Electrochemical, SEM/EDS and quantum chemical study of phthalocyanines as corrosion inhibitors for mild steel in 1 mol/l HCl

The inhibition effect of metal-free phthalocyanine (H₂Pc), copper phthalocyanine (CuPc) and copper phthalocyanine tetrasulfuric tetrasodium salt (CuPc·S₄·Na₄) on mild steel in 1 mol/l HCl in the concentration range of 1.0 × 10⁻⁵ to 1.0 × 10⁻³ mol/l was investigated by electrochemical test, scanning electron microscope with energy dispersive spectrometer (SEM/EDS) and quantum chemical method. The potentiodynamic polarization curves of mild steel in hydrochloric acid containing these compounds showed both cathodic and anodic processes of steel corrosion were suppressed, and the Nyquist plots of impedance expressed mainly as a capacitive loop with different compounds and concentrations. For all these phthalocyanines, the inhibition efficiency increased with the increase in inhibitor concentration, while the inhibition efficiencies for these three phthalocyanines with the same concentration decreased in the order of CuPc·S₄·Na₄ > CuPc > H₂Pc according to the electrochemical measurement results. The SEM/EDS analysis indicated that there are more lightly corroded and oxidative steel surface for the specimens after immersion in acid solution containing 1.0 × 10⁻³ mol/l phthalocyanines than that in blank. The quantum chemical calculation results showed that the inhibition efficiency of these phthalocyanines increased with decrease in molecule's LUMO energy, which was different from the micro-cyclic compounds.     

Influence of annealing treatment on the microstructure and mechanical performance of cold sprayed 304 stainless steel coating

In this study, 304 stainless steel coatings were deposited on interstitial-free steel substrate by cold spraying method. The effect of annealing treatment on microstructure, microhardness, ultimate tensile strength and fracture performance of the coatings were studied. The results showed that annealing treatment had made a dominant contribution to heal up the incomplete interfaces between the deposited particles. Both of the microstructure and the mechanical properties have been obviously optimized by annealing treatment. In addition, the coating microhardness decreased from 345 HV_0.2 for the as-sprayed coating to 201 HV_0.2 for the annealed coating. The coating ultimate tensile strength increased from 65 MPa for the as-sprayed coating to 357 MPa for the annealed coating, which resulted from the increase of the metallurgically bonded areas in the coating induced by annealing treatment. Fracture morphology of the coatings also revealed that annealing treatment changed the fracture character of the cold sprayed 304 stainless steel coating from brittle type to plastic type.     

Micro‐Raman spectroscopy and VP‐SEM/EDS applied to the identification of mineral particles and fibres in histological sections

Histological sections of a patient affected by an important respiratory disease were analysed firstly by optical microscope(OM)—crossed polarisers—to identify the presence of incorporated inorganic particles, with particular attention to the fibrous ones. Then, the particles/fibres that were found were studied both with micro‐Raman spectroscopy and variable‐pressure scanning electron microscopy with energy‐dispersive spectroscopy (VP‐SEM/EDS). The two techniques allowed the in situ characterisation of the inorganic phases without disintegration of the organic matter. Micro‐Raman spectroscopy was able to identify the vibrating chemical groups of the mineral phase associated with the inorganic grain while the crystalline structure was preserved by the biological system. The VP‐SEM/EDS characterisation, defining the elemental chemical composition of the analysed particle/fibre, allowed confirmation of the mineral phase deducible from spectroscopic data or its identification with certainty when the spectroscopic data were not exhaustive. Copyright © 2009 John Wiley & Sons, Ltd.     

The effect of deposition temperature on the surface coverage and morphology of iron-phosphate coatings on low carbon steel

The influence of deposition temperature and concentration of NaNO₂ in the phosphating bath on the surface morphology and coverage of iron-phosphate coatings on low carbon steel was investigated. The phosphate coatings were chemically deposited on steel from phosphate bath at different temperatures (30-70 °C) and with the addition of different amounts of accelerator, NaNO₂ (0.1, 0.5 and 1.0 g dm⁻³). The morphology of phosphate coatings was investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The composition of iron-phosphate coatings was determined using energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). Surface coverage was evaluated by the voltammetric anodic dissolution (VAD) technique.It was shown that the increase in temperature of the NaNO₂-free phosphating bath up to 70 °C caused an increase in surface coverage. The addition of NaNO₂ in the phosphating bath significantly increased the surface coverage of phosphate coatings deposited at temperatures lower than 50 °C. The phosphate crystals were of laminated and needle-like structures for deposits obtained at temperatures lower than 50 °C, while at higher temperatures needle-like structure was transformed to laminated structure. The increase in NaNO₂ concentration in the phosphating bath from 0.1 to 1.0 g dm⁻³ did not significantly increase the surface coverage, but decreased the crystals size, consequently favouring the phosphate nucleation and better packing of the crystals.     

Effect of spraying power on the microstructure and mechanical properties of supersonic plasma-sprayed Ni-based alloy coatings

The aim of this paper was to investigate the microstructure and mechanical properties of the supersonic plasma-sprayed Ni-Cr-B-Si-C coatings prepared at different spraying powers. The microstructure, phase composition, porosity, Young's modulus, micro-hardness, and residual stresses of the coatings were investigated and determined. The variations of the porosity, Young's modulus and micro-hardness of the coatings were evaluated by using statistical method. Results showed that the variations of porosity, Young's modulus and micro-hardness of the coatings followed the Weibull distributions. With increasing the porosity, the micro-hardness and Young's modulus of the coating decreased. The mean value of the Young's modulus of the coating calculated from Weibull plot was almost proportional to the square root of the micro-hardness of the coating. With increasing the power, Young's modulus of the coating increased, which, in turn, resulted in the increment of the residual stress at the coating surface.     

Laser surface remelting of plasma sprayed nanostructured Al2O3-13wt%TiO2 coatings on titanium alloy

Plasma sprayed nanostructured coatings were successfully fabricated on a titanium alloy (Ti-6Al-4V) substrate using the as-prepared nanostructured Al₂O₃-13wt%TiO₂ feedstock. A CO₂ laser was used to remelt the plasma sprayed coatings. The effects of laser remelting on the phase constituents, microstructure and properties of the ceramic coatings were investigated. The laser remelted coatings (LRmC) possessed a much denser and more homogenous structure and excellent metallurgical bonding to the substrate. The average porosity of the LRmC was reduced to 0.9%, compared with 6.2% of the as-sprayed coatings. The net-like structure in the as-prepared feedstock remained in the coatings before and after laser remelting. The metastable γ-Al₂O₃ phase in the as-sprayed coatings transformed to stable α-Al₂O₃ during laser remelting. The LRmC could remain nanostructure. The microhardness of the coatings was enhanced to 1000-1400 HV_0.3 after laser remelting, which was much higher than that of the plasma sprayed coatings and 2-3 times higher that of the substrate. Significant decreases in surface roughness were also found in the LRmC.     

H13钢激光熔覆Co基涂层组织及热疲劳性能

针对热作模具用H13钢工况下易产生热疲劳失效的问题,采用Nd:YAG激光器在H13钢表面制备Co基合金涂层。利用光学显微镜、扫描电镜、能谱仪和X射线衍射仪,对涂层组织、合金元素分布及物相组成进行检测。利用显微硬度计和热震实验法,测试热疲劳对Co基合金涂层和淬火回火态H13钢硬度影响。结果表明,Co基合金涂层从底部到表层,依次为平面晶、胞状晶、树枝晶和等轴晶。Co基合金涂层物相主要由-Co和M23C6相组成,热疲劳后涂层表面形成M2O3和M3O4(M=Fe,Co,Cr)氧化物。Co基合金涂层硬度最高可达706HV0.2且呈梯度降低;热循环1000次后,Co基合金涂层表面硬度降低24.4%,H13钢表面硬度降低37.7%,Co基合金涂层硬度下降幅度低于H13钢。热循环1000次后,Co基合金涂层表面未发现明显热裂纹,H13钢表面形成大量网状热裂纹。Co基合金涂层中,Cr元素形成致密Cr2O3氧化膜使其热疲劳性能优于H13钢。     

Influence of annealing temperature on the nanostructure and corrosivity of Ti/stainless steel substrates

Titanium films of 80 nm thickness were deposited on stainless steel type 304, and they were post-annealed under flow of oxygen at different temperatures. The prepared samples were corrosion tested in 1.0 M H₂SO₄ solution using potentiodynamic and galvanometric polarization technique. The variation of corrosion resistance of these samples showed that the optimum annealing temperature is 473 K. The reduction of corrosion resistance of the sample with increasing the temperature above 473 K is attributed to the phenomena which are confirmed by AFM results: (a) increase of surface roughness, and (b) formation of larger grains with large grooves between them on the film surface. Hence larger effective surfaces for chemical reactions are provided. The films’ crystallographic and morphological structures were analysed using XRD and AFM, respectively before corrosion test and SEM after corrosion test. It is observed that the crystallographic structure of the film goes through a sudden change at 943 K annealing temperature and three phases of titanium oxide (i.e., rutile, anatase and brookite) are formed.     

Wear resistance of reactive plasma sprayed and laser remelted TiB2-TiC0.3N0.7 based composite coatings against medium carbon steel

Wear resistance of reactive plasma sprayed TiB₂-TiC_0.3N_0.7 based composite coatings and the as-sprayed coating with laser surface treatment was investigated using plate-on-plate tests. Wear tests were performed at different normal loads and sliding speeds under dry sliding conditions in air. The surface morphologies of counterparts against as-sprayed and laser remelted coatings were investigated. The microstructure and chemical composition of wear debris and coatings were studied using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS), respectively. The results show that the wear resistance of the laser remelted coating is improved significantly due to their increased microhardness and reduced flaws. The primary wear mechanism of the remelted coating is oxidation wear and its minor wear mechanisms are grain abrasion and fatigue failure during the course of wear test. In contrast, the primary wear mechanism of the as-sprayed coating is grain abrasion at the low sliding speed (370 rpm) and fatigue failure at the high sliding speed (549 rpm). The oxidation wear mechanism is a minor contributor for the as-sprayed coating.     

Electroless Ni-P/Ni-B duplex coatings for improving the hardness and the corrosion resistance of AZ91D magnesium alloy

The Ni-P/Ni-B duplex coatings were deposited on AZ91D magnesium alloy by electroless plating process and their structure, morphology, microhardness and corrosion resistance were evaluated. The duplex coatings were prepared using dual baths (acidic hypophosphite- and alkaline borohydride-reduced electroless nickel baths) with Ni-P as the inner layer. The coatings were amorphous in as-plated condition and crystallized and produced nickel borides upon heat-treatment. SEM observations showed that the duplex interface on the magnesium alloy was uniform and the compatibility between the layers was good. The Ni-P/Ni-B coatings microhardness and corrosion resistance of having Ni-B coating as the outer layer was higher than Ni-P coatings. The Ni-P/Ni-B duplex coatings on AZ91D magnesium alloy with high hardness and good corrosion resistance properties would expand their scope of applications.     

Adsorption behavior and mechanism of multiple Mg atoms on the surface of AlNi compound at Mg alloy/steel interface

The interface between Mg alloy and the intermetallic compounds (IMCs) is the weak point during the welding of Mg alloy and steel. The models of AlNi surface under different number of absorbed magnesium atoms were established. The absorption energy and electronic properties of the Nth (N represents the number of Mg atoms, which may be 1, 2, 3, and 4 in this paper) Mg atom on the AlNi surface were calculated using first-principles calculations. The results show that the previously absorbed Mg atoms will promote the absorption of the latter Mg atom when the distance between them is equal or less than 2.89 Å. The absorption energy of the Mg atoms on the AlNi surface is related to the electronic exchange between different atoms. The results will provide a new perspective for understanding the atomic scale mechanism of the bonding between the Mg atom and AlNi IMCs.     

基于SEM与FTIR研究改性钢渣/橡胶复合材料的热氧老化机理

钢渣是冶金工业中产生的主要固体废弃物,其产量约为每年粗钢产量的15%~20%。由于技术的局限,导致我国钢渣利用率较低,仅为年钢渣产量的10%,同时加之管理制度的不健全,导致钢渣大量露天堆放,对土地资源、地下水源,以及空气质量形成严重影响。面对上述问题,以热闷渣、电炉渣和风淬渣研发改性钢渣微粉,并且将改性钢渣微粉与复合橡胶进行复合制备改性钢渣/橡胶复合材料。依据《硫化橡胶或热塑性橡胶热空气加速老化和耐热试验》（GB/T3512—2014）对改性钢渣/橡胶复合材料进行热氧老化处理,采用平衡溶胀法测定改性钢渣/橡胶复合材料的交联密度,扫描电子显微镜（SEM）、热重分析仪（TGA）和傅里叶转换红外光谱仪（FTIR）分别测试其微观形貌、失重率和结构组成,从微观层面阐述改性钢渣/橡胶复合材料的热氧老化机理。结果表明在热氧老化前期老化作用在改性钢渣/橡胶复合材料表面,其内部以交联键形成反应为主;在热氧老化中期老化作用已经作用改性钢渣/橡胶复合材料内部,造成交联键断裂反应速度高于交联键形成反应速度,形成大量断裂交联键;在热氧老化后期由于改性钢渣/橡胶复合材料内部已经存在大量断裂交联键,导致主链及交联键断裂速度降低,交联键形成反应占优势。改性钢渣微粉以热闷渣（SiO₂含量高）为原材料,有利于形成聚合物大分子链贯穿炭黑网络的结构,提高综合性能,尤其是物理机械性与滞后性;以电炉渣、风淬渣（Fe₂O₃含量高）制备改性钢渣微粉,有利于热传导性能的改善,不仅提高改性钢渣/橡胶复合材料的耐热性,而且提高其硬度与脆性。热氧老化过程中改性钢渣/橡胶复合材料内部在橡胶分子链α-H上发生了不同程度的氧化反应,并在橡胶分子链周围生成了羟基、羧基和醇类化合物,双键烯氢含量降低。     

Fretting wear behaviour of microarc oxidation coatings formed on titanium alloy against steel in unlubrication and oil lubrication

Ceramic coatings were formed on Ti6Al4V alloy surface by microarc oxidation (MAO) in a Na₂SiO₃ system solution. Unlubricated, smear oil and oil bath lubricated fretting tests were performed on MAO coatings against 52100 steel on a fretting wear tester. Microstructural investigation of the worn surfaces was performed and the wear mechanisms were studied. The results show that the coatings are mainly composed of rutile and a small amount of anatase TiO₂, both in nano grain structure. Friction coefficient of microarc oxidation coatings under oil bath lubrication was significantly reduced, favorable stable at 0.15, which indicates that the coatings with oil lubricated lowered the shear and adhesive stresses between contact surfaces, consequently alleviating the possibility of initiation and propagation of cracks in the inner layer of the coating or titanium alloy substrate.     

Effect of α-Al2O3 on the properties of cold sprayed Al/α-Al2O3 composite coatings on AZ91D magnesium alloy

Composite coatings using pure Al powder blended with α-Al₂O₃ as feedstock were deposited on AZ91D magnesium alloy substrates by cold spray (CS). The content of α-Al₂O₃ in the feedstock was 25 wt.% and 50 wt.%, respectively. The effects of α-Al₂O₃ on the porosity, microhardness, adhesion and tensile strength of the coatings were studied. Electrochemical tests were carried out in neutral 3.5 wt.% NaCl solution to evaluate the effect of α-Al₂O₃ on the corrosion behavior of the coatings. The results showed that the composite coatings possessed lower porosity, higher adhesion strength and tensile strength than cold sprayed pure Al coating. The corrosion current densities of the composite coatings were similar to that of the pure Al coating and much higher than that of bare AZ91D magnesium alloy.     

High-temperature oxidation studies of cold-sprayed Ni-20Cr and Ni-50Cr coatings on SAE 213-T22 boiler steel

The high-temperature oxidation behavior of cold-sprayed Ni-20Cr and Ni-50Cr coatings on SAE 213-T22 boiler steel has been investigated at 900 °C in air under cyclic heating and cooling conditions for 50 cycles. The kinetics of oxidation of coated and bare boiler steel has been established with the help of weight change measurements. It was observed that all the coated and bare steels obeyed parabolic rate law of oxidation. X-ray diffraction, FE-SEM/EDAX and X-ray mapping techniques were used to analyse the oxidation products of the coated and uncoated boiler steel. The uncoated steel suffered corrosion in the form of intense spalling and peeling of its oxide scale, which was perhaps due to the formation of unprotective Fe₂O₃ oxide scale. Both the coatings showed better resistance to the air oxidation as compared to the uncoated steel. The Ni-50Cr coating was found to be more protective than the Ni-20Cr-coated steel. The formation of oxides and spinels of nickel and chromium may be contributing to the development of air oxidation resistance in the coatings.     

液态三元Fe-Sn-Si/Ge偏晶合金相分离过程的实验和模拟研究

本文采用自由落体实验技术和格子玻尔兹曼计算方法研究了低重力条件下液态Fe-Sn-Si/Ge合金的相分离过程. 实验发现, 二种合金液滴在自由下落过程中均发生显著的液相分离, 形成了壳核和弥散组织. 当Fe-Sn-Si合金中的Si元素被等量的Ge元素替换后, 壳核组织中富Fe区和富Sn区的分布次序会发生反转. 计算表明, 在液相分离过程中冷却速率、Marangoni对流和表面偏析对壳核构型的选择和弥散组织的形成起决定性作用.     

Effect of spraying power on microstructure and bonding strength of MoSi2-based coatings prepared by supersonic plasma spraying

MoSi₂-based oxidation protective coatings for SiC-coated carbon/carbon composites were prepared using a supersonic plasma spraying at the power of 40 kW, 45 kW, 50 kW and 55 kW, respectively. Effect of spraying power on the microstructure and bonding strength of MoSi₂-based coatings was studied. The results show that coatings become more and more compact and the bonding strength increases when the spraying power increases from 40 kW to 50 kW. At the power of 50 kW, the coatings were dense and the bonding strength reached a maximum value of 14.5 MPa. As the spraying power is of sufficient magnitude, many cracks and pores reappaer in coatings and the bonding strength between coating and substrate also decreases.     

Influence of heat treatment on tribological properties of electroless Ni-P and Ni-P-Al2O3 coatings on Al-Si casting alloy

Evolution of tribological properties of electroless Ni-P and Ni-P-Al₂O₃ coating on an Al-10Si-0.3Mg casting alloy during heat treatment is investigated in this work. The pre-treated substrate was plated using a bath containing nickel hypophosphite, nickel lactate and lactic acid. For preparation of fiber-reinforced coating Al₂O₃ Saffil fibers pre-treated in demineralised water were used. The coated samples were heat treated at 400-550 °C/1-8 h. Tribological properties were studied using the pin-on-disc method. It is found that the best coating performance is obtained using optimal heat treatment regime (400 °C/1 h). Annealing at higher temperatures (450 °C and above) leads to the formation of intermetallic compounds that reduce the coating wear resistance. The reason is that the intermetallic phases adversely affect the coating adherence to the substrate. The analysis of wear tracks proves that abrasion is major wear mechanism, however due to the formed intermetallic sub-layers, partial coating delamination may occur during the pin-on-disc test on the samples annealed at 450 °C and above. It was found that fiber reinforcement reduces this scaling and increases wear resistance of coatings as compared to the non-reinforced Ni-P coatings.     

Corrosion and wear properties of PEO coatings formed on AM60B alloy in NaAlO2 electrolytes

Coatings with a thickness of 22-32 μm were formed on an AM60B magnesium alloy by plasma electrolytic oxidation (PEO) in electrolytes containing 12.0-24.0 g/l NaAlO₂ and other additives. SEM analyses of the coated samples showed that the coatings were compact with relatively low porosity. X-ray diffraction revealed that the coatings consisted of mainly MgAl₂O₄ and MgO phases. The relative amount of MgAl₂O₄ in the coating increased with increasing NaAlO₂ concentration. The relatively compact and thick coatings provide good corrosion protection for magnesium, as indicated by the results of potentiodynamic polarization tests. In addition, the PEO treatment also significantly improved the wear resistance of the alloy. Pin-on-disk wear tests showed that the PEO treatment reduced the wear volume loss by a factor of 10.     

The resistance to wear and corrosion of laser-cladding Al2O3 ceramic coating on Mg alloy

The paper presents a study on the preparation of Al₂O₃ ceramic coating on AZ91HP Mg alloy by laser remelting plasma-sprayed coating. It was found that after laser remelting, the coating exhibited obvious layer-like characteristics due to influence of temperature distribution, thermophysical parameters and layer thickness. According to the microstructural difference, the coating can be divided into the melted zone with the α-Al₂O₃ column-like crystal, the sintered zone with flock-like structure, the residual plasma-sprayed zone with loosened structure. Because of the dense column-like crystal, the hardness, wear and corrosion resistance of the laser remelted coating are much higher than those of the plasma-sprayed coating and as-received Mg alloy.