boundaries. Hot corrosion kinetics curves demonstrated the parabolic time dependency profile with two stages: the first parabolic stage is within the beginning ～50 ?h corrosion and follows by the second parabolic stage. With an increasing nominal Ce content the weight gain of the alloy significantly decreased from approximately 70.1 ?mg ?cm^?2 (0.01Ce) to 40.8 ?mg ?cm^?2 (0.2Ce) when exposed for 100 ?h. A two-layer corrosion scale formed, and the scale was composed of an outer layer of Co₃O₄ oxide with spinel compounds of CoAl₂O₄, CoWO₄and CoSO₄, and an inner γ/needle-like Co₃W/sulphide layer adhered to the substrate. Heavy spallation of the corrosion scale occurred in the 0.01Ce～0.1Ce alloys, however, spallation was slight in the 0.2Ce alloy. The excellent corrosion resistance of the 0.2Ce alloy could be attributed mainly to the formation of continuous Al₂O₃ lines in the corrosion scale, as well as the prolongation of the incubation period of the corrosion product spallation.     

Prediction model for atmospheric corrosion of 7005-T4 aluminum alloy in industrial and marine environments

Accelerated corrosion tests of the 7005-T4 aluminum alloy were conducted to determine a suitable service life prediction method by using alternating wet-dry cycles in three kinds of solutions. The morphology and composition analysis of the corrosion product revealed that slight corrosion occurred on the surfaces of the samples immersed in a 0.25wt% Na₂S₂O₈ solution. However, pitting corrosion occurred on the surfaces of the samples immersed in a 3.5wt% NaCl solution, whereas exfoliation corrosion occurred on the surfaces of the samples immersed in a mixture of 0.25wt% Na₂S₂O₈ and 3.5wt% NaCl solutions. A power exponent relationship was observed between the mass loss and exposure time of the 7005-T4 aluminum alloy immersed in the three kinds of solutions. In the mixture of 0.25wt% Na₂S₂O₈ and 3.5wt% NaCl solutions, the mass loss of the aluminum alloy yielded the maximum value. Based on the calculation of the correlation coefficients, the alternating wet-dry procedure in a 3.5wt% NaCl solution could be used to predict the corrosion behavior of 7005-T4 aluminum alloy exposed in the atmosphere of Qingdao, China. The prediction model is as follows:T=104.28·t0.91, where T is the equivalent time and t is the exposure time.     

Corrosion behavior of as-cast Mg–8Li–3Al+xCe alloy in 3.5wt% NaCl solution

Mg–8Li–3Al+xCe alloys (x = 0.5wt%, 1.0wt%, and 1.5wt%) were prepared through a casting route in an electric resistance furnace under a controlled atmosphere. The cast alloys were characterized by X-ray diffraction, optical microscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The corrosion behavior of the as-cast Mg–8Li–3Al+xCe alloys were studied under salt spray tests in 3.5wt% NaCl solution at 35°C, in accordance with standard ASTM B–117, in conjunction with potentiodynamic polarization (PDP) tests. The results show that the addition of Ce to Mg–8Li–3Al (LA83) alloy results in the formation of Al₂Ce intermetallic phase, refines both the α-Mg phase and the Mg₁₇Al₁₂ intermetallic phase, and then increases the microhardness of the alloys. The results of PDP and salt spray tests reveal that an increase in Ce content to 1.5wt% decreases the corrosion rate. The best corrosion resistance is observed for the LA83 alloy sample with 1.0wt% Ce.     

Electrodeposition of aluminium and aluminium-copper alloys from a room temperature ionic liquid electrolyte containing aluminium chloride and triethylamine hydrochloride

The electrodeposition of Al and Al-Cu binary alloys on to gold substrates from a room temperature ionic liquid electrolyte containing AlCl₃-Et₃NHCl was studied. The electrochemical behavior of the electrolyte and the mechanism of deposition were investigated through cyclic voltammetry (CV), and the properties of deposits obtained were assessed by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Al of 70 μm in thickness and an Al-Cu alloy of 30 μm in thickness with 8at% copper were deposited from the electrolyte. SEM images of the deposits indicate that the Al deposit was smooth and uniform, whereas the Al-Cu deposit was nodular. The average crystalline size, as determined by XRD patterns, was found to be (30 ± 5) and (29 ± 5) nm, respectively, for Al and Al-Cu alloys. Potentiodynamic polarization (Tafel plots) and electrochemical impedance spectroscopic (EIS) measurements showed that Al-Cu alloys are more corrosion resistant than Al.     

In vitro corrosion of Mg–1.21Li –1.12Ca –1Y alloy

The influence of the microstructure on mechanical properties and corrosion behavior of the Mg–1.21Li–1.12Ca–1Y alloy was investigated using OM, SEM, XRD, EPMA, EDS, tensile tests and corrosion measurements. The results demonstrated that the microstructure of the Mg–1.21Li–1.12Ca–1Y alloy was characterized by α-Mg substrate and intermetallic compounds Mg2 Ca and Mg24Y5. Most of the fine Mg2 Ca particles for the as-cast alloy were distributed along the grain boundaries, while for the as-extruded along the extrusion direction. The Mg24Y5 particles with a larger size than the Mg2 Ca particles were positioned inside the grains. The mechanical properties of Mg–1.21Li–1.12Ca–1Y alloy were improved by the grain refinement and dispersion strengthening. Corrosion pits initiated at the α-Mg matrix neighboring the Mg2 Ca particles and subsequently the alloy exhibited general corrosion and filiform corrosion as the corrosion product layer of Mg(OH)2and Mg CO3 became compact and thick.     

新型可焊6005A铝合金的腐蚀行为

采用电化学交流阻抗谱,极化曲线以及浸泡腐蚀实验研究了Cu含量变化对高速列车用6005A铝合金电化学腐蚀行为的影响.结果表明:在商用6005A铝合金基体中添加适量的Cu元素,可有效提高氧化膜的致密性.当添加Cu质量分数为0.4%时,轧制态6005A铝合金电化学交流阻抗图谱中腐蚀反应电阻Rct值较大,双电层电容Q2值较小,极化曲线出现了较宽电位范围的阳极钝化区.但合金自腐蚀电流小幅增加,显示合金局部耐蚀性下降.在质量分数为3.5%NaCl溶液中进行的浸泡实验显示,随着浸泡时间的延长,自制6005A铝合金依次发生点蚀、晶间腐蚀和剥蚀.合金表面氧化膜致密性是影响材料抗腐蚀能力的主要因素.     

静态再结晶处理对Co36Fe36Cr18Ni8Ti2合金力学性能与耐腐蚀性的影响

对冷变形后的Co₃₆Fe₃₆Cr₁₈Ni₈Ti₂合金在700 ℃和800 ℃下再结晶退火，制备成具有高强度及良好耐蚀性的多主元合金。采用电子背散射衍射（electron back-scattered diffraction, EBSD）表征了合金的相分布、再结晶组织以及晶界分布等微观结构特征，采用静态拉伸试验测试了合金的力学性能。结果表明，700 ℃退火的合金断后伸长率较低，但其抗拉强度与屈服强度分别达到了1 038和956 MPa。采用电化学工作站与扫描电子显微镜（scanning electron microscope, SEM）表征了合金在模拟体液中的耐蚀性。结果表明，700 ℃退火的样品具有较好的耐蚀性，腐蚀后的样品表面较为均匀。结合力学性能可知，700 ℃退火的样品具有作为新型医用金属材料的潜力。     

Photocatalytic activity of ferric oxide/titanium dioxide nanocomposite films on stainless steel fabricated by anodization and ion implantation

A simple surface treatment was used to develop photocatalytic activity for stainless steel. AISI 304 stainless steel specimens after anodization were implanted by Ti ions at an extracting voltage of 50 kV with an implantation dose of 3 × 1015 atoms·cm?2 and then annealed in air at 450℃ for 2 h. The morphology was observed by scanning electron microscopy. The microstructure was characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The photocatalytic degradation of methylene blue solution was carried out under ultraviolet light. The corrosion resistance of the stainless steel was evaluated in NaCl solution (3.5 wt%) by electrochemical polarization curves. It is found that the Ti ions depth profile resembles a Gaussian distribution in the implanted layer. The nanostructured Fe₂O₃/TiO₂ composite film exhibits a remarkable enhancement in photocatalytic activity referenced to the mechanically polished specimen and anodized specimen. Meanwhile, the annealed Ti-implanted specimen remains good corrosion resistance.     

Corrosion behavior of Mg–Y alloy in NaCl aqueous solution

The corrosion behavior of Mg–(0.25, 2.5, 5, 8 and 15)Y alloys in 3.5wt.% NaCl aqueous solution was investigated. It was found that the degree of corrosion deterioration increased with increasing immersion time up to 2 h. Corrosion modes for the alloys with low and high content of Y element were general corrosion and pitting corrosion, respective ly, and the threshold content for the corrosion mode change was 2.5% for the tested alloys. The experimental results showed that the addition of Y refined the grain of the alloy, and the distribution, i.e., continuous or not, of the Mg24Y5 phases had great effect on the corrosion rate and corrosion mode.     

Properties of a new type Al/Pb-0.3%Ag alloy composite anode for zinc electrowinning

An Al/Pb-0.3%Ag alloy composite anode was produced via composite casting. Its electrocatalytic activity for the oxygen evolution reaction and corrosion resistance was evaluated by anodic polarization curves and accelerated corrosion test, respectively. The microscopic morphologies of the anode section and anodic oxidation layer during accelerated corrosion test were obtained by scanning electron microscopy. It is found that the composite anode (hard anodizing) displays a more compact interfacial combination and a better adhesive strength than plating tin. Compared with industrial Pb-0.3%Ag anodes, the oxygen evolution overpotentials of Al/Pb-0.3%Ag alloy (hard anodizing) and Al/Pb-0.3%Ag alloy (plating tin) at 500 A·m?2 were lower by 57 and 14 mV, respectively. Furthermore, the corrosion rates of Pb-0.3%Ag alloy, Al/Pb-0.3%Ag alloy (hard anodizing), and Al/Pb-0.3%Ag alloy (plating tin) were 13.977, 9.487, and 11.824 g·m?2·h?1, respectively, in accelerated corrosion test for 8 h at 2000 A·m?2. The anodic oxidation layer of Al/Pb-0.3%Ag alloy (hard anodizing) is more compact than Pb-0.3%Ag alloy and Al/Pb-0.3%Ag alloy (plating tin) after the test.     

晶粒尺寸对含铜锡中铬铁素体不锈钢耐蚀性的影响

以含低熔点元素Cu和Sn的超纯165%(质量分数)Cr铁素体不锈钢为实验材料,通过在35℃恒温6%(质量分数)FeCl3溶液中对实验钢进行浸泡腐蚀实验,并采用三电极体系测定实验钢的极化曲线,初步研究了晶粒尺寸对这种铁素体不锈钢耐蚀性能的影响.实验中,采用经典的失重法计算腐蚀速率,利用动电位扫描法测绘极化曲线,以进一步探究实验钢的腐蚀过程.研究表明,这种铁素体不锈钢的点蚀电位值随晶粒尺寸增大而大幅提高.浸泡腐蚀实验结果证实,存在一个相对合理的晶粒尺寸范围,晶粒尺寸过小或过大都不利于提高耐蚀性能.     

Antibacterial properties and corrosion resistance of AISI 420 stainless steels implanted by silver and copper ions

Silver or copper ions are often chosen as antibacterial agents. But a few reports are concerned with these two antibacterial agents for preparation of antibacterial stainless steel (SS). The antibacterial properties and corrosion resistance of AISI 420 stainless steel implanted by silver and copper ions were investigated. Due to the cooperative antibacterial effect of silver and copper ions, the Ag/Cu implanted SS showed excellent antibacterial activities against both Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) at a total implantation dose of 2×1017 ions/cm2. Electrochemical polarization curves revealed that the corrosion resistance of Ag/Cu implanted SS was slightly enhanced as compared with that of un-implanted SS. The implanted layer was characterized by X-ray photoelectron spectroscopy (XPS). Core level XPS spectra indicate that the implanted silver and copper ions exist in metallic state in the implanted layer.     

In vitro degradation and biocompatibility of Mg-Nd-Zn-Zr alloy

In this study,in vitro degradation and biocompatibility of Mg-Nd-Zn-Zr(NZK) alloy were investigated to determine its suitability as a degradable medical biomaterial.Its corrosion properties were evaluated by static immersion test,electrochemical corrosion test,scanning electron microscopy(SEM),and energy dispersive spectroscopic(EDS) analysis,and in vitro biocompatibilities were assessed by hemolysis and cytotoxicity tests.Pure magnesium was used as control.The results of static immersion test and electrochemical corrosion test in simulated body fluid(SBF) demonstrated that the addition of alloying elements could improve the corrosion resistance.The hemolysis test found that the hemolysis rate of calcium phosphate coated NZK alloy was 4.8%,which was lower than the safe value of 5%.The cytotoxicity test indicated that NZK alloy extracts did not significantly reduce MC3T3-E1 cell viability.Hemolysis test and cytotoxicity test display excellent hemocompatibility and cytocompatibility of NZK alloy in vitro.Our data indicate that NZK alloy has excellent biocompatibility and thus can be considered as a potential degradable medical biomaterial for orthopedic applications.