Effects of benzotriazole on anodized film formed on AZ31B magnesium alloy in environmental-friendly electrolyte

An environmental-friendly electrolyte of silicate and borate, which contained an addition agent of 1H-benzotriazole (BTA) with low toxicity (LD50 of 965 mg/kg), was used to prepare an anodized film on AZ31B magnesium alloy under the constant current density of 1.5 A/dm² at room temperature. Effects of BTA on the properties of the anodized film were studied by scanning electron microscopy (SEM), energy dispersion spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), loss weight measurement, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS), respectively. The results demonstrated that anodized growth process, surface morphology, thickness, phase structure and corrosion resistance of the anodized film were strongly dependant on the BTA concentration, which might be attributed to the formation of an BTA adsorption layer on magnesium substrate surface. When the BTA concentration was 5 g/L in the electrolyte, a compact and thick anodized film could provide excellent corrosion resistance for AZ31B magnesium alloy.     

The susceptibility of 90Cu-10Ni alloy to stress corrosion cracking in seawater polluted by sulfide ions

Electrochemical polarization measurements and slow strain rate tests (SSRT) of a 90Cu-10Ni alloy in highly sulfide polluted seawater were conducted to investigate stress-corrosion cracking (SCC) behavior. The severity of the SCC depends on the sulfide concentration in the seawater. The severity increases as the concentration increases. Because the major time in SCC is spent in the initiation process of the propagating crack, the fracture toughness has only a minor effect in the component life failed by SCC. The SCC behavior of CDA706 is strictly linked to sulfide concentration in the range of 100 to 1000 ppm. The general corrosion of Cu-Ni alloys in low (<100 ppm) and high (>100 ppm) sulfide polluted seawater increases due to the selective copper dissolution. Cyclic polarization measurements confirmed that the corrosion rate decreases slightly as the sulfide concentration increases. Pitting tendency was high in the low concentration range of sulfide and low in the high concentration range. The presence of stresses in SCC removes the protective layer as it increases during testing of the specimen or during the actual service of a component. The authors propose that film rupture occurred, and two proposed SCC mechanisms were operational, namely sulfide stress cracking associated with the anodic dissolution in the low sulfide concentration range and hydrogen embrittlement, which was dominant in the high sulfide concentration range. It was found that a synergism exists between sulfide and stress that enhances the effect of the latter.     

The characterisation of the protective film formed by benzotriazole on the 90/10 copper-nickel alloy surface in H2SO4 media

The nature of the protective film formed by benzotriazole (BTAH) on the surface of the 90/10 CuNi alloy in deaerated 0.5 mol L⁻¹ H₂SO₄ solution containing Fe(III) ions as oxidant was investigated by weight-loss, calorimetric measurements, and by surface-enhanced Raman spectroscopy (SERS). The SERS measurements show that the protective film is composed by the [Cu(I)BTA]_n polymeric complex and that the BTAH molecules are also adsorbed on the electrode surface. A modification of the BET isotherm for adsorption of gases in solids is proposed to describe the experimental results obtained from weight-loss experiments that suggest an adsorption in multilayers. Electrochemical studies of copper and nickel in 0.5 mol L⁻¹ H₂SO₄ in presence and absence of BTAH have also been made as an aid to interpret the results. The calculated adsorption free energy of the cuprous benzotriazolate on the surface of the alloy is in accordance with the value for pure copper.     

The synergistic inhibition effect of organic silicate and inorganic Zn salt on corrosion of Mg-10Gd-3Y magnesium alloy

The inhibition effects of organic sodium aminopropyltriethoxysilicate (APTS–Na) and inorganic zinc nitrate on the corrosion of Mg-10Gd-3Y magnesium alloy (GW103) in ASTM D1384-87 corrosive water are investigated by electrochemical techniques and immersion test. The results show that individual organic or inorganic inhibitor has low inhibition efficiency. However, when these organic and inorganic inhibitors are used together, a synergistic inhibition behavior is observed. The Mg alloy surfaces after immersion test were analyzed using scanning electron microscope (SEM), X-ray diffractometer (XRD) and X-ray photoelectron spectroscopy (XPS). The surface in the inhibitor containing solution is found to be covered by a film composed of Mg(OH)₂ and silicate. It is believed that the formation of this surface film is responsible for the synergistic inhibition effect of the organic and inorganic inhibitors.     

高压处理对La62.0Al15.7(Cu,Ni)22.3非晶合金显微组织和腐蚀行为的影响

采用电弧熔炼铜模吸铸法制备La62.0Al15.7(Cu,Ni)22.3非晶合金,在室温下对该非晶合金进行高压处理(压力为3-5 GPa),研究高压处理对非晶合金显微组织的影响;并对非晶合金在3.5%NaCl溶液中的电化学性能进行测试.结果表明:室温下的高压处理使该非晶合金发生结构驰豫,从而导致其玻璃转变温度、第一晶化温度及驰豫激活体积发生改变;高压处理后,非晶合金的自腐蚀电位增加,自腐蚀电流密度减小,临界点蚀电位下降,因此,高压处理提高该了非晶合金的抗均匀腐蚀能力,但降低了其抗点蚀的能力.     

Cu-Ti合金在模拟S2-污染海水中的腐蚀行为研究

通过浸泡实验与电化学测试,研究了固溶态Cu-4wt.%Ti合金在模拟污染海水(含S2-的3.5wt.% NaCl溶液)的腐蚀行为。借助扫描电子显微镜(SEM)、X射线衍射(XRD)以及X射线光电子能谱仪(XPS)对铜钛合金表面腐蚀产物进行测试分析。结果表明：含Cl-溶液中铜钛合金的腐蚀形式为点蚀,点蚀坑尺寸较小,分布均匀。添加S2-后点蚀更容易被诱发,点蚀坑尺寸较大。当NaCl溶液中的S2-浓度达到60ppm时,点蚀坑在合金表面相互连接,呈现出均匀腐蚀的形态;S2-<和Cl-对铜钛合金的腐蚀存在竞争吸附,S2-吸附性强对铜钛合金的腐蚀剧烈;在含S2-的NaCl溶液中腐蚀产物主要为CuS、Cu2S、Cu2O以及Cu2(OH)3Cl。S2-浓度较大时会导致溶液中OH-浓度增加,使腐蚀产物膜层厚度与致密度增加,因此当S2-浓度达到100ppm时铜钛合金能够发生钝化从而减缓腐蚀。     

Mg65Cu25Y10非晶态合金的形成及其晶化行为

采用水淬法制备出厚度为2mm的片状Mg65Cu25Y10非晶态合金,衡量其非晶成形能力的参数过冷液态区域宽度△Tx（△Tx=58.3K）、约化玻璃转变温度Trg（Trg=0.56）均较高,表明此合金具有很强的非晶形成能力;并测出了它的硬度为263.2HV.通过恒速升温和等温晶化试验,采用差热分析、X射线衍射等研究了它的热行为,结果表明,此合金在433K以下还是稳定的,如进一步升高温度,材料将由非晶态结构逐步向晶态结构转变,当退火温度达到623K时,则完全转变为晶态结构.     

Evolution of the Corrosion Product Film and Its Effect on the Erosion–Corrosion Behavior of Two Commercial 90Cu–10Ni Tubes in Seawater

The composition and structural evolution of the corrosion product film of two commercial 90Cu–10Ni tubes, namely Tube A and Tube B, after being immersed in natural seawater for 1, 3, and 6 months were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, and its effect on the erosion–corrosion behavior of the tubes was determined through a rotating cylinder electrode system using various electrochemical techniques. For the freshly polished samples used as contrast samples, the flow velocity mainly enhanced the cathodic reaction at low flow velocities while both the anodic and the cathodic reactions were remarkably accelerated at higher flow velocities. The corrosion product films formed on the two commercial 90Cu–10Ni tubes after being immersed in seawater for up to 6 months are of a complex three-layer or multilayer structure. The structural evolution of the films is out of sync for the two tubes. A continuous residual substrate layer depleted of Ni was observed in the inner layer of the films on Tube B after 30, 90, and 180 days' immersion, while it was observed in the film on Tube A only after 180 days' immersion. The nature of the inner layer plays a crucial role in the erosion–corrosion resistance of the 90Cu–10Ni tubes at higher flow velocity. The film with a compact and continuous inner layer of Cu_2O doped with Ni~(2+)and Ni~(3+)which bonds firmly with the substrate could survive and even get repaired with the increased flow velocity. The film on Tube B possessing a hollow and discontinuous inner layer composed of the residual substrate was degraded rapidly with increasing rotation speed in spite of its quite good resistance at the stagnant or lower speed conditions.     

Effects of different inorganic anions on equipment material corrosion behaviour in subcritical water oxidation

In this work, possible corrosion mechanisms of Fe- and Ni-based alloys are discussed which are protected by Cr₂O₃, NiO and MoO₂ surface layers. But chloride ions can dissolve these oxide films and there is a strong synergistic effect between hydronium ions and oxygen, leading to severe local alloy corrosion. On the other hand, titanium and Zr-3 alloys show good corrosion resistance in acidic oxidising subcritical water containing different inorganic salts. A double-layer oxide film (TiO and TiO₂) is formed on the surface of TA2 and TA9 alloys, while a triple oxide layer (TiO, Ti₂O₃ and TiO₂) is formed on TA10 surfaces in such aqueous solutions containing chloride and sulphate ions. In addition to the two oxide layers, Ti₃(PO₄)₄ deposits are also formed on the surface of TA2 and TA9 alloys when the subcritical water contains phosphates. Moreover, (TiO)₂P₂O₇ deposits form besides Ti₃(PO₄)₄ layers on the surface when the TA10 alloy is oxidised under the latter conditions.     

Zr41.2Ti13.8Cu12.5Ni10Be22.5合金凝固过程热力学

利用真空冷壁坩埚感应熔炼及铜模离心铸造的方法制备了大尺寸非晶态Zr41．2Til3．8Cul2．5Ni10Be22．5材料，采用DTA和DSC分别研究了该合金的凝固特性及非晶态晶化行为。结果表明：Zr41．2Til3．8Cul2．5Ni10Be22．5合金具有较低的熔点，表现出良好的深共晶特性，在较低的冷却速度下即可制备出大块部分非晶及全部非晶材料。Zr41．2Til3．8Cul2．5Ni10Be22．5大块非晶材料在339．5℃发生玻璃转变，晶化温度为420℃。     

Sodium monocarboxylates as inhibitors of AZ31 alloy corrosion in a synthetic cooling water

This research investigated the inhibiting effects that sodium salts of linear monocarboxylic acids displayed towards the corrosion process of AZ31 Mg alloy in ASTM D 1387 saline solution (a synthetic industrial cooling water). The length of the aliphatic chain of the acids ranged between 7 and 15 carbon atoms. The inhibiting action of these salts can be related to the precipitation of an insoluble magnesium salt, which mainly affected the anodic reaction. The aliphatic chain length controlled the anion solubility and the reaction rate of magnesium carboxylate formation. For all the salts, an optimum concentration was experienced: 10⁻² M for sodium decanoate (caprate), 10⁻³ M for sodium dodecanoate (laurate), 10⁻⁴ M for sodium tetradecanoate (myristate); when this concentration was exceeded, a diminution (even a disappearance) in the inhibiting action was found.     

CeCl3和苯并三唑对自然时效和人工时效AA2024铝合金耐蚀性的协同效应(英文)

分析自然时效和人工时效AA2024铝合金在0.5 mol/dm³ NaCl溶液中的腐蚀行为,溶液中分别加入环境友好的缓蚀剂:10 mmol/dm³ CeCl₃,10 mmol/dm³ BTA和5 mmol/dm³ CeCl₃+5 mmol/dm³ BTA混合缓蚀剂。本研究的目的是确定混合缓蚀剂的协同效应水平,并解释这种效应的本质。采用电化学阻抗谱(EIS)研究缓蚀剂层的腐蚀性能,通过动电位极化试验研究其抑制点蚀形成和点蚀生长的能力。扫描电子显微镜(SEM/EDS)的结果表明,自然时效铝合金中形成的点蚀尺寸小于人工时效合金中形成的点蚀尺寸。在自然时效合金测试的96 h内以及在人工时效合金测试的后期,均观察到混合缓蚀剂对腐蚀性能的协同效应,但没有发现混合缓蚀剂对点蚀形成和点蚀生长的协同效应。     

Crystallization behavior of amorphous Zr70Cu20Ni10 alloy annealed at 380℃

Crystallization behavior of amorphous Zr70Cu20Ni10 alloy isothermally annealed at 3800℃ was first investigated by employing the differential scanning calorimetry (DSC) and transmission electron microscopy(TEM). It has been found that an exothermic peak appears in the DSC trace when the annealing time is about 17-18min,in dicating a certain phase transformation occurs in the matrix of amorphous Zr70 Cu20 Ni10 alloy.Meanwhile,isothermal annealing experiments for amorphous Zr70Cu20Ni10 alloy ranging from 370℃ to 400℃with a temperature interval of 10℃ were also carried out,from which no exothermic reaction can be observed except for the case of 380℃.This behavior indicates that the phase transformation during isothermal annealing of amorphous Zr70Cu20Ni10 alloy is strongly temperature-and time-dependent.Further investigations are required to reveal the nature of such phenome non.     

扩散温度对TC4合金表面Cu/Ni复合镀层结构及腐蚀性能的影响

论文采用扩散热处理研究了Cu/Ni/Ti复合镀层不同温度下的扩散行为,分析了扩散层结构,并讨论了扩散过程对镀层结构及腐蚀性能的影响。结果表明：由于Cu/Ni/Ti原子之间的互扩散,形成稳定的扩散层,可以有效提高镀层表面耐蚀性能;随着热扩散温度上升到700℃,膜层结构致密,在扩散层中形成了NixTiy金属间化合物及少量的CuxTiy金属间化合物,镀层表面的耐蚀性最好;温度升高到800℃时,在膜层界面处引发了Kirkendall效应,所形成的Kirkendall空位相互聚集长大,形成裂纹或孔洞,使得镀层疏松多孔,从而低了耐蚀性。     

Wear and corrosion properties of laser cladded Cu47Ti34Zr11Ni8/SiC amorphous composite coatings on AZ91D magnesium alloy

To improve the wear and corrosion properties of AZ91D magnesium alloys, Cu-based amorphous composite coatings were fabricated on AZ91D magnesium alloy by laser cladding using mixed powders of Cu47Ti34Zr11Ni8 and SiC. The wear and corrosion behaviours of the coatings were investigated. The wear resistance of the coatings was evaluated under dry sliding wear condition at room temperature. The corrosion resistance of the coatings was tested in 3.5% （mass fraction） NaCl solution. The coatings exhibit excellent wear resistance due to the recombined action of amorphous phase and different intermetallic compounds. The main wear mechanisms of the coatings and the AZ91D sample are different. The former is abrasive wear and the latter is adhesive wear. The coatings compared with AZ91D magnesium alloy also exhibit good corrosion resistance because of the presence of the amorphous phase in the coatings.     

轧制变形量对Zn-3Cu合金显微组织、力学和耐腐蚀性能的影响

本文以Zn-3Cu合金为研究对象。研究了轧制变形量对Zn-3Cu合金的显微组织、力学性能和耐腐蚀性能的影响。研究结果表明,随着轧制变形量的增加,Zn-3Cu合金基体晶粒细化程度不断加深,合金中的CuZn5相沿着轧制方向不断被拉长并出现部分断裂。Zn-3Cu合金的强度先增后减,塑性不断增强,60%变形量的Zn-3Cu合金具有最高的屈服强度,达到了263.1 ± 4.9 MPa。 随着变形量增加,轧态Zn-3Cu合金的耐腐蚀性能逐渐减弱,铸态Zn-3Cu合金表现优异的耐腐蚀性能。     

Effects of solution heat treatment on corrosion resistance of 5083F Al alloy

Aluminum alloys are used as substitutes for fiber reinforced polymer(FRP) in ships and boats. However, ships constructed with 5000-series Al alloy suffer a little corrosion in the marine environment, when they run in high speed, and high flow rate, etc. Therefore, solution heat treatment was carried out to prevent corrosion. The optimal heat treatment involved heating specimens for 120 min at 420 °C and then cooling them in water. In addition, the optimal ageing condition involved ageing specimens for 240 min at 180 °C. The slow strain rate test(SSRT) in a seawater revealed that heat treatment under optimal conditions produced improved elongation, time-to-fracture and amount of dimples compared with the as-received specimen.     

合金元素对Cu60Zr30Ti10合金的非晶形成能力与显微硬度的影响

用铜模吸铸法制备直径2~3 mm的Cu60-xZr30Ti10M2(M=Mg、Al、Sn)系列非晶合金。用X射线衍射、差式扫描量热仪和硬度实验等研究它们的非晶形成能力、热稳定性与显微硬度。该系列非晶合金均表现出两级晶化行为。Cu60Zr30Ti10的玻璃转变温度为426.5℃,晶化起始温度为467.7℃,过冷液相区为41.2℃。添加Mg、Mo、Al对过冷液相区影响比较小,而添加Sn则使过冷液相区明显增大,达到51.6℃,合金的非晶形成能力有较明显提高,热稳定性增强。Cu60Zr30Ti10非晶合金的显微硬度为HV594.3,添加2%(摩尔分数)的Mg、Mo和Al对显微硬度影响不大,而添加2%Sn(摩尔分数)却使显微硬度达到HV755.7,提高27%。