Metal dusting of binary iron aluminium alloys at 600 °C

In this work experiments on metal dusting of binary iron aluminium alloys with 15, 26 and 40 at.% Al were performed in strongly carburising CO‐H₂‐H₂O gas mixtures at 600 °C. The mass gain kinetics was measured using thermogravimetric analysis (TGA). The carburised samples were characterised by means of light optical microscopy (LOM), scanning electron microscopy (SEM), X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). It was found that the mass gain kinetics depends on the CO content of the gas mixtures and on the Al content of the alloys. With decreasing carbon activity the carburisation reaction kinetics decreases and the onset of metal dusting is retarded for increasing time periods. With increasing Al content of the alloys the carburisation reaction is slower and metal dusting sets on at later times. The samples were not pre‐treated for the formation of a protective oxide scale. By X‐ray Photoelectron Spectroscopy (XPS) analyses of the carburised iron aluminium samples it was found that the formation of Al₂O₃ layers has taken place in the CO‐H₂‐H₂O gas atmospheres. Needle‐ or plate‐like κ‐phase (Fe₃AlC_x) precipitates close to the surface of the carburised Fe‐15Al sample were detected by means of XRD and LOM. The coke on top of the carburised samples mainly consists of filamentous carbon with metal particles at their tips.     

Electrochemical characteristics of titanium based biomaterials in artificial saliva

In the last decade, new titanium alloys have been developed in different areas of dentistry, such as Ti6Al7Nb, Ti6Al2Nb1Ta1Nb, and Ti5Al2.5Fe. The aim of this study was to compare the Ti6Al7Nb, Ti6Al2Nb1Ta1Nb, Ti5Al2.5Fe, and Ti6Al4V alloys with the commercial titanium, regarding the corrosion resistance in artificial saliva. In the electrochemical estimations the polarization data are converted into instantaneous corrosion rate values (I_corr). The passivation properties were comparable for the four alloys. The EIS spectra are best fitted using an equivalent circuit (EC), which corresponds to the model of a two‐layer structure for the passive film. High impedance values (in the order of 10⁶ Ω cm²) were obtained from medium to low frequencies for all materials suggesting high corrosion resistance in artificial saliva. The electrochemical and corrosion behavior of Ti6Al4V is not affected on substituting vanadium with niobium, iron, molybdenum, and tantalum.     

α‐Fe layer formation during metal dusting of iron in CO‐H2‐H2O gas mixtures

The formation of an α‐Fe layer between cementite and graphite was observed and investigated during metal dusting of iron in CO‐H₂‐H₂O gas mixtures at both 600°C and 700°C. The condition to form this phenomenon is determined by the gas composition which depends on temperature. The iron layer formation was observed for CO content less than 1 % at 600°C and less than 5 % at 700°C. With increasing CO contents, no α‐Fe layer was detected at the cementite/graphite interface by optical microscopy. In this case cementite directly contacts with the coke layer. The morphologies of the coke formed in the gas mixtures with low CO contents were also analysed. Three morphologies of graphite have been identified with 1 % CO at 600°C: filamentous carbon, bulk dense graphite with columnar structure, and graphite particle clusters with many fine iron containing particles embedded inside. At 700°C with 5 % CO the coke mainly consists of graphite particle clusters with some filamentous carbon at the early stage of reaction. Coke analysis by X‐ray diffraction shows that both α‐Fe and Fe₃C are present in the coke. The mechanism of α‐Fe accumulation between cementite and graphite is discussed in this paper.     

Coke formation during metal dusting of iron in CO‐H2‐H2O gas with high CO content

Iron carburisation and coke formation during metal dusting of iron have been investigated in the gas mixture of 75%CO‐24.8%H₂‐0.2%H₂O at 600°C and 700°C. In all cases, cementite is formed at the surface, together with a coke layer on the top. In the coke layer, two morphologies of graphite are identified: compact bulk graphite with a uniform thickness and a columnar structure, and filamentous carbon with iron‐containing phases at the tip or along its length. The examination of coke formation in different stages of reaction at 700°C reveals that the coke contains two layers. The inner layer is composed of filaments, while the outer layer consists of the compact columnar graphite. After 2 h reaction the top compact graphite layer has suffered a serious deformation and has formed fractures because of the growth of catalytic filamentous carbon underneath. These filaments grow outside from these fractures and finally cover the whole surface after 4 h reaction. At 600°C, however, the coke contains a thick bulk graphite layer and non‐uniformly distributed filaments on the top. The bulk graphite layer is composed of many graphite columns which are loosely piled and are vertical to the surface. Each graphite column consists of many fine graphite fibres in parallel with the columnar axis. Filaments grow outside preferably from the gaps among these graphite columns and along the grinding scratches. TEM analysis of the coke detects very convoluted filaments with iron‐containing particles at the tip or along their length. XRD and TEM analyses show that these particles are Fe₃C rather than metallic iron.     

Effect of H2S on metal dusting of iron

A review is given on the effect of H₂S on metal dusting of iron which has been studied by gas carburisation in CO‐H₂‐H₂O‐H₂S and CH₄‐H₂‐H₂S mixtures at 500 and 700°C. The presence of H₂S in carburising gas atmospheres leads to sulphur adsorption on the iron surface, which retards carbon transfer. Segregation experiments and surface analyses have shown that sulphur segregates (and thus adsorbs) on cementite surfaces as well as on iron surfaces. The adsorbed sulphur also suppresses graphite nucleation and thus can stop the reaction sequence of metal dusting. Experiments by thermogravimetric analysis (TGA) have shown that the extent of retardation of metal dusting depends on temperature, carbon activity and H₂S content. The higher the carbon activity, the higher is the H₂S content required for suppression of metal dusting. At carbon activities a_C > a_C(Fe/Fe₃C) the metastable iron carbide, cementite (Fe₃C), occurs as an intermediate phase during metal dusting. Carburisation experiments in CO‐H₂‐H₂O‐H₂S mixtures at 500°C and X‐ray diffraction analysis (XRD) of carburised samples have revealed that at very high carbon activities a second iron carbide, Hägg carbide (Fe₅C₂), forms on the cementite surface. Microstructural investigations have shown that both metastable carbides decompose during metal dusting. Metal dusting experiments on iron at 700°C have been performed in CH₄‐H₂‐H₂S gas mixtures. By adding 15 ppm H₂S to the CH₄‐H₂ atmosphere the onset of metal dusting can be retarded for more than 350 hours. By means of Auger electron spectroscopy (AES), scanning electron microscopy (SEM) and energy dispersive X‐ray analysis (EDX) it was shown that coke contains graphite, cementite and iron particles with adsorbed sulphur.     

Oxidation of orthorhombic Ti2AlNb alloys at 800 °C in air

Aerospace activities as well as the power generation and automotive industries would definitely benefit from the potential weight savings and increased operation temperatures made possible by the use of orthorhombic titanium aluminides. A high effort is nowadays given in the development of these materials, based on the composition Ti₂AlNb. They are attractive in comparison to the conventional titanium aluminides because of their good balance of specific mechanical properties at both room‐ and high‐temperatures combined with good thermomechanical processing capabilities and a very good ignition resistance. Three orthorhombic alloys with various β‐stabilising elements contents (Ti‐23Al‐25Nb‐0.35Si, Ti‐22Al‐25Nb‐1Mo‐0.2Si, Ti‐23Al‐13Nb‐5Ta‐3Mo) were investigated, with respect to their oxidation resistance in air at 800 °C. Oxidation kinetics are discussed with regard to the influence of the alloying elements. Complete scale spallation occurred after 10 × 100 h and a multilayered oxide scale of alternating TiO₂‐rich and AlNbO₄‐rich layers with segregation of the refractory elements had developed. In addition to this catastrophical scale formation, two types of subsurface morphologies were obtained, which appeared to be successive development states of the inward progress of the oxidation mechanism. The orthorhombic materials were very sensitive to interstitial diffusion leading to severe embrittlement. A third type of subsurface morphology was found together with a thin adherent alumina rich oxide scale on the Ta‐containing specimen. The protective morphology was associated with an interfacial zone of (Ti, Nb)‐nitride and (Al, Nb)‐rich metal phase. These observations and the “Ta‐effect” are discussed in consideration of the literature data.     

Effect of pre‐oxidation on coke formation and metal dusting of electroplated Ni3Al–CeO2‐based coatings in CO–H2–H2O

Pre‐oxidation was introduced to improve the resistance of electroplated pure, 5 µm CeO₂‐dispersed, and 9–15 nm CeO₂‐dispersed Ni₃Al coatings to coke formation and metal dusting in 24.4%CO–73.3%H₂–2.3%H₂O at 650 °C. Coke formation and metal dusting of pre‐oxidized Ni₃Al‐based coatings were retarded up to 200 h owing to a thin Al₂O₃ scale induced during pre‐oxidation. The long‐term effectiveness of pre‐oxidation nonetheless depended on the integrity of Al₂O₃ scale. The pure Ni₃Al coating suffered severe spallation after pre‐oxidation and thereby showed the worst long‐term resistance. Two pre‐treated 9–15 nm CeO₂‐dispersed Ni₃Al coatings exhibited the best long‐term resistance to carbon attack because nano‐CeO₂ particles maintained a full coverage of Al₂O₃ scale on the coatings. Two 5 µm CeO₂‐dispersed Ni₃Al coatings showed significant spallation after pre‐oxidation because of an overdoping effect and experienced coke formation and metal dusting during long‐term exposure.     

Corrosion behavior of Ti‐xNb‐13Zr alloys in Ringer's solution

Ti‐6Al‐4V alloy has been widely used in restorative surgery due to its high corrosion resistance and biocompatibility. Nevertheless, some studies showed that V and Al release in the organism might induce cytotoxic effects and neurological disorders, which led to the development of V‐free alloys and both V‐ and Al‐free alloys containing Nb, Zr, Ta, or Mo. Among these alloys, Ti‐13Nb‐13Zr alloy is promising due to its better biomechanical compatibility than Ti‐6Al‐4V. In this work, the corrosion behavior of Ti, Ti‐6Al‐4V, and Ti‐xNb‐13Zr alloys (x = 5, 13, and 20) was evaluated in Ringer's solution (pH 7.5) at 37 °C through open‐circuit potential measurements, potentiodynamic polarization, and electrochemical impedance spectroscopy. Spontaneous passivity was observed for all materials in this medium. Low corrosion current densities (in the order of 10^?7 A/cm²) and high impedance values (in the order of 10⁵ Ωcm² at low frequencies) indicated their high corrosion resistance. EIS results showed that the passivating films were constituted of an outer porous layer (very low resistance) and an inner compact layer (high resistance), the latter providing the corrosion resistance of the materials. There was evidence that the Ti‐xNb‐13Zr alloys were more corrosion resistant than both Ti and Ti‐6Al‐4V in Ringer's solution.     

Surface analytical studies of metal dusting of iron in CH4‐H2‐H2S mixtures

The metastable iron carbide, cementite (Fe₃C), occurs as an intermediate phase during the high temperature corrosion process called “metal dusting”. The kinetics and thermodynamics of metal dusting of iron have been studied by Grabke et al. [1–5] using CO‐H₂‐H₂O and CH₄‐H₂ gas mixtures. H₂S additions to carburising atmospheres impede the carbon transfer and retard the onset of metal dusting [6–14], thus allowing to study the early stages of the process. In this work the metal dusting process was studied in CH₄‐H₂‐H₂S atmospheres at 700 °C. Segregation experiments and surface analyses showed that S segregates on iron surfaces as well as on cementite surfaces. By means of Auger electron spectroscopy (AES), scanning Auger electron microscopy (SAM) and energy dispersive X‐ray analysis (EDX) it was shown that coke contains graphite, cementite and iron particles with adsorbed sulphur.     

The corrosion behavior of Fe-Nb-Al alloys in H2/H2O/H2S atmospheres

The corrosion behavior of eight Fe-Nb-Al ternary alloys was studied over the temperature range 700–980°C in H₂/H₂O/H₂S atmospheres. The corrosion kinetics followed the parabolic rate law for all alloys at all temperatures. The corrosion rates were reduced with increasing Nb content for Fe-x Nb -3Al alloys, the most pronounced reduction occurred as the Nb content increased from 30 to 40 wt.%. The corrosion rate of Fe-30Nb decreased by six orders of magnitude at 700°C and by five orders of magnitude at 800°C or above by the addition of 10 wt.% aluminum. The scales formed on low-Al alloys (3 wt.% Al) were duplex, consisting of an outer layer of iron sulfide (with Al dissolved near the outer-/inner-layer interface) and an inner complex layer of Fe_xNb₂S₄(FeNb₂S₄ or FeNb₃S₆), FeS, Nb₃S₄ (only detected for Nb contents of 30 wt.% or higher) and uncorroded Fe₂Nb. No oxides were detected on the low-Al alloys after corrosion at any temperature. Platinum markers were found to be located at the interface between the inner and outer scales for the low-Al alloys, suggesting that the outer scale grew by the outward transport of cations (Fe and Al) and the inner scale grew by the inward transport of sulfur. The scales formed on high-Al alloys (5 wt.% Al) were complex, consisting primarily of Nb₃S₄, Al₂O₃ and (Fe, Al)_xNb₂S₄, and minor amounts of (Fe, Al)S and uncorroded intermetallics (FeAl and Fe₂Nb). The formation of Nb₃S₄ and Al₂O₃ blocked the transport of iron through the inner scale, resulting in the significant reduction of the corrosion rates.     

Study of the metal dusting behaviour of high‐temperature alloys

The corrosion phenomenon named metal dusting has been observed in many high‐temperature industrial plants. An experimental research programme is being carried out into the degradation resistance of wrought and cast commercial and development high‐temperature alloys in H₂/CO gas mixtures at temperatures of 550°C to 750°C. Emphasis is placed on very high carbon activities, consistent with the next generation of steam‐reforming and similar plants that are susceptible to metal dusting. The overall programme is concerned with the mechanisms of initiation and propagation of dusting and the sensitivity to damage of the more resistant alloys, as a function of environmental parameters. Initial tests have been carried out on a number of commercial alloys: Alloy 600, 693, 602CA, 601, 603 XL, 671, 617, 690 (wrought), and H46M (cast). The specimens were exposed to a gas mixture of high carbon activity at 650°C for a total of 1000 hours. Many of the alloys showed at least the initial stages of metal dusting. Preliminary analysis using electron microscopy revealed that initiation of metal dusting is influenced by microstructure, stress state and composition. In some cases, attack was enhanced at stress points, such as corners and edges. Sample holders were found to influence strongly the length of the initiation period for the onset of the corrosion phenomenon. The reaction layers in the alloy beneath areas of damage were analysed by EDX and EPMA. Mechanical characterisation of such areas has been carried out using nanoindentation methods. These early results are discussed in terms of the effectiveness of oxide scales in inhibiting the onset of damage and presence of impurities in the ceramic holder in initiating the onset of damage.     

The site occupancies of alloying elements in TiAl and Ti3Al alloys

The site occupancies of V, Cr, Mn, Fe, Ni, Zr, Nb, Mo, Ta, Ga and Sn (1–5 at.%) in TiAl alloys with different compositions, and in Ti₃Al with the compositions of Ti–26 at.%Al–(1–2 at.%)X, were measured by the atom location channelling enhanced microanalysis (ALCHEMI) method. For TiAl alloys, the results show that Zr, Nb and Ta atoms invariably occupy Ti sites, while Fe, Ni, Ga and Sn atoms occupy Al sites, the alloy composition having no significant influence on their site preference. By contrast, the site preference of V, Cr, and Mn changes considerably with alloy composition (the Ti/Al ratio in particular), the probability of these elements substituting for Ti decreasing in the above order. For quaternary Ti–Al–V–Cr alloys, the site occupancies of V and Cr do not show much mutual influence. In general, with increasing atomic number, elements in the same period show increasing tendency to substitute for Al, as is the tendency to substitute for Ti for elements in the same group of the periodic table. For Ti₃Al alloys, Ga and Sn atoms occupy Al sites, while V, Cr, Mn, Zr, Nb, Mo and Ta atoms occupy Ti sites, the site preference of V, Cr, Mn and Mo in TiAl alloys being different from that in Ti₃Al. The experimental results are interpreted in terms of a Bragg–Williams-type model and bond-order data obtained from electronic structure calculation. Qualitative agreement between the model and measurements is reached.     

Improving metal dusting resistance of. transition‐metals and Ni‐Cu alloys

The present study focuses on a new technique for the prevention of metal dusting in carbonaceous gas environments at intermediate temperature. Preliminary laboratory metal dusting test was conducted for transition‐metals and Ni‐x%Cu binary alloys in a simulated 60%CO‐26%H₂‐11.5%CO₂‐2.5%H₂O (in vol.%) gas mixture at 650°C for 100 h. The metal dusting caused no coke deposition on transition‐metals of Cu, Ag, and Pt, while those of Fe, Co, and Ni have a large amount of coke and lost mass. Whether or not coking behavior of Ni‐Cu binary alloys formed any oxide scales in the simulated gas environment depended on the Cu content. Specimens containing low Cu were entirely covered with coke and showed rough metal surfaces due to the degradation of metal. Alloys of 20% and more Cu, on the contrary, had no coke deposition and smooth metal surfaces, suggesting alloys with an adequate Cu do not react with CO in the gas mixture without an oxide scale barrier. Based on these results, we conclude that Cu does not protect by formation of the oxide scale but has a “Surfactant‐Mediated Suppression” against metal dusting. This effect can be explained in terms of atomistic interaction of CO with transition‐metal surfaces by electronic structure analyses. The concept can be also useful for the practical material design of Ni‐Cr base alloy with excellent metal dusting resistance.     

Metal dusting resistance of high chromium alloys

Samples of 5 high Cr‐alloys were discontinuously exposed for 10,000 hours under severe metal dusting conditions, i. e. in flowing 49%CO‐49%H₂‐2%H₂O at 650°C. After each of the 11 exposure periods the mass change was determined and any coke removed and weighed. Metallographic cross sections were prepared after about 4,000 h and 10,000 h. The high Cr‐alloys: 1. PM 2000 (Fe‐19%Cr‐5.5%Al‐0.5%Ti‐0.5%Y₂O₃), 2. Cr‐44%Fe‐5%Al‐0.4%Ti‐0.5%Y₂O₃, 3. Cr‐50%Ni, 4. Cr‐5%Fe‐1%Y₂O₃ and 5. porous chromium showed no or only minute metal dusting attack. Compared to the attack on reference samples of Alloy 601 (Ni‐23%Cr‐14%Fe‐1.4%Al), the metal dusting symptoms were negligible on the 5 high Cr‐alloys, minor coking and pitting and no internal carburization was observed. Because of the high Cr‐content, carbon solution and ingress should be minute, and in addition are inhibited by the formation of a chromia scale, as confirmed for four of the Cr‐rich alloys, and formation of an alumina scale on PM 2000. These alloys could be used for parts exposed to severe metal dusting conditions, and in fact, 50Cr‐50Ni has been applied successfully under such conditions.     

Metal dusting behaviour of several nickel‐ and cobalt‐base alloys in CO?H2?H2O atmosphere

The metal dusting behaviour of total 11 nickel‐ and cobalt‐base alloys at 680 °C in a gas of 68%CO? 31%H₂? 1%H₂O (a_C = 19.0, = 5.4 × 10^?25 atm) was investigated. All samples were electropolished and reacted in a thermal cycling apparatus. On the basis of their reaction kinetics, these alloys can be classified into three groups: the first, with rapid carbon uptake and significant metal wastage, consists of alloys of relatively high iron content (AC 66, 800H and NS‐163); the second, with intermediate rates, consists of some Co‐base alloys (HAYNES 188, HAYNES 25 and ULTIMET) and the third, with very low reaction rates, consists of nickel‐base alloys with high chromium levels (601, HAYNES HR 160, 230, G‐35 and EN 105). An external chromia scale protected group 3 alloys from carburization and dusting. However, this protective scale was damaged and not rehealed for group 1 and group 2 alloys, allowing carbon attack. In all cases, coke deposited on the surface with two typical morphologies: filaments and graphite particle clusters. Subsurface spinel formation in high iron‐content alloys led to rapid dusting due to the significant volume expansion. Alloy carbon permeability was calculated from a simple law of mixtures, and shown to correlate reasonably well with initial dusting rate except for one cobalt‐base alloy in which iron spinel formation was significant.     

Partition behavior of alloying elements and phase transformation temperatures in Co–Al–W-base quaternary systems

The phase equilibria among γ (A1), γ′ (L1₂), χ (D0₁₉), β (B2) and μ (D8₅) phases and the γ′ solvus and γ solidus temperatures were investigated in the Co–Al–W-based quaternary systems with alloying elements of Ti, V, Nb, Ta, Cr, Mo, Mn, Fe, Ni, Si, Zr, Hf, Ru and Ir by electron probe microanalysis (EPMA) using multiphase alloys and by differential scanning calorimetry (DSC). It was found that Ta, Nb, Ti, V, Mo and W are partitioned to the γ′ or χ phase rather than to the γ phase, while Cr, Mn and Fe tend to be distributed to the γ phase. The correlation between the partition coefficient of alloying elements between γ/γ′, γ/χ and γ/β phases and ab initio formation energy of Co₃X (L1₂), Co₃X (D0₁₉) and CoX (B2) was respectively obtained. It was also found that the γ′ solvus temperature increases by the addition of the γ′ former elements such as Ta, Nb and Ti, which decreases the γ solidus temperature.     

Nanoquasicrystalline Al–Fe–Cr-based alloys. Part I: Phase transformations

Nanoquasicrystalline Al–Fe–Cr-based alloys composed of sub-micro-sized icosahedral quasicrystalline particles embedded in α-Al matrix have a higher strength at elevated temperature compared with commercial Al alloys. However, further improvement of the microstructural stability is desirable in order to maximize the elevated temperature strength. A detailed study of the effect on the microstructure and the phase transformations by the addition of Ti, V, Nb or Ta to a ternary Al₉₃(Fe₃Cr₂)₇ alloy was carried out using heat treatment and microstructural characterization. The addition of the fourth element leads to a refined microstructure and can stabilize the icosahedral topology, delaying the quasicrystalline icosahedral phase decomposition until a higher temperature is reached. The addition of Nb or Ta enabled a greater stabilization effect than the addition of Ti or V, retaining a microstructure similar to the as-spun state after heat treatment between 450 and 550 °C and even retaining icosahedral particles up to 550 °C. The outstanding microstructural stabilization obtained with addition of Nb or Ta leads to very promising applications in the automotive and aeronautic industries.     

Corrosion behaviour of a new Ti‐6Al‐2Nb‐1Ta alloy in various solutions

A new Ti‐6Al‐2Nb‐1Ta alloy was obtained for to satisfy the mechanical and anticorrosion requirements in neutral corrosive environment. The corrosion behaviour of this new Ti‐6Al‐2Nb‐1Ta alloy in 0.1 M Na₂SO₄, 3% NaCl solutions and synthetic sea water was studied in this paper, using potentiodynamic and linear polarisation method, electrochemical impedance spectroscopy (EIS) and monitoring of the open circuit potentials. The structure of the alloy represents an α + β uniform structure with un‐oriented grains. From the potentiodynamic polarisation curves it resulted that the studied alloy is self‐passivated in all three solutions having a very good and very easy tendency to passivation. The most favourable values of the electrochemical parameters were registered in 0.1 M Na₂SO₄ solution due to its reduced corrosivity. EIS measurements proved the improvement of the passive layer resistance with the immersion time. An electric equivalent circuit with two time constants was fitted. The values of the polarisation resistances showed very good protective capacities which improved in time. The open circuit potentials have the general tendency to ennoble in time, suggesting the thickening of the passive films and the increase of their protective capacities.     

Effect of Al on high-temperature corrosion of Co-15a/oNb alloys in H2-H2O-H2S environments

Co–15 at.% Nb alloys containing up to 15 at.% Al were corroded in gaseous H₂–H₂O–H₂S mixtures over the temperature range of 600–900°C. The corrosion kinetics followed the parabolic rate law at all temperatures. Corrosion resistance improved with increasing Al content except at 900°C. Duplex scales formed on alloys consisting of an outer layer of cobalt sulfide and a heterophasic inner layer. A small amount of Al₂O₃ was found only on Co–15Nb–15Al. Contrary to what formed in Co–Nb binary alloys, neither NbS₂ nor NbO₂ were found in the inner layer of all alloys, but Nb₃S₄ did form. The absence of NbS₂ and NbO₂ is due to the formation of stable Al₂O₃ and Al₂S₃ that effectively blocked the inward diffusion of oxygen and sulfur, respectively, and to the reduction of activity of Nb by Al additions in the alloys. Intercalation of ions in the empty hexagonal channels of Nb₃S₄ is associated with the blockage of the transport of cobalt. An unknown phase (possibly Al_0.5NbS₂) was detected. Alloys corroded at 900°C were abnormally fast and formed a scale containing CoNb₃S₆ and Co. Pt markers were found at the interface between the inner and outer layers.     

Einflüsse von Mo,V, Nb,Ti, Zr und deren Karbiden auf die Korrosion und Wasserstoffaufnahme von Eisen in H2S-haltigen Lösungen

Effects of Mo, V, Nb, Ti, Zr and their carbides on the corrosion and hydrogen uptake of iron in H₂S-solutions Effects of the transition metals Mo, V, Nb, Ti, Zr and their carbides as well as of phosphorous on the corrosion and hydrogen uptake of iron in acid to weakly acid NaCl solutions with and without H₂S are discussed. Investigations were carried out on binary, ternary and quaternary iron based alloys, using electrochemical and surface analytical methods. No specific effect of one of the alloying elements or the carbides on the corrosion or hydrogen uptake is observed. Due to the experimental conditions, sulphur and oxygen enriched surface scales form, by which the kinetics of the corrosion processes are determined. The alloying elements are enriched on the iron surface only as a carbide. Phosphorous is enriched as a phosphide at low pH and as a phosphate at higher pH. H₂S and phosphides increase the corrosion rate and hydrogen uptake. In pure iron or low strength iron alloys, at the very high H₂S affected hydrogen activities new lattice defects are induced permanently resulting in extremely high hydrogen concentrations.