KR20020059810A - PRODUCT MADE FROM AN ALLOY CONTAINING ONE OR MORE OF Cr, Al, Si, Ti AND SO CALLED ODE AND METHOD TO PRODUCE SAID PRODUCT - Google Patents

Abstract

The present invention relates to a metal product comprising at least one of metal chromium, aluminum, silicon and / or titanium and a method for producing the metal product, wherein the metal chromium, aluminum, silicon and / or titanium is formed on a metal surface in an oxidizing atmosphere. It is contained in an amount which forms a corrosion resistant oxide layer. A feature of the present invention is that, in at least the layer following the metal surface, the metal article comprises a yttrium and rare earth metal consisting of elements of the atomic number 57-71, scandium, hafnium, zirconium, niobium, tantalum, titanium, palladium, platinum, and rhodium One or more elements in elemental and / or oxide form belonging to the (REM) group and referred to as oxygen separation elements (ODEs) and capable of effectively separating oxygen at the interface between the oxide layer of the product and the surrounding gas phase. A metal product comprising at least 0.01 wt% and at least 0.5 wt ppm hydrogen.

Description

Products made of alloys containing at least one of Cr, Al, Si, Ti and so-called oxygen-separated elements, and methods for manufacturing the product {PRODUCT MADE FROM AN ALLOY CONTAINING ONE OR MORE OF Cr, Al, Si, Ti AND SO CALLED ODE AND METHOD TO PRODUCE SAID PRODUCT}

It is known that the corrosion resistance of the aforementioned alloys depends on the ability to form a thin corrosion resistant oxide layer of chromium, silicon, aluminum and / or titanium oxide on the metal surface. However, it is also known that the oxide layer generally does not provide complete protection due to the presence of micropores and cracks in the oxide layer. In particular, when metal products made from alloys are exposed to high temperatures in an oxidizing atmosphere, significant oxidation of the metal can occur due to defects in the oxide layer.

It is also known that growth and adhesion of protective oxide layers are associated with the movement of metal ions from the alloy. From SE 462 395 it can be seen that addition of 0.01-0.15% of rare earth metals to the silicon alloyed heat resistant austenitic material can reduce oxide cracking at high temperatures.

The amounts of cerium (Ce) and other rare earth metals described above in relation to silicon have a positive effect on the growth of the protective SiO ₂ layer on the metal surface when exposed to high temperatures in an oxidizing atmosphere, particularly in metal ions, in particular chromium. The SiO ₂ layer, which inhibits exit from this alloy, reduces the cracking of the oxide.

From SE 421 325 and SE 446 636, it can be seen that the addition of yttrium to the chromium aluminum iron alloy and the chromium aluminum silicon iron alloy yields a high temperature material with good oxidation resistance. However, the oxidation resistance improvement due to yttrium addition is not described in this publication. However, SE 421 325 citing GB 1 045 993 discloses that alloys having up to 20% by weight of chromium and small amounts of yttrium lose oxidation resistance. According to SE 446 363, citing US 3,027,252, iron, chromium, aluminum and yttrium alloys have high heat resistance and good oxidation resistance.

Hydrogen is generally regarded as an impurity in the alloy. In certain types of steel, hydrogen dissolved in molten steel may cause so-called flakes during cooling after hot working. To eliminate this risk, it is common to anneal such types of steel for several days to remove hydrogen. Hydrogen pick-up during pickling of steel in non-oxidizing acids may, for example, result in fracture of the material under less tension than usual. This is called hydrogen embrittlement and can be avoided by heating the material to remove hydrogen. Hydrogen is also known to reduce the oxidation resistance of alloys of the aforementioned types. For some reason, hydrogen is generally considered to have no beneficial effects and is harmful.

As mentioned above, the corrosion resistance of materials of the kind described in the introduction depends on the presence of a corrosion resistant oxide layer on the metal surface, the oxide layer having good adhesion to the metal substrate and having defects in the form of micropores and / or cracks. This should not be as possible. It can be expected that the growth of the oxide at the interface between the metal and the oxide promotes the adhesion of the oxide. "Hydrogen in chromium as described by B Tveten et al. In Oxidation of metals No. 3/4 51 published in 1999; high temperature oxidation rates of O ₂ , kinetics of oxide growth, And effect on scale adhesion ", undesirable oxide growth at the oxide / gas-interface depends on the migration of cations through the oxide layer, while desirable oxide growth at the oxide / gas-interface is diffusion or It is described that it depends on oxygen from other means. The cited paper also discloses that hydrogen in the metal increases the movement of the metal in the oxide layer while reducing the movement of oxygen and in this way the hydrogen impairs the corrosion resistance of the material in the oxidizing environment.

The present invention relates to a metal product of an alloy comprising at least one of metal chromium, aluminum, silicon and / or titanium, wherein the metal chromium, aluminum, silicon and / or titanium has a corrosion resistant layer on the surface of the metal product in an oxidizing atmosphere. It is contained in an amount to form. The invention also relates to a method of making a product and its use in various applications.

The present invention is particularly applicable to heat resistant materials. Examples of such heat resistant materials are heat resistant ferrite and austenitic stainless steels and other alloys, which typically contain significant amounts of chromium and nickel. Also significant amounts of silicon can be present in this type of stainless alloy. The metal products according to the invention can also be made of heating elements or materials for heating elements, which typically comprise 20-25% of chromium and about 5% of aluminum and are able to withstand extremely high temperatures. Among the aluminum alloy materials are ferritic stainless steels such as catalytic combustion steels for automobiles. Other applicable applications include superalloys, alloys containing chromium as the main component, alloys containing aluminum as the main component, and metal products made of titanium matrix alloys or alloys containing sufficient amounts of titanium. However, it should be noted that the field of application of the present invention is not limited to the specific types of materials described above, but such specific materials are merely examples of numerous uses.

In the following description of the experiments performed, reference is made to the following figures. In other words,

FIG. 1 shows oxygen intrusion in commercial Fe, Cr, Ni, Si alloy samples containing 0.05% Ce at various exposure times in an O ₂ -H ₂ O atmosphere at 900 ° C. A plot plotted as a function of

FIG. 2 is a diagram showing a larger enlarged view of the portion A indicated by the border of FIG. 1. FIG.

3 is a diagram obtained from FIG. 2, showing the intrusion time of a particular amount of oxygen for the same samples as a function of the hydrogen intrusion time of the samples.

FIG. 4 is a plot showing the oxidation kinetics at 1000 ° C., 20 mbar O ₂ of Fe, Cr, Al alloys with different yttrium content and essentially free of hydrogen.

FIG. 5 is a chart showing the oxidation rates at 1000 ° C., 20 mbar O ₂ , of commercial Fe, Cr, Al alloy strips with various hydrogen concentrations.

FIG. 6 is a plot showing oxidation at 20 mbar O ₂ + H ₂ O of test specimens of Fe, Cr, Al alloys containing 1% Yt for various different hydrogen intrusion times, in the same manner as FIG. .

FIG. 7 is a diagram obtained from FIG. 6 in the same manner as FIG. 3, showing a certain amount of oxygen intrusion time as a function of hydrogen intrusion time; FIG.

8A-8C show the surfaces of test specimens exposed to hydrogen intrusion for 0, 9 and 120 minutes respectively and evaluated according to FIGS. 6 and 7.

FIG. 9 is a plot showing oxidation in an oxidizing atmosphere at 900 ° C. of essentially pure chromium test specimens, each with and without 1% yttria and with different hydrogen levels.

Unless otherwise stated in the specification and drawings, the terms are based on weight percent and weight ppm.

The basis of the present invention is that hydrogen in the above-described type of alloys favorably completes the protective oxide layer, i.e. by removing micropores and other defects to make the oxide layer more dense and / or improving the adhesion of oxides. It is based on the surprising finding that it can be seen to improve the corrosion resistance of a material in an oxidizing atmosphere, wherein the hydrogen is in elemental form and / or capable of effectively separating oxygen at the interface between the surrounding gas phase and the oxide layer of the product. Or in combination with one or more elements in the form of oxides, in which case the elements are yttrium, elements of atomic numbers 57-71 and rare earth metals of scandium (referred to as REM), hafnium, zirconium, niobium, tantalum, titanium, palladium, platinum, And "oxygen-separating element (ODE)" belonging to a group consisting of a metal such as rhodium. In addition, anodic dissolution becomes smaller in liquid chloride atmosphere, which means improved corrosion resistance in liquid media containing chloride ions. In order to significantly improve the metal product, at least the layer next to the metal surface (about 1 mm thick) should contain at least 0.5 ppm by weight of hydrogen and ODE with a total amount of at least 0.01% by weight. The hydrogen content in the surface layer should preferably be combined with at least 1 ppm by weight, more preferably at least 2 ppm by weight, and at the same time with 0.03% by weight of ODE, more preferably at least 0.05% by weight of ODE. In order to achieve the best effect, the layer after the metal surface of the metal article should contain at least 5 ppm by weight of hydrogen and at least 0.1 wt.% Of ODE in total. Higher levels of hydrogen and ODE are also preferred, as described in the claims. In a preferred embodiment, the ODE can be one or more of scandium, hafnium, palladium, platinum, and rhodium and REM or basically REM.

From the experimental results,

That hydrogen in non-ODE alloy materials of the kind described at the beginning of this specification deteriorates the oxidation resistance of the material at high temperatures,

The addition of ODE to this type of alloy without hydrogen also deteriorates the oxidation resistance of the material at high temperatures,

The addition of both ODE and hydrogen to this type of alloy improves the oxidation resistance of the material at high temperatures and in at least somewhat aggressive liquid media such as chloride containing liquids,

An optimum hydrogen level can be found that provides optimum oxidation resistance at high temperatures of this type of ODE alloy material, the optimum hydrogen level being in the composition of the alloy, and in part in the content of the ODE, and in part. Depending on the metal chromium, aluminum, silicon, and / or titanium forming the oxide layer,

That the optimal hydrogen level providing optimum oxidation resistance of this type of ODE alloy material can be determined by measuring the time at which the hydrogen content reaches some degree of oxygen infiltration in samples with different hydrogen content, and

Significant improvements in oxidation resistance can also be shown that both higher and lower hydrogen contents than the optimum hydrogen content of the alloy can be achieved, ie in the hydrogen content range including the optimal hydrogen content of the alloy.

From these observations, it can be concluded that the hydrogen content of the alloy according to the present invention should generally satisfy the following relationship.

_{H min = 0.1 × H opt ≤H} opt ≤10 × H opt = H max

More preferably, the following relation is satisfied.

_{H min = 0.3 × H opt ≤H} opt ≤3 × H opt = H max

In this case, H _opt is an alloy within the basic composition of the composition for the metal element described in the claims, which is responsible for a certain degree of oxygen invasion when the material is exposed to an oxidizing atmosphere at a high temperature, for example, in the range from 800 ° C. to 1100 ° C. The hydrogen content that results in the longest time. In most cases, at least the hydrogen level in the surface layer should be at least 10 ppm by weight, preferably at least 15 ppm by weight, more preferably at least 20 ppm by weight. It should contain at least 0.8% ODE.

The maximum ODE level depends to some extent on whether the metal product as a whole contains an ODE or whether the ODE is present only in the surface layer. In the first case the ODE level should be 3% and in the latter case the maximum should be 10%. In the first case, the ODE is in the form of a metal, for example yttrium or in the form of a so-called misch metal which basically contains cerium and lanthanum (La), and / or for example y ₂ O ₃ Is added to the alloy in an oxide form such as) in an amount corresponding to up to 3 wt% ODE levels. In the latter case, the ODE may be applied directly onto the metal surface such that the surface layer contains a significant amount of ODE up to 70% by weight of ODE. Such application can be effected, for example, by coating the surface of the ODE with an independent carrier or by dipping the product into a liquid medium comprising the ODE and then heating and / or drying.

R _min

The experiments conducted indicate that in the surface layer of the product to achieve optimum corrosion resistance, there is an optimal relationship R _min between the hydrogen level and the ODE level expressed in weight ppm H / wt% ODE, and according to the following relationship It is indicated that the levels of hydrogen and ODE should be adjusted to each other such that the relationship between the levels of hydrogen and ODE is R _min and maximum R _max . In other words,

R _min ≤ R _opt ≤ R _max

At this time, R _min is 3, preferably 10, and R _max is 200, preferably 50.

Hydrogen can be added to the molten alloy, for example by steam injection in connection with the metallurgical treatment of the melt. Alternatively, or preferably, hydrogen may be added to the metal product in the solid metal phase by diffusion of hydrogen. In the case where the metal product is in the form of a strip or wire, the diffusion of hydrogen into the product is, for example, led by a continuous guide through the strip, wire or the corresponding product and a bright annealing furnace filled with hydrogen gas. It can be carried out in a furnace such as 900-1200 ℃, preferably at a high temperature of 1050-1200 ℃.

In addition, the alloy can be produced by conventional methods by common melting processes, casting, hot rolling and the like. By spray molding or other known techniques, the alloy may also be produced using powder metallurgy. It is also possible to use newly known techniques.

Experiment 1.

The base material in this experiment is wt.% Avesta 353MA ^{? With a} nominal composition of 0.05 C, 0.15 N, 25 Cr, 35 Ni, 1.3 Si, and 0.05 Ce and the remaining iron and impurities in weight percent ^. Heat-resistant austenitic Fe, Cr, Ni alloys. A sample of 0.1 mm thick foil machined with 2400 mesh SiC paper was prepared from the material, which was subsequently washed with 99.5% ethanol. The test specimen is exposed to hydrogen intrusion, i.e., the specimen is hydrogen invaded by diffusion to different degrees by exposure to hydrogen intrusion for several different times. Hydrogen intrusion is carried out by electrolytic method in which the test specimen is immersed in the electrolyte at room temperature and atmospheric pressure, and the electrolytic method consists of a specimen as a cathode and water. Hydrogen intrusion times for different specimens are 2, 8, 33, 115 and 350 minutes, respectively. Experimental specimens with a hydrogen level of 1 ppm or less without exposure to hydrogen intrusion were used as reference materials. After exposure to hydrogen intrusion, the test specimens were allowed to stand for a predetermined time to ensure a uniform hydrogen gradient in the specimens.

Thereafter, the test specimen is exposed to an oxidizing atmosphere of about 20 mbar 0 ₂ + ₂ mbar H ₂ 0, 900 ° C. Oxygen infiltration in test specimens expressed in μmol O / cm ² is recorded after several different oxidizing atmosphere exposure times have elapsed. 1 shows oxygen intrusion expressed in μmol O / cm ² as a function of the square root of the exposure time of the oxidizing atmosphere of the specimen.

In FIG. 2, the portion A indicated by the frame of FIG. 1 is enlarged and shown. Based on this plot, the time required for infiltration of 11.5 μmol O / cm ² is obtained for each specimen. In FIG. 3, this time is expressed as a function of hydrogen intrusion time for different specimens. In this case, the intrusion time of a certain amount of oxygen of 11.5 μmol O / cm ² indicates the result of measuring the corrosion resistance of the specimen in an oxidizing atmosphere; The longer the time required for a certain level of oxygen intrusion time, the better the corrosion resistance. Thus, the optimum values for corrosion resistance were recorded in test specimens exposed to hydrogen intrusion for 115 minutes. Longer hydrogen intrusion times worsen corrosion resistance. The time of showing the worst oxidation resistance expressed as 11.5 μmol O / cm ² , i.e. 69 minutes, was found in the specimen which was not exposed to hydrogen invasion, i.e. 0 minutes hydrogen intrusion time. The response time of the best specimen exposed to hydrogen intrusion for 115 minutes is 89 minutes, which corresponds to an extension of oxygen intrusion time of about 30%. Thus, the first series of experiments showed that a significant improvement in oxidation resistance can be achieved by the support of a certain amount of hydrogen in the liver, and that there is an optimal value with respect to the hydrogen content necessary to achieve optimum corrosion resistance. However, the improvement in corrosion resistance of these materials, including 0.05% Ce, is shown to be relatively small at all hydrogen levels of the material.

Experiment 2.

In this experiment, the trade names KANTHAL ^{? With a} nominal basis composition of up to 0.08 C, up to 0.7 Si, up to 0.4 Mn, about 5 Al, remaining iron and inevitable impurities in weight percent, differing in the content of yttrium and hydrogen; An FeCrAl alloy known as was tested. Experimental materials were each made of 1 mm thick plates and 0.1 mm thick foil. Test specimens were prepared in the same manner as in Experiment 1.

First, the oxidation resistance of 1 mm thick samples having different yttrium contents and low hydrogen contents as a reference material, such as 0.3% Y, 1.26% Y and yttrium free base alloy, was tested. After vacuum heating at 200-400 ° C. and holding at 1000 ° C. for 3-4 minutes under vacuum, the specimen was oxidized at 1000 ° C., about 20 mbar O ₂ . Oxygen intrusion was recorded as a function of time in the oxidation chamber. The results are shown graphically in FIG. 4. As can be seen from the diagram, oxidation increases rapidly as the yttrium content increases, that is, oxidation resistance deteriorates. The best corrosion resistance can be seen in samples that do not contain yttrium.

Thereafter, as 0.1 mm thick test specimens of the same base alloy without yttrium, a specimen containing no hydrogen and a specimen containing 40 ppm H were tested. Oxidation was carried out under the same conditions as in the previous experiment. In this case, as it turned out, the reference material without hydrogen showed the best corrosion resistance. As can be seen in FIG. 5, the material comprising about 40 ppm H exhibited significantly greater oxygen intrusion.

In the following experiments, 0.1 mm thick specimens of the same base material containing 1% Y were tested after different periods of exposure to hydrogen intrusion. Samples were oxidized under the same conditions as in Experiment 1. Oxidation intrusion after treatment in an oxidizing atmosphere for different times was recorded and shown schematically in FIG. 6. Thereafter, for the test specimens exposed to different hydrogen intrusion times, the time taken for specific oxygen intrusion, in this case 6.5 μmol O / cm ² , was calculated in the same manner as in Experiment 1. The results are shown graphically in FIG.

From the diagram of FIG. 7, it can be seen that the yttrium alloyed material significantly improves the corrosion resistance after exposure to hydrogen intrusion for a short time of 9 minutes. Longer exposure to hydrogen intrusion reduces oxidation resistance, and after exposure to hydrogen intrusion for a very long time, the corrosion resistance is worse than that of materials not exposed to hydrogen intrusion. Experimental results show that when the alloy contains 1% Y, there is an important optimal level for obtaining good results for the alloy of the given base composition described above. The shorter hydrogen intrusion time to reach the optimal hydrogen level for optimal corrosion resistance in Fe, Cr, and Al alloys results in a lower hydrogen diffusion rate in the alloy of the former. Lays. The improvement, expressed as the time required for invasion of 6.5 μmol O / cm ² , is about 650% improvement over the material in which yttrium is alloyed and not exposed to hydrogen intrusion.

In FIG. 8A, the photograph which shows the high magnification of the surface of the material which was not exposed to hydrogen intrusion but instead removed the gas by the hydrogen level of 1 ppm or less was shown. The oxidized material presents a number of defects in the form of micropores in the surface layer, which accounts for the limitation of the oxidation resistance of the material. 8C shows a high magnification of the surface of the material exposed to hydrogen intrusion for the longest period of 120 minutes. On the surface of this material, thick oxides in the form of isolated islands between thin oxides can be seen. This indicates that high metal mobility occurs in the oxide of the material of high hydrogen content, and explains that the oxidation resistance of the material deteriorates not only in the material having the best corrosion resistance but also in the material which is not hydrogen alloyed. The material exposed to hydrogen intrusion for 9 minutes is shown in FIG. 8B. This material represents an essentially uninterrupted oxide layer free of visible micropores and other defects.

Experiment 3.

In this experiment, powder metallurgy produced chromium was tested. More specifically, so-called Planse chromium having yttrium in the form of 1% Y ₂ O ₃ and no yttrium and having different hydrogen levels was tested. Specimens were prepared in the same manner as in Experiment 1. Exposure to hydrogen intrusion was carried out in the same manner as in Experiments 1 and 2.

Experimental specimens with a thickness of 1 mm were oxidized at about 20 mbar O ₂ + 2 mbar H ₂ O and 900 ° C. Oxygen ingress at different times in an oxidizing atmosphere was recorded and shown graphically in FIG. 9.

From the diagram of FIG. 9, specimens containing no yttria in the yttria form and containing significant amounts of hydrogen by "natural" hydrogen intrusion due to prolonged atmospheric exposure or by 4 hours of exposure for hydrogen intrusion are the worst corrosion resistance. It can be seen that Materials that are not alloyed with yttria and are free of hydrogen and materials that are alloyed with yttria and are free of hydrogen have the same tendency for oxygen penetration. Materials alloyed with yttria and exposed to hydrogen intrusion for a long time of 8 hours have a rather good oxidation resistance, although not to a considerable extent. The lowest oxygen intrusion occurs in the yttria-alloyed material exposed to hydrogen intrusion for four hours.

From the present experiments and the results shown in FIG. 9, it can be seen that the positive effects combined with respect to corrosion resistance can be achieved by the presence of certain amounts of yttrium and optimal levels of hydrogen.

The amount of hydrogen in the material exposed to hydrogen intrusion for 4 hours was measured at about 25 ppm. In contrast to the gravimetric results, it was found that the reference material which was not exposed to hydrogen intrusion increased by 40% more compared to the material according to the invention comprising yttrium in the form of 1% yttria and about 25 ppm hydrogen.

Claims (30)

A metal product of an alloy comprising at least one of metal chromium, aluminum, silicon, and / or titanium at a level that forms a corrosion resistant oxide layer on a metal surface in an oxidizing atmosphere, At least in the layer following the metal surface, the metal product belongs to a group of yttrium, rare earth metals (REM) containing elements and scandium, and hafnium, zirconium, niobium, palladium, platinum, and rhodium And at least 0.01% by weight of one or more elements in elemental form and / or oxide form, which are called oxygen separation elements (ODE) and which are capable of effectively separating oxygen at the boundary between the oxide layer of the product and the surrounding gas phase. Metal product comprising at least 0.5 wtppm. The metal article of claim 1, wherein the ODE level in the surface layer is at least 0.03% by weight, preferably at least 0.05% by weight. The metal article according to claim 1 or 2, wherein the hydrogen level in the surface layer is at least 1 ppm by weight, preferably at least 2 ppm by weight. 4. A metal product according to any one of the preceding claims, wherein the level of the ODE is at least 0.1% by weight. 4. A metal article according to claim 3, wherein the hydrogen level in the surface layer is at least 5 ppm, preferably at least 10 ppm by weight. 6. Metal article according to claim 5, characterized in that the hydrogen content in at least the layer next to the metal surface is at least 15 ppm by weight, preferably 20 ppm by weight. The metal article of claim 1, wherein the alloy comprises at least 0.2 wt.% ODE. 8. A metal article according to claim 7, wherein the alloy comprises at least 0.5 wt% ODE, preferably at least 0.8 wt% ODE. 9. The metal article of claim 8, wherein the ODE is present only in the surface layer of the metal article and the ODE level in the surface layer is at most 5-80 wt%. 9. The metal article according to claim 1, wherein the ODE is uniformly distributed in the article and present at a level of 3% by weight. 10. Claim 1 to claim 10 according to any one of claims, wherein the hydrogen content of the alloy satisfies a relation _{H min = 0.1 × H opt ≤H} opt ≤10 × H opt = H max, preferably a relational expression H = _min 0.3 × H _{opt opt} ≤H sikimyeo ≤3 meet × H _opt = H _{max, Wherein} H _opt is a hydrogen content in each alloy in the base composition associated with the metal element as defined in claim 1 which takes a long time to invade specific oxygen when the alloy is exposed to a high temperature oxidizing atmosphere. . 12. The method according to any one of claims 1 to 11, wherein the ratio of hydrogen content and ODE content in the surface layer satisfies the relationship R _min ≤ weight ppm H / wt% ODE ≤ R _max , wherein R _min is 3 Preferably it is 10, and _Rmax is 200 preferably 50. 13. The metal article of claim 1, wherein the ODE consists essentially of any of REM and / or metal scandium, hafnium, palladium, platinum, and rhodium. The metal article of claim 13, wherein the ODE consists essentially of a REM. A method for producing a metal product of an alloy comprising at least one of metal chromium, aluminum, silicon, and / or titanium in an amount that can form a corrosion resistant oxide layer on the metal surface in an oxidizing atmosphere, In at least the layer following the metal surface, the metal product consists of a rare earth metal (REM) comprising yttrium, elements 57-71 and scandium, hafnium, zirconium, niobium, tantalum, titanium, palladium, platinum, and rhodium The total amount of one or more elements in elemental form and / or oxide form, belonging to the group and referred to as oxygen separation element (ODE), which can effectively separate oxygen at the interface between the oxide layer of the product and the surrounding gas phase To at least% by weight and at least 0.5 ppm by weight of hydrogen. Method according to claim 15, characterized in that the metal product comprises at least 1 ppm hydrogen, preferably at least 2 ppm hydrogen. 17. The method of claim 15 or 16, wherein the surface layer of the metal product comprises at least 0.1% ODE. 13. A method according to claim 12, wherein the metal product contains at least 5 ppm hydrogen, preferably at least 10 ppm hydrogen. 19. A method according to claim 18, wherein the metal article comprises at least 15 ppm hydrogen, preferably at least 20 ppm hydrogen. 18. The method of claim 17 wherein the metal article comprises at least 0.2% ODE. 21. The method of claim 17, wherein the surface layer of the metal article comprises at least 0.5% ODE, preferably at least 0.8% ODE. 22. The method of claim 15, wherein the ODE is added to the alloy in a primarily molten state. 22. A method according to claim 15, wherein ODE is basically added to the surface layer of the article by applying it on the surface of the article and the ODE is added at a level of 5-80% by weight. 23. The method of claim 15, wherein at least a substantial portion of the hydrogen in the surface layer is added by diffusion into the material at a high temperature, preferably in the range of 900-1200 ° C. 23. Metal according to claim 15, characterized in that at least a substantial part of the hydrogen in the surface layer is added by electrochemical means and preferably cathodic polarization / electrolytically in an aqueous solution. Product manufacturing method. 26. The metal article according to claim 15, wherein the added ODE is basically one of REM and / or scandium, hafnium, palladium, platinum, and rhodium, preferably basically only REM. Manufacturing method. Use of the metal product according to claim 1 as an electrical resistive material. Use of the metal product according to claims 1 to 14 as a carrier for the catalyst. Use of the metal product according to claims 1 to 14 as part of a structural member for use in an oxidizing atmosphere at a temperature of 400 ° C. or higher. Use of the metal product according to claims 1 to 14 as part of a structural member, vessel or tubing designed for a liquid medium comprising chloride or hydrogen ions.