In-situ identification of iron--zinc intermetallics in galvannealed steel coatings and iron oxides on exposed steel

Identification of all the compounds present in various coatings on steels is particularly difficult. Non-destructive, in-situ analysis is necessary if the fraction of each compound as well as its probable layering within the coating, is to be determined. Mössbauer spectroscopy is one valuable probe capable of uniquely identifying all iron compounds which form as coatings on steel and other iron alloy surfaces. To investigate a complete coating several criteria need to be considered. Removing the coating inevitably leaves a small and perhaps important component intact on the substrate. Therefore investigating the coating as it remains intact on the steel is important if complete identification of the iron compounds is to be made. This also preserves crystalline texture or preferred growth orientation within the coating to which the Mössbauer effect is sensitive. Mössbauer spectroscopy is a non-destructive technique which allows the integrity of the coating to be maintained during analysis. The combined transmission and scattering Mössbauer geometries generally result in accurate analysis of the coating composition. For the scattering geometry added information on compound layering is obtained if separate Mössbauer spectra are recorded using the re-emitted gamma rays as well as the conversion electrons and subsequently emitted X-rays. In-situ scattering Mössbauer spectroscopy has been used to characterize the iron--zinc alloys which form in the coatings of commercially produced corrosion resistant galvannealed sheet steel, a product of great interest to automotive producers. The results show that different amounts of four iron--zinc phases are present depending on the production conditions of the coating. The different phases are also distinctly layered. Mössbauer analyses of corrosion coatings formed on the surface of steels which have been exposed to different environments has also been undertaken. Materials include structural steels exposed for up to 25 years in marine, rural and industrial environments, and the interior surfaces of boiler pipes subjected to adverse chemical and temperature environments.     

Zinc-iron phases formed on galvannealed steel

Mössbauer spectroscopy has been used to identify the zinc-iron intermetallic phases present in the coating of three galvannealed steels, two of which were produced on commercial galvanizing lines and one in the laboratory. Both CEMS and XMS have been used in order to determine the depth dependence of each phase. Three main zinc-iron phases have been identified with the proportion of each dependent on the preparation conditions. In the commercially produced coatings, CEMS, probing near the top of the coating, indicates that the zinc rich χ-FeZn₁₃ and δ-FeZn₁₀ alloys are present. XMS indicates the presence of some Π-Fe₃Zn₁₀ closer to the steel. In contrast, the laboratory produced sample contains nearly pure χ-FeZn₁₃ through the entire coating thickness. Subphases of the delta and gamma alloys were also identified. These subphases appear to be mixed with a preference for the higher zinc subphase of each to form closer to the surface of the coating.     

Studies on corrosion protection of Al2024 T6 alloy by electropolymerized polyaniline coating

Aqueous electropolymerized polymer coatings on aluminum alloys can replace the carcinogenic chromate coating. In this work, the corrosion protection ability of electropolymerized polyaniline coating on Al2024 T6 alloy has been found out. The polyaniline coatings on aluminum were formed by galvanostatic and potentiostatic methods from a bath of 0.5 M oxalic acid containing 0.1 M aniline. The corrosion protection ability of the coating was found out by Tafel polarization and EIS in 1% NaCl solution. It has been found that polyaniline coated aluminum alloy has exhibited higher corrosion activity due to the presence of pores in the coating. However, the corrosion resistant property of polyaniline coated aluminum has been found to be improved to 90% by post-treatment in cerium containing solution at 60 °C.     

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。     

Microstructure and properties of 6FeNiCoSiCrAlTi high-entropy alloy coating prepared by laser cladding

The content of each constituent element in the newly developed high-entropy alloys (HEAs) is always restricted in equimolar or near-equimolar ratio in order to avoid the formation of complex brittle phases during the solidification process. In this study, a 6FeNiCoSiCrAlTi high-entropy alloy coating with simple BCC solid solution phase has been prepared by laser cladding on a low carbon steel substrate. The microstructure, hardness and magnetic properties have been investigated. The experimental results show that the tendency of component segregation in the conventional solidification microstructure of multi-component alloy is effectively relieved. The microstructure of the coating is mainly composed of equiaxed polygonal grains, discontinuous interdendritic segregation and nano-precipitates. EBSD observation confirms that the polygonal grains and interdendritic segregation have similar BCC structure with lots of low angle grain boundaries at the interface. The microhardness of the coating reaches 780 HV_0.5, which is much higher than most of the HEAs prepared by other methods. In addition, the coating shows excellent soft magnetic properties.     

Si,Al对激光熔覆MoFeCrTiW高熵合金涂层组织性能的影响

为了提高材料表面的耐磨性和高温抗氧化性,利用激光熔覆技术在Q235钢表面制备了MoFeCrTiW高熵合金涂层,并采用X射线衍射仪(XRD)、扫描电镜(SEM)和磨损试验机等研究了Si,Al添加对高熵合金涂层组织、相结构、耐磨性和高温抗氧化性能的影响。结果表明:激光熔覆MoFeCrTiW高熵合金涂层组织为等轴晶,单独添加等物质的量的Si或Al时,涂层分别为共晶组织或树枝晶,同时添加等物质的量的Si和Al时,涂层组织为细小的等轴晶。各高熵合金涂层的主体相均为BCC相,随着Si,Al的添加,BCC相的晶格常数减小。添加等物质的量的Al有助于抑制涂层中金属间化合物的形成,使涂层耐磨性降低;添加等物质的量的Si则会形成含Si的金属间化合物和一些未知相,提高涂层耐磨性。激光熔覆MoFeCrTiW高熵合金涂层在800℃的抗氧化性较高,Si、Al的添加可使涂层的高温抗氧化性进一步提高。     

Ultrasonic semi-solid coating soldering 6061 aluminum alloys with Sn–Pb–Zn alloys

In this paper, 6061 aluminum alloys were soldered without a flux by the ultrasonic semi-solid coating soldering at a low temperature. According to the analyses, it could be obtained that the following results. The effect of ultrasound on the coating which promoted processes of metallurgical reaction between the components of the solder and 6061 aluminum alloys due to the thermal effect. Al₂Zn₃ was obtained near the interface. When the solder was in semi-solid state, the connection was completed. Ultimately, the interlayer mainly composed of three kinds of microstructure zones: α-Pb solid solution phases, β-Sn phases and Sn–Pb eutectic phases. The strength of the joints was improved significantly with the minimum shear strength approaching 101 MPa.     

Preparation of a novel Ni/Co-based alloy gradient coating on surface of the crystallizer copper alloy by laser

A high wear-resistant gradient coating made of Ni/Co-based alloys on the surface of a Cu alloy substrate was synthesized using a YAG laser induced in situ reaction method. The coating consists of three layers: the first is a Ni-based alloy layer, the second and third are Co-based alloy layers. The microhardness increases gradually from 98 HV in the Cu alloy substrate to the highest level of 876 HV in the third layer. The main phase of the Co-based alloy layer is CoCr₂(Ni,O)₄, coexisting with the Fe₁₃Mo₂B₅, Cr(Co(Mo, and FeCr_0.29Ni_0.16C_0.06 phases. Wear tests indicate that the gradient coating has good bond strength and wear properties with a wear coefficient of 0.31 (0.50 for the Cu alloy substrate). Also, the wear loss of the coating is only 0.01 g after it has been abraded for 60 min, which is only one fifth of that of the Cu alloy of the crystallizer. Wear tests of the gradient coating reveal good adhesive friction and wear properties when sliding against steel under dry conditions. This novel technique may have good application to make an advanced coating on the surface of the Cu alloy crystallizer in a continuous casting process.     

X-ray photoelectron spectroscopy study of the passive films formed on thermally sprayed and wrought Inconel 625

There is a well known performance gap in corrosion resistance between thermally sprayed corrosion resistant coatings and the equivalent bulk materials. Interconnected porosity has an important and well known effect, however there are additional relevant microstructural effects. Previous work has shown that a compositional difference exists between the regions of resolidified and non-melted material that exist in the as-sprayed coatings. The resolidified regions are depleted in oxide forming elements due to formation of oxides during coating deposition. Formation of galvanic cells between these different regions is believed to decrease the corrosion resistance of the coating. In order to increase understanding of the details of this effect, this work uses X-ray photoelectron spectroscopy (XPS) to study the passive films formed on thermally sprayed coatings (HVOF) and bulk Inconel 625, a commercially available corrosion resistant Ni-Cr-Mo-Nb alloy. Passive films produced by potentiodynamic scanning to 400 mV in 0.5 M sulphuric acid were compared with air-formed films. The poorer corrosion performance of the thermally sprayed coatings was attributed to Ni(OH)₂, which forms a loose, non-adherent and therefore non-protective film. The good corrosion resistance of wrought Inconel 625 is due to formation of Cr, Mo and Nb oxides.     

Characterization of surfaces by soft X-ray spectroscopy

Soft X-ray spectroscopy has important capabilities for investigating the surface region of metals and alloys. By calibrating the changes in the soft X-ray emission bands from both the metal and the oxygen, it is possible to determine the oxide thickness, the degree of oxidation, the element in the alloy with which the oxygen has combined, the relative amounts of alloying elements in the surface oxide, and the oxide state of a substrate metal that has a protective coating. For Ti-6Al-4V alloys there was an increase in surface oxygen after prebond treatment which was due to a change in the degree of oxidation rather than in oxide thickness, and the oxygen was combined with the titanium in the surface oxide. The oxygen K intensity distribution, from aluminum that was given a surface chromate treatment, showed that the oxygen is combined with the chromium. In Fe-Cr alloys there is an increase in the amount of chromium combined with oxygen relative to bulk chromium with decreasing chromium content. The oxide surface of steel with a 50 Å metal protective coating was reduced when the oxide of the protective metal coating had a heat formation greater than that of the iron oxide.     

Nanocrystalline soft ferromagnetic Ni-Co-P thin film on Al alloy by low temperature electroless deposition

Soft ferromagnetic ternary Ni-Co-P films were deposited onto Al 6061 alloy from low temperature Ni-Co-P electroless plating bath. The effect of deposition parameters, such as time and pH, on the plating rate of the deposit were examined. The results showed that the plating rate is a function of pH bath and the highest coating thickness can be obtained at pH value from 8 to10. The surface morphology, phase structure and the magnetic properties of the prepared films have been investigated using scanning electron microscopy (SEM), X-ray diffraction analysis (XRD) and vibrating magnetometer device (VMD), respectively. The deposit obtained at optimum conditions showed compact and smooth with nodular grains structure and exhibited high magnetic moments and low coercivety. Potentiodynamic polarization corrosion tests were used to study the general corrosion behavior of Al alloys, Ni-P and Ni-Co-P coatings in 3.5% NaCl solution. It was found that Ni-Co-P coated alloy demonstrated higher corrosion resistance than Ni-P coating containing same percent of P due to the Co addition. The Ni-Co-P coating with a combination of high corrosion resistance, high hardness and excellent magnetic properties would be expected to enlarge the applications of the aluminum alloys.     

The influence of surface microchemistry in protective film formation on multi-phase magnesium alloys

The high strength:weight ratio of magnesium alloys makes them an ideal metal for automotive and aerospace applications where weight reduction is of significant concern. Unfortunately, magnesium alloys are highly susceptible to corrosion particularly in salt-spray conditions. This has limited their use in the automotive and aerospace industries, where exposure to harsh service conditions is unavoidable. The simplest way to avoid corrosion is to coat the magnesium-based substrate by a process such as electroless plating, which is a low-cost, non line of sight process.Magnesium is classified as a difficult to plate metal due to its high reactivity. This means that in the presence of air magnesium very quickly forms a passive oxide layer that must be removed prior to plating. Furthermore, high aluminium content alloys are especially difficult to plate due to the formation of intermetallic species at the grain boundaries, resulting in a non-uniform surface potential across the substrate and thereby further complicating the plating process.The objective of this study is to understand how the magnesium alloy microstructure influences the surface chemistry of the alloy during both pretreatment and immersion copper coating of the substrate.A combination of scanning electron microscopy, energy dispersive spectroscopy and scanning Auger microscopy has been used to study the surface chemistry at the various stages of the coating process. Our results indicate that the surface chemistry of the alloy is different on the aluminum rich β phase of the material compared to the magnesium matrix which leads to preferential deposition of the metal on the aluminum rich phase of the alloy.     

Effect of the high-speed impact of a shaped-charge jet on the strength of titanium alloys

The effect of the high-speed impact of a shaped-charge jet on the structure and strength of commercially pure VT1 titanium and VT22, VT3-1, and PT-3V titanium alloys is studied in comparison with AK6 aluminum alloy and Br OTsS bronze. The strength is characterized in terms of the microhardness. The microhardness versus structure is analyzed in the near-surface layer along the channel formed by the shaped-charge jet. The results obtained are used to qualitatively estimate the structural modification, type of fracture, and strength of targets made of the alloys.     

二次铝灰中氟氮物相的光谱分析

二次铝灰是电解铝、铝加工、铝回收行业产生的危险废物,不同生产过程排放的二次铝灰具有矿相复杂、化学组成波动大的特点,造成现有处置技术对各类二次铝灰的处理效果差异较大,资源化利用率低。通过明确典型铝合金生产过程排放二次铝灰中含氮、含氟物相等毒害组分的赋存形态及分布规律,判断氟氮物相形成途径,有利于开发高适性的二次铝灰无害化技术,实现二次铝灰中毒害组分和有价组分的高效分离,有效解决其资源化利用难题。结合化学与仪器分析,利用X射线衍射、 X射线荧光光谱定量研究了生产过程中不同系列三种铝合金产生的二次铝灰中含氟物相、含氮物相等物相含量,采用X射线光电子能谱、扫描电子显微镜与能谱系统分析氟、氮元素的结合形态和分布特征。结果表明,使用光谱分析方法与化学分析方法对二次铝灰中氮化物、氟化物的定量检测结果基本相符。铝-硅、铝-镁、铝-镁-硅三种系列铝合金生产过程得到的二次铝灰中含氮物相含量为4.30%～5.48%,含氮物相均主要以AlN形式存在,由生产过程中铝熔体与氮气反应生成物进入二次铝灰。AlN主要分布在体相中,颗粒形貌呈球端条状或棱块状,以游离单独颗粒或与含铝物相连生的形式存在;二次铝灰中含氟物相含...     

基于XGBoost的铝合金LIBS光谱分类识别方法

铝合金作为重要的金属材料,广泛应用于各领域,但大量的铝合金废料却难以进行分类回收。二次资源的回收利用是我国工业绿色、可持续发展的助推器,如何快速、简便地对铝合金废料进行识别分类则成为了铝合金废料回收利用的先决条件。激光诱导击穿光谱（LIBS）是近年来发展快速的一种分析技术,具有快速、全元素分析、实时、原位、远距离检测等优点,已广泛应用于塑料、土壤、肉类、钢铁等识别研究,大多采用最小二乘判别分析法、簇类独立软模式、人工神经网络、支持向量机、随机森林等算法来建立模型。基于迭代型树的XGBoost算法具有正则化、并行处理运算、内置交叉验证和高度的算法灵活性等优势,其模型结构相对简单、运算量较小,且准确率较高,成为近年来机器学习中极受欢迎的算法,因而被广泛应用。基于六种铝合金样品的600组光谱数据,根据NIST原子发射光谱数据库进行光谱特征提取,确定光谱特征谱线的分类依据。利用XGBoost算法进行自动分类及排序,将处理后的光谱数据随机划分为训练集和测试集,通过训练集构建算法模型,提取其分类特征;利用测试集检验模型的稳定性和可用性,防止出现过拟合。XGBoost在固定参数下得到的模型具有一定的自适应性,较少受数据集的影响,总体准确率可达96.67%。其分类特征与已知的元素含量信息相吻合,证明了基于光谱的特征谱线数据,可为分类识别提供参考;同时还可根据XGBoost生成的特征评分来对光谱谱线特征的重要性进行排序。实验结果表明,LIBS可用于不同种类铝合金的快速识别,为废弃金属的分类回收提供了一种新的技术。     

Heat treatment induced intermetallic phase transition of arc-sprayed coating prepared by the wires combination of aluminum-cathode and steel-anode

A method to prepare intermetallic composite coatings employing the cost-efficient electric arc spraying twin wires assistant with suitable heat treatment was developed. In this study, a Fe-Al composite coating was produced by spraying twin wires, i.e. a carbon steel wire as the anode and an aluminum wire as the cathode. The inter-deposited Fe-Al coating was transformed in-situ to Fe-Al intermetallic composite coating after a post annealing treatment. The effect of annealing treatment conditions on phase composition, microstructure and mechanical properties of the coating was investigated by using XRD, SEM, EDS and OM as well as microhardness tester. The results show that the desirable intermetallic phases such as Fe₂Al₅, FeAl and Fe₃Al are obtained under the annealing condition. The main oxide in the coating is FeO which can partially transform to Fe₃O₄ up to the annealing condition.     

Al–Cu intermetallic coatings processed by sequential metalorganic chemical vapour deposition and post-deposition annealing

Sequential processing of aluminum and copper followed by reactive diffusion annealing is used as a paradigm for the metalorganic chemical vapour deposition (MOCVD) of coatings containing intermetallic alloys. Dimethylethylamine alane and copper N,N′-di-isopropylacetamidinate are used as aluminum and copper precursors, respectively. Deposition is performed on steel and silica substrates at 1.33 kPa and 493–513 K. Different overall compositions in the entire range of the Al–Cu phase diagram are obtained by varying the relative thickness of the two elemental layers while maintaining the overall thickness of the coating close to 1 μm. As-deposited films present a rough morphology attributed to the difficulty of copper to nucleate on aluminum. Post-deposition annealing is monitored by in situ X-ray diffraction, and allows smoothening the microstructure and identifying conditions leading to several Al–Cu phases. Our results establish a proof of principle following which MOCVD of metallic alloys is feasible, and are expected to extend the materials pool for numerous applications, with innovative thin film processing on, and surface properties of complex in shape parts.     

High-resolution valence band XPS studies of thin film Au–Al alloys

The Maximum Entropy Method (MEM) has been used to deconvolute the valence-band XPS spectra of thin film Au–Al alloys. The enhanced resolution allows fine changes in the electronic structures of the thin film alloys to be distinguished with the aid of the Au4f core-level spectra. This particular alloy series allows one to examine the 5d electronic interaction between gold atoms as aluminum is gradually added to the matrix. Aluminum is shown to have a much stronger quenching effect on such interactions than has been found previously for copper.     

Mössbauer and XRD study of hot dip galvanized alloy

Mössbauer spectroscopy has been used to investigate the nature of the Zinc-Iron alloys present within the Hot Dip Galvanized (HDG) layers of steel with a silicon content of 0.35 %. The investigation also studied the impact of the powder coating pretreatment on the nature of the alloy layers. The acid etching process within the pretreatment process in particular would be expected to have a significant impact on the HDG layer. This study utilized ⁵⁷Fe Mössbauer spectroscopy to examine identically processed samples prior to and post pre treatment. XRD and ⁵⁷Fe CEMS measurements were performed on hot galvanized S355J2 + N samples, forming sandwiched structure. Both XRD and CEMS reveal the presence of dominant steel phase in accordance with its estimated occurrence on the surface of the sandwiched samples. Minor Γ-Fe3Zn10, ζ-FeZn15 and solid solution Fe-Zn as well as minor Fe-Si phases could also be identified.     

Nano-Fabrication by Cathodic Plasma Electrolysis

Cathodic plasma electrolytic (CPE) techniques are new groups of coating processes, which can be used for fabrication of nanostructured layers on surface of a wide range of metallic substrates. The most exciting visible feature of these atmospheric-based plasma techniques is continuous sparking on processed surface inside an electrolyte. Unlike the anodic part of plasma electrolysis (usually known as plasma electrolytic oxidation (PEO) or micro arc oxidation (MAO)), which is commonly used for oxidation of light metals/alloys such as aluminum, titanium and magnesium, CPE techniques can clean and coat different metals and alloys such as steel, copper, and light metals/alloys with formation of wide range of nanostructures including complex carbides, carbonitrides, intermetallics, and even oxides. It has been observed that the properties of obtained layers depend on the characteristics of achieved nanostructures such as average size, distribution and average coordination number of nanocrystallites. Furthermore, the properties of the processed surface can be tailored by tailoring the nanostructure characteristics. There is limited literature available on the mechanism of CPE and its connection to the morphology of nanostructured layers. This article addresses the two important aspects of CPE, namely characterization of nanostructured layers and mechanism of cathodic plasma electrolysis, which are reviewed in accordance to the morphology of fabricated nanostructures.