Long-term oxidation kinetics of aluminide coatings on alloy steels by low temperature pack cementation process

The long-term oxidation kinetics of the P92 steel and iron aluminide diffusion coating formed on its surface by the pack cementation process have been investigated at 650 °C over a period of more than 7000 h both in 100% steam and in air under normal one atmospheric pressure by intermittent weight measurement at room temperature. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques were used to analyse the oxidised surfaces. For the P92 steel substrate, the scale formed by oxidation is largely magnetite (Fe₃O₄) in steam and haematite (Fe₂O₃) in air. Despite this difference in the type of oxide scales formed, it was found that the long-term oxidation kinetics of the P92 steel substrate in both steam and air can be described by a logarithmic time relationship: Δm _t = k _lln(t/t° + 1); the constants k _l and t° were subsequently determined using a closest fit process for oxidations in steam and air. For the coating, the oxide scale formed in both steam and air was Al₂O₃, which provided the long-term oxidation resistance. It was observed that the long-term oxidation kinetics of the coating in both steam and air can be best described by Δm _t = Δm ₀ + k _c t ^1/3; the rate constant k _c of oxidation in steam and air was then determined by the least squares method. For both the P92 steel substrate and coating, the rate of oxidation is faster in steam than in air at 650 °C particularly in the case of the P92 steel substrate.     

Deposition of silicon modified aluminide coatings on nickel base superalloys by pack cementation process

Abstract

The equilibrium partial pressures of vapour species generated in halide activated pack powder mixtures at high temperatures were calculated for a series of compositions using thermochemical analysis tools. The results obtained were applied to identify suitable activators and pack compositions for codepositing Al and Si to form diffusion coatings on nickel base superalloys by the pack cementation process. The calculation results suggested that compositions of the packpowder mixtures activated by CrCl₃.6H₂O may be adjusted to create deposition conditions favourable for codepositing Al and Si, but, those activated byAlF₃or AlCl₃ may only deposit Al.A series of coating deposition experiments were also carried out at 1000 ° C and 1100 ° C and the results obtained confirmed that, with adequate control of pack compositions and deposition conditions, codeposition of Al and Si can be achieved with CrCl₃.6H₂O activated pack powder mixtures. A mixture of elemental Al and Si powders may be used as a depositing source instead of using Al-Si master alloy powders as conventionally recommended. The coatings could be formed either through the inward diffusions of Al and Si or through the outward diffusion of Ni together with other substrate elements such as Cr and Co, depending on the deposition temperature used. Prolonged deposition at 1100 ° C ledtothe formationofa coatingwith amultilayeredstructure consistingofanouter nickelsilicide layerand a middle Simodified NiAl layer followed by a diffusion zone. The pack compositions and deposition conditions may be adjusted to control the microstructure of the coatings formed by the codeposition process.     

Low temperature aluminisation of alloy steels by pack cementation process

Abstract

The pack aluminisation process is normally applied at temperatures >973 K at which the mechanical properties of alloy steels would degrade. Thus, the present study was undertaken to apply this process to aluminising the alloy steels at temperatures <973 K in order to increase their high temperature oxidation resistance while maintaining their microstructure and hence mechanical strength and creep resistance. A type of commercial alloy steel P92 (9Cr–1Mo) was used for the present study. Pack powder mixtures consisting of Al, AlCl₃ (anhydrous) or NH₄Cl and Al₂O₃ were used to carry out the process. The aluminising temperature was varied from 773 to 973 K, pack Al content from 1 to 30 wt-% and aluminising time from 1 to 16 h to investigate their effects on the coating growth kinetics in the AlCl₃ activated packs. It was observed that all the coatings formed in the AlCl₃ activated packs were of a single layer structure with Fe₂Al₅ as the main coating phase. It was established that the interrelationship between the thickness h (in μm) of this coating layer and aluminising temperature T (in K), time t (in h) and pack Al content W (in wt-%) can be described by h=83005·9W^1/2t^1/2e^?73330/(RT). In the NH₄Cl activated packs, it was found that coating formation and dissolution took place simultaneously at 923 K and stable growth of a coating layer was only possible when the pack Al content was sufficiently high. However, the coatings formed in these packs had highly uneven regions.     

活化剂对渗铬层结构和成分的影响

采用粉末包埋法,分别以氯化铵、氯化钠、氯化镍为活化剂在镍基高温合金上于950℃进行了渗铬处理。扫描电镜和能谱分析结果表明,以氯化铵或氯化钠为活化剂得到的渗铬层以向外生长模式为主,但前者在与基体界面处夹杂氮/氧化物颗粒较多,同时含有高达约11.4%(质量分数)的Fe杂质,而后者在与基体界面处夹杂较少,渗铬层Fe含量仅为约1.4%(质量分数),远低于前者。以氯化镍为活化剂得到的渗铬层则以向内扩散为主,与基体无明显界面,但Ni及杂质Fe(19.7%(质量分数))含量最高。氯化钠表现出净化渗铬层成分的作用,而氯化镍具有增强与基体互扩散的作用,因此,活化剂种类对渗铬层成分及结构具有重要影响。     

The effect of the deposition temperature and activator concentration on the structure of NiCrBSi coatings deposited on low carbon steels by pack cementation process

The feasibility of NiCrBSi powder deposition on low alloy steels with pack cementation is investigated at different temperatures (800-1000 °C) and with various halide salt activator content in the pack powder (1-6 wt.%), while the deposition time was set at 4 h. The as-coated samples were examined with Scanning Electron Microscopy (SEM) associated with Energy Dispersive Spectroscopy (EDS), and X-Ray diffraction analysis (XRD). It was revealed that both parameters affect the coating thickness, but not the phase composition of the as deposited coating, which in every case is composed by a Cr₂O₃ thin layer on the top, which enhances the corrosion resistance and Cr-B, Ni-B and Fe-Ni phases in the rest of the coating which increase the hardness and wear resistance. The activator content has also effect on the coating quality and integrity. In cases where its concentration is low or at higher levels (> 6%wt.) the as formed coatings are inhomogeneous and of low cohesion.     

包埋法制备TiC内涂层的影响因素分析

用包埋法制备了碳/碳复合材料TiC内涂层.对制备涂层的影响因素进行了分析.最终确定的制备条件为制备温度2173K、保温时间为2h、Ti和C的配比为3:1.     

Aluminide coating formation on nickel-base superalloys by pack cementation process

A detailed study was carried out to investigate the effects of pack powder compositions, coating temperature and time on the aluminide coating formation process on a superalloy CMSX-4 by pack cementation. With the aid of recently developed thermodynamic analytical tools, powder mixtures that are activated by a series of fluoride and chloride salts were analysed and the effectiveness of these activators in transferring and depositing Al was evaluated at a range of coating temperatures. The Al chloride vapours formed at coating temperatures from 900°C to 1100°C were also analysed thermodynamically as a function of Al concentration in the original pack for the powder mixtures activated by 4 wt% CrCl₃·6H₂O. Based on the thermochemical calculations, a series of coating experiments was carried out. Aluminide coatings were formed at temperatures from 850°C to 1100°C for periods varying from 4 hours to 8 hours using powder mixtures activated by NH₄Cl, NaCl and CrCl₃·6H₂O and AlF₃. The effects of changing Al concentration as well as adding small quantities of Cr in the powder mixtures on the coating formation process were also investigated. The aluminide coatings were analysed using a range of techniques including SEM, EDX and XRD. The relationships between the mass gain and coating thickness and structure were investigated. The experimental results were compared with the predictions from thermochemical calculations. Based on the understandings established, an effective approach to control the aluminide coating parameters and structures was identified, which made it possible to optimise powder mixture compositions and coating conditions for different coating requirements.     

原位生成SiC-MoSi_2-TiSi_2涂层的工艺条件研究

用一次包埋法制备了C/C复合材料SiC-MoSi2-TiSi2复相陶瓷内涂层,对制备涂层的影响因素进行了分析。最终确定的制备条件为制备温度2573K,保温时间为2h,MoSi2和TiC的配比为5∶2。结果表明C/C复合材料表面SiC-MoSi2-TiSi2复相陶瓷涂层在1500℃有氧环境下氧化49h,失重仅仅2.18%,失重率为1.17×10-4g/（cm2.h）,具有良好的抗氧化性能。     

Oxidation behavior of aluminide coatings on carbon steel with and without electrodeposited Ni-CeO2 film by low-temperature pack cementation

A CeO₂-dispersed aluminide coating was fabricated through aluminizing the electrodeposited Ni-CeO₂ nanocomposite film on carbon steel using pack cementation method at 700 °C for 4 h. The isothermal and cyclic oxidation behavior of the CeO₂-dispersed aluminide coating at 900 °C, including the growth of oxide scale and the microstructure of the coatings, have been investigated comparing with the aluminide coating on carbon steel. The results show enhanced oxidation performance of the CeO₂-dispersed aluminide coating, which is concerned with not only CeO₂ effect on the microstructure and oxidation, but also decreased interdiffusion between the aluminide and the Ni film. The CeO₂ benefit effects and interdiffusion are discussed in detail.     

Formation and properties of diffusion coatings applied to steels by boronizing in melts

We propose the optimum modes for the formation of diffusion boride coatings on steels of various classes from liquid-metal melts. The microstructure and physical properties of boronized steels 20, 30, 45, R18, DI22, and U10 are analyzed. The advantages of boronizing from lithium-based melts, which enables one to combine the process of deposition with heat treatment, over the familiar methods of creation of a coating from powder mixtures are established. Karpenko Physicomechanical Institute, Ukrainian Academy of Sciences, L'viv. Translated from Fizyko-Khimichna Mekhanika Materialiv, Vol. 35, No. 2, pp. 86–91, March–April, 1999.     

NbSi基原位复合材料表面包埋渗制备SiCrY共渗涂层

通过热力学计算分析了分别使用NH₄Cl和CrCl₃·6H₂O两种不同激活剂时, 各个共渗元素的卤化物蒸汽压分压的变化, 得到了实现Nb-Si基原位复合材料上Si-Cr-Y三元包埋共渗的最佳条件。采用包埋共渗法在Nb-Si基原位复合材料表面制备了Si-Cr-Y共渗涂层, 研究了涂层的组织形貌、 成分及其相组成。结果表明: 使用NH₄Cl做激活剂, 通过调整包埋渗料的成分, 可以在适当的温度下实现Si-Cr-Y的三元共渗。当渗料成分为12Cr-6Si-0.75Y₂O₃-5NH₄Cl-76.25Al₂O₃(质量分数)时, 在1350℃可以实现Si-Cr-Y三元共渗。制备的涂层具有多层结构, 分为外层、 内层和明显的互扩散层。互扩散层的存在, 表明涂层的形成是一个连续生长过程, 伴随着Cr、 Si、 Y元素向基体内的扩散。涂层的主要成分由Cr₂(Nb,Ti)、 (Nb,Ti)₅Si₃和HfSi₂组成, Y元素的添加起到了细化涂层的作用。     

Development of mechanical properties of structural high-carbon low-alloy steels through modified heat treatment

The modified heat treatment, which produces a mixed structure of martensite and lower bainite through short-term isothermal transformation at just above the martensitic transformation temperature,M _s temperature, followed by oil quenching (after conventional austenitization), has been applied to three high-carbon low-alloy steels with different levels of nickel and chromium contents at similar molybdenum levels, in which carbon was allowed to replace relatively expensive additions of nickel and chromium, for their ultra-high strength application. The significant conclusions are as follows: an ultra-high strength steel of 1900 M Pa yieldstress grade with a high toughness level can be obtained when about 60 vol % lower bainite is associated with 473 K tempered martensite of 0.60% C-1.80% Ni-0.80% Cr-0.25% Mo steel. If approximately 25 vol % lower bainite appears in 673 K tempered martensite of the steel, a 1700 M Pa yield-stress grade steel with high toughness and moderate ductility levels can be attained. However, alloying nickel is essential to some extent for development of the mechanical properties with the modified heat treatment suggested in the present work.     

Effects of pack composition on the formation of aluminide coatings on alloy steels at 650°C

This is a detailed study aimed to understand the effects of pack composition on the formation and growth of aluminide coatings on alloy steels by pack aluminisation at 650°C, a temperature below the melting point of Al (660°C), using pack powders consisting of Al as depositing source, a halide salt as an activator and Al₂O₃ as inert filler. The packs activated by AlCl₃, NH₄Cl, AlF₃ and NH₄F were used to investigate the effects of the type of halide salt on the coating formation and growth process and subsequently to identify the most suitable activator for pack aluminising alloy steels at 650°C. The effects of pack Al content on the rate of coating growth were then studied by varying the pack Al content from 1.4 wt% to 10 wt% whilst fixing the pack activator content at 2 wt%. It was observed that among the halide salts studied, AlCl₃ is the only suitable activator for pack aluminising alloy steels at 650°C and the rate of coating growth increases with the pack Al content. The equilibrium partial pressures of vapour species generated at the deposition temperature in packs activated by different types of halide salts were calculated and the results were discussed in relation to the observed deposition tendency of packs activated by different types of activators. A vapour phase transportation model was applied to elucidate the relationship between the rate of coating growth and the pack Al content. It was also demonstrated that by combining the low temperature pack aluminising parameters identified in this study with electroless or electro Ni plating, coherent nickel aluminide coatings free of microcracking can be produced on alloy steels at 650°C.     

Pack cementation process for the formation of refractory metal modified aluminide coatings on nickel-base superalloys

The vapour phase compositions of a series of pack powder mixtures containing elemental Al and Hf or W powders as depositing sources and CrCl₃·6H₂O or AlF₃or CrF₃as activators were analysed in an attempt to further develop the pack cementation process to codeposit Al and Hf or W to form diffusion coatings on nickel base superalloys. The results suggested that Al could be codeposited with Hf, but not with W, from the vapour phase. Compared with both AlF₃and CrF₃, CrCl₃·6H₂O has been shown to be a more suitable activator for codepositing Al with Hf. The optimum coating temperature was identified to be in the range of 1050°C to 1150°C. Based on the thermochemical analysis, a series of coating deposition studies were undertaken, which confirmed that codeposition of Al and Hf could be achieved at a deposition temperature of 1100°C in the CrCl₃·6H₂O activated packs containing elemental Al and Hf powders. The coating obtained had a multilayer structure consisting of a Ni₇Hf₆Al₁₆top layer and a NiAl layer underneath, followed by a diffusion zone, which revealed that the coating was formed by the outward Ni diffusion. It is suggested that the compositions suitable for codeposition of Al and Hf could be effectively identified by comparing the vapour pressures of HfCl₄and HfCl₃with that of AlCl in the packs activated by chloride salts. It has also been experimentally demonstrated that, although W could not be deposited from the vapour phase, a high volume of fine W particles can be entrapped into the outer NiAl coating layer formed by the outward Ni diffusion using a modified pack configuration. This leads to the formation of a composite coating layer with W particles evenly distributed in a matrix of NiAl. It is suggested that this modified pack process could be similarly applied to develop nickel aluminide coatings containing other refractory metals that may not be codeposited with Al from the vapour phase.     

Properties of TiN coatings deposited by the modified IPD method

The paper describes the very first observations of the effect of pulsed gas injection to the coaxial accelerator during impulse plasma deposition (IPD) on the structure and properties of deposited material. As a test material a TiN coating deposited on high-speed steel substrates was chosen. The morphology and wear-resistance properties were determined. The structure obtained with modified IPD method is characterized by a crystalline structure built of rectangular nanograins (with size a few tens of nm) in contrast to the nanocrystalline structure based on three-dimensional (3D) agglomerates of nanoparticles typical for the standard IPD synthesis. The wear-resistance of the TiN coatings deposited in the modified IPD apparatus demonstrate very good properties with the best results more than ten times better compared with the uncoated steel substrates.     

包埋法制备SiC涂层内残留Si的高温抗氧化作用机制

采用包埋法在C/C基体上制备了SiC涂层, 借助X射线衍射仪(XRD)和扫描电镜(SEM)对涂层的相组成及微观形貌进行了观察和分析, 研究了涂层在1500℃静态空气中的氧化行为, 并进一步阐述了涂层的抗氧化机制。结果显示: 包埋法制备的涂层由α-SiC、 β-SiC及游离Si组成, 经XRD半定量分析得到不同工艺制备的涂层中游离Si含量不同; 游离Si含量越高涂层越致密; 氧化性能显示涂层中适量的游离Si有利于涂层的抗氧化, 当涂层中游离Si质量分数为1.3%和2.9%时其抗氧化性能均较好, 在1500℃静态空气中氧化7 h失重率分别为0.19%和0.16%。      

Formation of nickel aluminide/nickel hybrid coatings on alloy steels by two step process of nickel plating and low temperature pack aluminisation

Abstract

The present study investigates the conditions required for forming a hybrid coating consisting of an outer nickel aluminide layer and an inner nickel layer on alloy steels. A commercial alloy steel of 9Cr–1Mo was used as a substrate. Electroless and electronickel plating processes were used to form an initial nickel layer on the steel. The AlCl₃ activated packs containing pure Al as a depositing source were then used to aluminise the nickel deposit at temperatures ≤650°C. The effect of phosphorus or boron content in the initial nickel layer deposited with the electroless nickel plating solutions using hypophosphite or boron–hydrogen compound as reducing agent was investigated in relation to the spallation tendency of the coating either immediately after the aluminising process or during the thermal annealing post-aluminising process. Under the aluminising conditions used, the outer nickel aluminide layer formed was Ni₂Al₃. For the electroplated nickel deposit, the growth kinetics of the outer Ni₂Al₃ layer during the pack aluminising process was found to obey the parabolic rate law with a parabolic rate constant being 12·67 μm at 650°C for 2 wt-%AlCl₃ activated pack containing 4 wt-% pure Al as a deposition source.     

Influence of manganese and sulphur on overheating of some low-alloy steels

Abstract

An assessment has been made of the overheating behaviour of three low-alloy steels used in the electric power generating industries. The steels, 1Cr–Mo–V, 2·25Cr–1Mo, and 3·5Ni–Cr–Mo–V have been prepared as high-purity versions with low tramp element contents, sulphur contents of 0·001%, and manganese contents of 0·02 and 0·2%. For comparison, commercial steels produced by good practice and containing 0·006–0·011%S and 0·17–0·21%Mn have also been examined (all compositions in wt-%). The upper shelf energies of the high-purity versions of the steels in the fully heat treated condition indicate that these steels do not overheat after treatment at temperatures up to 1400°C, whereas the commercial versions do overheat and, in some cases, show a severe reduction in their impact energy levels. In some cases, the high-purity steels show an unusually low tendency to austenite grain growth after reheating at temperatures up to 1400°C. The results obtained show that new specifications for low–alloy steels could be developed which would give freedom from overheating during forging and greatly improved upper shelf energies after heat treatment.

MST/362