The influence of laboratory test procedures on scale growth kinetics and microstructure during steam oxidation testing

Abstract

Laboratory exposures cannot reproduce all the features present in service conditions. The experimentalist is faced with the conflict between increasing the complexity of laboratory tests to replicate service more closely and keeping testing costs low by maintaining a simple procedure. The influence of various experimental parameters, which can be controlled in the laboratory, on the steam oxidation response of materials is reviewed and recommendations for best practice are proposed.     

Microstructural studies of NiAl-based model alloys and commercial coatings after isothermal oxidation

Abstract

Four commercial aluminide diffusion coatings (one Pt-free) and four polycrystalline NiAl model materials, isothermally oxidised in laboratory air at 1050°C for 1 hour, have been investigated. The coatings were deposited on a single crystal Ni-based superalloy, CMSX-4. Two of the model materials are binary alloys containing different Al amounts. The two other have the same Ni/Al ratio as the binary alloys but were alloyed with 4 at% Pt. In order to control the surface roughness, all materials were polished prior to oxidation. Microstructural studies have been conducted using X-ray diffraction and scanning electron microscopy. To get a deeper insight on the platinum influence on the oxide structure, two commercial coatings (one Pt free and the other modified with Pt) were also investigated using transmission electron microscopy. The results obtained are discussed according to the influence of Al and Pt contents in the materials.     

Fracture and adhesion of coatings for use in steam environments

Abstract

The fracture and adhesion properties of five different commercial high velocity oxygen fuel (HVOF) coatings have been evaluated as a function of temperature. Tests were carried out on coatings in the as-received, aged and densified conditions. Under all conditions the adhesion of the coatings was excellent. The strain to cracking was generally low for coatings in the ‘as-coated’ condition, however this was improved by densification or thermal ageing. It was observed that in some cases the crack path changed with treatment.     

Formation of diffusion cells in LPPS MCrAlY coatings

Abstract

The formation of diffusionally isolated regions in air plasma-sprayed, APS, MCrAlY bond coat or overlay coatings has been established. The ‘diffusion cells’ experience greatly accelerated depletion of aluminium and an early onset of breakaway oxidation associated with the morphology and extent of the internal oxides. In this paper the effect of internal oxides produced in low pressure plasma sprayed, LPPS, CoNiCrAlY coatings are presented. Isothermal tests in laboratory air at 1200°C were conducted with post-test characterisation performed using scanning electron microscopy and energy dispersive X-ray analysis. A parabolic correlation was found between TGO growth rate and time at temperature. Importantly, compositional profiles of cross sections through the coatings demonstrated that no barriers to diffusion occurred throughout the body of the coating. What has been found in the LPPS coatings is a mechanism whereby diffusion cell formation is possible at sites where splat boundaries containing internal oxides intersect the outer surface. Gas access is possible at these sites and, with increasing time at temperature, formation of a continuous internal oxide layer forms. The sequence of events at these sites follows that of the diffusion cell model presented earlier and a prediction of time to failure is made.     

The influence of platinum on the oxidation and sodium sulfate induced hot corrosion of NiAl diffusion coatings

Abstract

Oxidation and corrosion properties at 900°C of two coatings, one containing platinum and the other platinum-free, on IN792 were investigated. During the corrosion exposures, sodium sulfate salt was situated in the furnace together with the coated specimens. The temperature of the salt was kept above its melting point but lower than the temperature of the coating i.e. 900°C. The exposure times ranged from 100 to 1000 h. The formed oxide scales were studied by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy and scanning transmission electron microscopy techniques. It is shown that the presence of Pt improves the protective properties of the coating against corrosion. The propagation stage of corrosion on the platinum-free coating is reached already after 100 h of exposure. On the other hand the scale formed on the platinum-rich samples still appeared to be protective even after 500 h. The details concerning structure and chemistry of the scales formed are presented and discussed.     

Cyclic oxidation behaviour of plasma sprayed metallic coatings

High temperature Co- and Ni-based metallic coatings of various compositions were applied on SS-310 samples using plasma spray technique. The coated samples were exposed to air under cyclic conditions at 900°C for upto 100?h. Adhesion of coatings was measured using standard ASTM C 633-79 method. Scanning electron microscopy coupled with energy dispersive X-ray spectroscopy was used to determine the surface morphology and microchemical constitution of coatings. X-ray diffraction was used to identify different phases formed during oxidation. Experimental results indicated that high temperature oxidation of SS-310 alloy was greatly reduced by all coatings. The plasma sprayed metallic coatings on SS-310 alloy performed better than that of bare SS-310 under the selected test conditions. Moreover, when compared among the selected metallic coatings used in the study, the Co-based coatings with higher Cr concentration exhibited superior performance compared to Ni-based coating with lower Cr concentration during the reported cyclic exposure.     

Japanese experience with steam oxidation of advanced heat-resistant steel tubes in power boilers

Abstract

Japanese experience of steam oxidation behavior of advanced heat-resistant steel tubes in power boilers is discussed. Severe scale separation, cracking, and exfoliation were observed in T91 pendant reheater tubing in a Japanese utility boiler after around 40,000 hours of operation. Separation occurred at the interface between the inner and outer layers of scale. A high-pressure steam oxidation test rig in which the steam conditions could be controlled in a similar manner to that of an actual boiler was developed and T91 steel samples were tested up to 10,269 hours. The scale separation behavior of T91 was reproduced in the steam oxidation test. The growth rate of T91 was lower than that for conventional 9Cr-1Mo steel reported by EPRI. The scale separation was related to void formation at the interface between the inner and outer layers of scale, as well as the transformation of magnetite into hematite in the outer layer. Field exposure testing was carried out for T23 and T122 for 80,000 hours, and the properties of steam oxidation scale were obtained.     

氧化处理时间对Ti6Al4V微弧氧化陶瓷膜的影响

采用交流微弧氧化法于：Na：SiO3-KOH-(NaPO3)6溶液中在％6A14V表面形成了氧化物陶瓷膜．利用扫描电镜、电子探针及X射线衍射研究了陶瓷膜的组织形貌、元素的分布和相组成．研究表明：在恒定的微弧氧化电参数(U =500V，U-=100V和f=600Hz)下，随氧化时间延长，电流密度逐渐降低，膜层厚度不断增加；相对致密均匀的膜分为3层：过渡层、致密层与疏松层．膜层主要由TiO2(锐钛矿和金红石)相组成，延长处理时间，锐钛矿相及金红石相的相对含量发生变化，金红石相TiO2逐渐增多，而锐钛矿相TiO2减小．膜层相的形成过程可分为两个阶段。     

The effect of yttrium content on the oxidation-induced degradation of NiCoCrAlY coatings and the influence of surface roughness on the oxidation of NiCoCrAlY and platinum aluminide coatings

Abstract

It has been found that the yttrium content of NiCoCrAlY coatings affects the useful lives of such coatings during cyclic oxidation. In particular, NiCoCrAlY coatings with 0.1wt% yttrium have more than twice the lifetime at 1100°C compared to NiCoCrAlY coatings with 0.5wt% yttrium. The mechanism by which the yttrium concentration influences the degradation of NiCoCrAlY coatings will be described. It has also been observed that the adverse effect of yttrium can be inhibited by reducing the roughness of the coating surface. The influence of surface condition on the oxidation of yttrium in NiCoCrAlY coatings will be examined in detail and the effects of surface roughness on the oxidation of NiCoCrAlY and platinum aluminide coatings will be compared. Finally the effects of yttrium in the substrate alloy on the oxidation of platinum aluminide coatings will be discussed.     

Long term steam oxidation of TP 347H FG in power plants

Abstract

The long term oxidation behaviour of TP 347H FG at ultra supercritical steam conditions was assessed by exposing the steel in test superheater loops in a Danish coal-fired power plant. The steamside oxide layer was investigated with scanning electron microscopy and energy dispersive X-ray diffraction in order to reveal the effect of oxidation time and temperature on the microstructure.

A double layered oxide formed during steam oxidation. The morphology of the inner Cr-containing layer was influenced by the oxidation temperature. At temperatures below 585°C, it consisted of regions of Fe–Ni–Cr spinel surrounded by Fe–Cr oxide. At higher temperatures almost the entire inner oxide layer was composed of Fe–Cr oxide. Possible mechanisms for the oxide growth are discussed and it is suggested that faster Cr transport within the alloy at higher temperatures explains the change in morphology.

The thickness of the inner oxide layer appeared to be independent of oxidation time and temperature for exposes less than 30 000 h; however, after 57 554 h, the thickness had increased significantly at the lowest temperatures.     

SiC颗粒的高温氧化动力学

研究了SiC颗粒在927℃、1027℃和1127℃空气中的高温氧化动力学.结果表明,温度越高SiC颗粒的氧化速率常数越大,氧化反应越容易进行;SiC颗粒的高温氧化分为氧化前期和氧化后期两个阶段.氧化前期的反应速率受界面化学反应的控制;氧化后期受扩散控制,其表观活化能远比氧化前期的大.SiC颗粒的高温氧化过程符合两个阶段式模型:氧化前期的氧化速率常数k_c=143.37exp(-70994/RT)(mg·m~(-2)·min~(-1)),氧化后期的氧化速率常数k_D=3.61×10~8exp(-192758/RT)(mg·m~(-2)·min~(-1)).     

The outward-inward growth behavior of microarc oxidation coatings in phosphate and silicate solution

Microarc oxidation (MAO) coatings have a unique outward-inward growth behavior, which is crucial to the dimensional matching of precision-matching parts after surface treatment. Here, a notably different outward-inward growth behavior of MAO coatings was observed in phosphate solution and silicate solution, respectively. The results indicate that the outward-growth dimension of MAO coating in Na₂SiO₃ solution is notably larger than that in (NaPO₃)₆ solution, especially at the initial stage of MAO treatment, but as an increase of oxidation time, the inward-growth behavior enhances in both solutions. It is considered that the different adsorptive capacity of solute anions leads to the various outward-inward growth behaviors of MAO coatings in phosphate solution and silicate solution.     

Computer simulation of the cyclic oxidation of the Al–Si coatings

A model (COSP) useful in predicting the cyclic oxidation behaviors of coating on nickel-base superalloys is presented. The content of the Al–Si coatings is calculated and the oxidation kinetics curve is simulated under cyclic conditions. The predicting result is fairly exact.     

钛合金微等离子体氧化陶瓷膜结构与耐酸腐蚀

在铝酸钠溶液中,利用微等离子体氧化技术,在TC4钛合金表面原位生长复合氧化物陶瓷膜,研究了陶瓷膜的相组成、形貌和陶瓷膜对钛合金耐酸腐蚀的影响。陶瓷膜由Al2TiO5,α-Al2O3和金红石型TiO2构成;整个膜层由致密层和疏松层组成。在盐酸和硫酸中陶瓷膜使得钛合金耐酸腐蚀特性提高了5倍左右。带有陶瓷膜的钛合金在硝酸中的腐蚀速率为膜层的溶解速率。     

纳米SiCp增强NiCoCrAlY涂层的组织和抗氧化性能

为了研究纳米SiCp对NiCoCrAlY涂层的组织和抗氧化性能的影响,采用激光熔覆技术在镍基高温合金表面制备了4种不同含量纳米SiCp增强的NiCoCrAlY熔覆涂层,考察了它们的组织及其在1050℃下的等温氧化行为,并初步分析了纳米SiCp的影响机制.结果表明,加入纳米SiCp涂层的组织和抗氧化性能较未加纳米颗粒的涂层均得到了不同程度的改善.其中,添加质量分数1%的纳米SiCp对涂层组织和抗氧化性能的改善作用最为显著.纳米SiCp的加入,不仅改变了界面处的结晶形态,而且细化了熔覆层的组织.熔覆层组织的细化对提高涂层的抗氧化性能有着积极的作用.     

Influence of chromium diffusion and different surface finishes on the oxidation behaviour of chromium steels

Abstract

The present contribution is focused on the systematic investigation of the effects of different surface finishes (ground, polished, electropolished) on the oxidation behaviour of chromium steels. The specimens were oxidized in a H2–2.5%H₂O atmosphere at 872 K for 1 h to 100 h. Depth profiles were recorded by secondary neutral mass spectrometry (SNMS) to determine the elemental composition of the oxide scale and the diffusion profiles below the scale. The surface finish was found to influence both the thickness of the oxide scale and the depletion of the selectively oxidized elements.     

Mg-Li合金微弧氧化陶瓷膜的制备及其耐蚀性能

通过三种优化工艺体系在Mg-5%Li合金表面上生长陶瓷膜层,分析了膜层的厚度、显微结构、相组成和耐蚀性.结果表明,三种膜层都含有MgO相,微弧氧化试样的耐蚀性能都明最提高.使用Na3PO4体系制备的膜层含有MgF2,膜层最厚、表面有大量裂纹;使用Na2SiO3体系制备的膜层含有橄榄石型Mg2SiO4,耐点蚀性能最好;使用Na2SiO3-Na3PO4体系制备的膜层含有MgSiO3,致密性最好,膜层酎均匀腐蚀性能最好.     

New insight to the oxidation kinetics of silicon-containing steel at high temperature

This study investigated the oxidation kinetics of silicon-containing steel at 1150–1300 °C using a Simultaneous Thermal Analyzer under atmospheric conditions similar to that of an industry reheating furnace. There is a critical time point for the oxidation kinetics at an oxygen concentration of 4·0 vol.-%., following which the oxidation rate constant increases with the increasing oxidation temperature. The model coefficient A in the kinetic oxidation equation was found to be constant. However, before the critical time point, the oxidation rate constant remained unchanged; the model coefficient A decreased with the increasing temperature. Therefore, the kinetic model of silicon-containing steel for isothermal oxidation was observed to be a modified one on the basis of the experimental data. In addition, the critical time point was prolonged with the increasing isothermal oxidation temperature. Moreover, the oxidation activation energy of the tested silicon-containing steel was 366·16 kJ mol^?1.