EP1717330A1 - Metallrohr zur verwendung in aufkohlungsgasatmosphäre - Google Patents

Metallrohr zur verwendung in aufkohlungsgasatmosphäre Download PDF

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Publication number
EP1717330A1
EP1717330A1 EP05709298A EP05709298A EP1717330A1 EP 1717330 A1 EP1717330 A1 EP 1717330A1 EP 05709298 A EP05709298 A EP 05709298A EP 05709298 A EP05709298 A EP 05709298A EP 1717330 A1 EP1717330 A1 EP 1717330A1
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Prior art keywords
metal
oxide scale
content
enriched layer
acel
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EP05709298A
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French (fr)
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EP1717330B1 (de
EP1717330A4 (de
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Yoshitaka Sumitomo Metal Ind. Ltd. NISHIYAMA
Nobuo Sumitomo Metal Industries Ltd. OTSUKA
Takeo Sumitomo Metal Industries Ltd. KUDO
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Nippon Steel Corp
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Sumitomo Metal Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/325—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with layers graded in composition or in physical properties
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F15/00—Other methods of preventing corrosion or incrustation

Definitions

  • This invention relates to a metal tube which has good high-temperature strength and excellent corrosion resistance and which can be used in a carburizing gas atmosphere containing hydrocarbon gases or CO gas.
  • a metal tube according to the present invention has improved protecting ability against carburizing gases, and it is suitable for use as a material for tubes for pyrolysis furnaces or reforming furnaces, tubes for heating furnaces, or heat exchanger tubes in petroleum refinery or petrochemical plants.
  • the present invention makes it possible to control the ability of a metal tube used in a carburizing gas atmosphere to be protected against carburizing gas.
  • JP H09-78204A indicates that an Fe-based alloy or an Ni-based alloy containing 11 - 60% (here and below, percent refers to mass percent) of Cr has improved resistance to metal dusting in an atmospheric gas containing H 2 , CO, CO 2 , and H 2 O at 400 - 700° C.
  • the materials disclosed in that patent document are an Fe-based alloy containing at least 24% of Cr and at least 35% of Ni, an Ni-based alloy containing at least 20% of Cr and at least 60% of Ni, and these alloys to which Nb is further added.
  • JP H11-172473A in order to suppress corrosion due to metal dusting of a high-temperature alloy containing iron, nickel, and chromium, at least one metal selected from Group VIII, Group IB, Group IV, or Group V of the periodic table or mixtures thereof is deposited on the surface of a metallic material by a conventional physical or chemical method, and the material is subjected to annealing in an inert atmosphere to form a thin layer with a thickness of 0.01 - 10 micrometers on the surface thereof. Sn, Pb, Bi, and the like are particularly effective in this method. However, even though this method is initially effective, its effect seems to disappear during long periods of use due to spalling of the thin layer.
  • JP 2003-73763A as a result of investigating the interaction of C with dissolved elements in iron with respect to resistance to metal dusting in an atmospheric gas containing H 2 , CO, CO 2 , and H 2 O at 400 - 700 ° C, it is described that an alloying element which has a positive value of the interaction coefficient ⁇ is effective at suppressing metal dusting.
  • a metallic material is disclosed in which the contents of Si, Al, and Ni as well as Cu and Co are controlled. These alloying elements serve to greatly increase resistance to metal dusting, but increasing the content of alloying elements such as Si, Al, and Cu decreases hot workability and weldability of the material. Therefore, in view of stable supply and manufacture and plant layout, there is room for improvement.
  • JP S53-66832A and JP S53-66835A disclose a method in which a 25Cr-20Ni (HK40) low-Si heat resistant steel or a 25Cr-35Ni low-Si heat resistant steel is subjected to pre-oxidation for at least 100 hours at around 1000° C in air.
  • JP S57-43989A discloses a technique in which an austenitic heat-resistant steel containing 20 - 35% Cr is subjected to pre-oxidation in air.
  • JP H11-29776A discloses a method for increasing resistance to carburization by heating a high Ni-Cr alloy in a vacuum to form a scale coating.
  • JP 2000-509105 discloses a method of increasing resistance to carburization by forming a surface layer enriched with Si and Cr by surface treatment.
  • the present invention provides a metal tube which has the ability to protect against a carburizing gas, thereby exhibiting improved resistance to metal dusting, resistance to carburization, and resistance to coking, and which is suitable for use as a tube for a pyrolysis furnace for use in an ethylene plant or a reforming furnace or the like.
  • the present inventors analyzed the surface condition of various metal tube materials. They found that if an oxide layer which forms on the surface of a metal tube is dense, the above-described corrosive phenomena do not occur, but if the oxide layer has locally formed defects such as cracking or spalling, C which is present in a gas penetrates through these defects, and at the same time, the exposed metal serves as a catalyst to induce deposition of carbon.
  • the content of these elements is preferably made as low as possible without losing the above-described resistance to carburization, resistance to metal dusting, and resistance to coking.
  • the gas adsorption is a phenomenon which occurs on the surface of a metal material, and thought that if a Cu-enriched layer is present only on a metal surface, it should be possibly to essentially reduce dissociation of adsorbed gas to suppress carburization and metal dusting. They carried out experiments to confirm whether a desired performance can be obtained by limiting the Cu content in a metal material (alloy) to a level which does not cause problems with respect to manufacturability and weldability and at the same time treating the material to increase the Cu concentration in the surface portion.
  • Figure 1(A) and Figure 1(B) show the relationship between the Cu concentration at the surface and the length of time until the occurrence of pitting of plate-shaped test pieces made of 25% Cr-35% Ni-bal.
  • Fe alloys [ Figure 1(B)] which are different in Cu content and hence in Cu concentration at the surface when they were subjected to a corrosion test which was carried out in a 60% CO-26% H 2 -11.5% CO 2 -2.5% H 2 O (volume %) gas at 650° C. From these figures, it can be seen that the effect of suppressing pitting, i.e., metal dusting appears when the Cu concentration in the metal surface exceeds 0.1 atom percent.
  • the Cu concentration was obtained by converting into atomic percent the measured value of elemental analysis which was performed in the depth direction from the surface of the metal by AES (Auger electron spectroscopy).
  • AES Alger electron spectroscopy
  • Figure 2(A) and Figure 2(B) show the relationship between the thickness of a Cu-enriched layer and the occurrence of pitting when a Cu-enriched layer is formed under different conditions on the surface of a 25% Cr-35% Ni-0.5% Cu-bal. Fe alloy [ Figure 2(A)] or a 25% Cr-55% Ni-2.5% Al-0.3% Cu-bal. Fe alloy [ Figure 2(B)].
  • the corrosion test conditions were the same as those described above.
  • the Cu concentration in the Cu-enriched layer of the test alloys was in the range of approximately 0.4 - 0.8 atomic percent [Figure 2(A)] or approximately 0.2 - 0.5 atomic percent [ Figure 2(B)].
  • the thickness of the Cu-enriched layer is at least 0.3 nm (nanometers)
  • the time until the occurrence of pitting is increased i.e., the Cu-enriched layer has an effect on resistance to metal dusting.
  • an invention based on these findings is a metal tube for use in a carburizing gas atmosphere formed from a base metal containing, in mass percent, Cr: 15 - 35%, Ni: 30 - 75%, Al: 0.001 - 10%, and Cu: 0.01 - 10%, characterized in that the metal tube has a Cu-enriched layer in a surface region, the Cu-enriched layer having a Cu concentration of at least 0.1 atomic percent and a thickness of at least 0.3 nm.
  • This metal tube may further have a layer of an oxide scale on the outside of the Cu-enriched layer, the oxide scale having a Cr content of at least 50 mass percent or a total content of Cr + Al of at least 50 mass percent.
  • the metal tube may have a second layer of an oxide scale having an Si content of at least 50 mass percent between the first oxide scale and the Cu-enriched layer.
  • the inner surface and/or the outer surface of a metal tube according to the present invention may have an irregular shape.
  • the base metal preferably has a chemical composition comprising, in mass percent, C: 0.01 - 0.6%, Si: 0.01 - 5%, Mn: 0.01 - 10%, P: at most 0.08%, S: at most 0.05%, Cr: 15 - 35%, Ni: 30 - 75%, Cu: 0.01 - 10%, N: 0.001 - 0.25%, Al: 0.001 - 10%, O (oxygen): at most 0.02%, and a remainder of Fe and impurities.
  • This chemical composition may further contain, in mass percent, at least one element selected from below-described (i) through (vi).
  • the present invention is a method of improving the resistance to metal dusting, resistance to carburization, and resistance to coking of a metal tube used in a carburizing gas atmosphere and comprising a base metal containing, in mass percent, Cr: 15 - 35%, Ni: 30 - 75%, Al : 0.001 - 10%, and Cu: 0.01 - 10%, characterized by forming a Cu-enriched layer in a surface region of the metal tube, wherein the Cu-enriched layer has a Cu concentration of at least 0.1 atomic percent and a thickness of at least 0.3 nm.
  • an oxide scale having a Cr content of at least 50% or having a total content of Cr + Al of at least 50 mass percent may be formed on the outer side of the Cu-enriched layer, and an Si-based second oxide scale having an Si content of at least 50% may be formed between the above-described oxide scale and the Cu-enriched layer.
  • a metal tube according to this invention has the ability to protect against a carburizing gas, and it has improved resistance to metal dusting, to carburization, and to coking. Therefore, it can be used in tubes for pyrolysis furnaces, tubes for reforming furnaces, tubes for heating furnaces, piping, or heat exchanger tubes or the like in petroleum refinery or petrochemical plants, and it can greatly increase the durability and operating efficiency of equipment.
  • a metal tube according to the present invention is formed from a base metal containing Cr: 15 - 35%, Ni: 30 - 75%, Al: 0.001 - 10%, and Cu: 0.01 - 10%, and it has a Cu-enriched layer in its surface region.
  • a Cu-enriched layer can be provided on one or both of the inner and outer surfaces of a metal tube.
  • the object of the present invention can be achieved if a Cu-enriched layer is formed only on the surface of the metal tube which is exposed to a carburizing gas atmosphere.
  • a Cu-enriched layer can be formed on the inner surface of a reaction tube or a pyrolysis furnace tube, or can be formed on the outer surface of a heat exchanger tube.
  • a Cu-enriched layer may be formed on both surfaces of a metal tube.
  • a Cu-enriched layer refers to a region having a Cu concentration (mass percent) which is higher than the average Cu concentration (mass percent) of the base metal.
  • the thickness of the Cu-enriched layer is the distance in the depth direction (namely, in the radial direction of the metal tube) from the metal surface (when at least one layer of oxide scale is present on the metal surface, from the interface with the innermost oxide scale) to a position where the Cu concentration is the same as the average Cu concentration of the base metal (namely, the interface between the Cu-enriched layer and the base metal).
  • the Cu concentration of the Cu-enriched layer means the average value of the Cu concentration inside the layer.
  • the Cu concentration is measured by AES as in the examples, the average of the measured values in the layer (a value converted to atomic percent) is made the Cu concentration of the Cu-enriched layer.
  • the Cu concentration and the thickness of the Cu-enriched layer can be measured using AES.
  • AES the surface being measured is irradiated with an electron beam, and the concentration of metallic elements in the surface can be measured by detecting the emission of Auger electrons.
  • a small piece is cut from a portion of the metal tube, and analysis can be carried out in the depth direction from the surface by carrying out AES while the surface is gradually removed by sputtering.
  • the thickness of the Cu-enriched layer can be measured by measuring the Cu concentration of the surface of the material in the depth direction up to where the Cu concentration is constant, and the Cu concentration of the Cu-enriched layer can be found as the average Cu concentration within the enriched layer.
  • the Cu-enriched layer is provided in a surface region of a metal tube.
  • the surface region of a metal tube means a region in the vicinity of the tube surface. Its location depends upon the method of forming the Cu-enriched layer. There are cases in which the Cu-enriched layer is the outermost layer of the metal tube, but when one or more layers of oxide scales are present on the outer side of the Cu-enriched layer, the Cu-enriched layer is present between the oxide scales and the base metal.
  • the Cu concentration of the Cu-enriched layer is at least 0.1 atomic percent. If the Cu concentration of the Cu-enriched layer is less than 0.1 atomic percent, it is not possible to achieve a protecting effect by suppressing adsorption of a C-dissociating gas such as a hydrocarbon or CO gas present in a carburizing gas during plant operation. In addition, even when an oxide scale is present on the metal surface as described above, if the Cu concentration of the Cu-enriched layer immediately beneath the scale layer is less than 0.1 atomic percent, if the oxide scale undergoes damage such as cracking or spalling, it is not possible to suppress adsorption of gas by the exposed metal surface.
  • the Cu concentration of the Cu-enriched layer is preferably at least 0.3 atomic percent, and more preferably it is at least 1.0 atomic percent.
  • the thickness of the Cu-enriched layer is at least 0.3 nm. If the thickness of the Cu-enriched layer is less than 0.3 nm, it is not possible to achieve protecting by suppressing adsorption of a C-containing gas such as a hydrocarbon or CO gas in a carburizing gas at the time of plant operation.
  • the thickness of the Cu-enriched layer is preferably at least 0.5 nm.
  • the thickness of the Cu-enriched layer can be easily adjusted by varying the conditions of alternating current electrolysis or controlled atmospheric heat treatment, for example. There is no particular upper limit on the thickness of the Cu-enriched layer, but normally it does not exceed 100 nm.
  • Methods of forming a Cu-enriched layer include, but not limited to, alternating current electrolysis, controlled atmospheric heat treatment, and pickling treatment. Two or more of these methods may be used.
  • Alternating current electrolysis is a method in which an applied voltage is swept to a noble potential which causes some alloying elements to dissolve in the electrolytic solution, and then is swept to a base potential to cause Cu to precipitate on the surface.
  • Cu is electrically more noble than Ni, Cr, or Fe, and it is preferentially precipitated by electrolysis in a base potential.
  • This treatment can form a Cu-enriched layer on the surface of a metal tube which is in contact with the electrolytic solution. It can form a Cu-enriched layer with certainty.
  • the thickness and the Cu content of the resulting Cu-enriched layer can be varied based upon the applied voltage and the duration of application of the voltage for each of the noble and base potential.
  • an oxide scale When an oxide scale is provided on a metal surface, it is possible to form a Cu-enriched layer by the formation of an oxide scale comprising predominantly Cr or Cr + Al or a second oxide scale comprising predominantly Si by controlled atmospheric heat treatment, since the formation of such an oxide scale causes the concentrations of Cr, Al, and Si in a region immediately beneath the scale to decrease so that the Cu concentration in that region becomes higher than that inside the base metal.
  • a Cu-enriched layer can also be formed by utilizing pickling treatment which causes elements other than Cu to preferentially dissolve out so that the Cu concentration in the surface layer is increased.
  • a Cu-enriched layer can be formed between the oxide scale and the base metal alloy.
  • oxide scale a layer or film of oxide scale
  • a first oxide scale comprising predominantly Cr or Cr + Al [referred to below as oxide scale (A)] is preferably present on the surface of the metal tube, and a second oxide scale comprising predominantly Si [referred to below as oxide scale (B)] may also be formed on the inner side of layer (A).
  • Oxide scale (A) is a layer of an oxide scale comprising predominantly Cr or Cr + Al. Whether this oxide scale comprises predominantly Cr or Cr + Al depends upon the Al content in the alloy. In general, if the Al content of the base metal is at least 1.5%, the oxide scale predominantly comprises Cr + Al, and if the Al content is less than 1.5%, the oxide scale predominantly comprises Cr.
  • Oxide scale (A) can be formed by heating a metal tube in an oxidizing atmosphere to a temperature at which surface oxidation takes place.
  • the thickness of the resulting oxide scale can be varied depending upon conditions such as the heating temperature, the heating time, and the partial pressure of oxygen in the atmosphere.
  • the partial pressure of oxygen should be at least the dissociation pressure of an oxide comprising predominantly Cr.
  • the composition of the oxide scale is primarily determined by the alloy composition of the base metal.
  • An oxide scale comprising predominantly Cr or Cr + Al is extremely important from the standpoints of resistance to metal dusting, resistance to carburization, and resistance to coking.
  • a Cr-based oxide scale having a Cr content of at least 50% has a high denseness, and it has a good ability to protect against penetration of carbon into steel.
  • a (Cr+Al)-based oxide scale in which the total content of Cr and Al is at least 50% has a still higher denseness, and it exhibits excellent protective properties.
  • Each of these oxide scales is thermodynamically stable up to a high temperature even in a high-temperature carburizing environment as encountered in a pyrolysis furnace for ethylene production, and it has protective properties over a long period.
  • any of these oxide scales has a low catalyzing effect with respect to coking, and it can suppress coking of the metal surface.
  • the thermal conductivity to the fluid flowing inside the tube can be maintained at a satisfactory level for long periods, and the yield of reaction products such as olefins is stabilized.
  • the Cr content or the total content of Cr + Al (in the case in which the oxide scale includes Al) of the oxide scale is at least 80%, the scale layer becomes denser, and it acts as a strong protecting layer against penetration of carbon into the steel. As a result, resistance to carburization greatly increases. More preferably, the Cr content or the Cr + Al content is at least 85%.
  • Oxide scale (B) is a layer of an oxide scale comprising predominantly Si. This oxide scale can be formed by heating a metal tube in an oxidizing atmosphere at a temperature at which surface oxidation occurs. The thickness of the resulting oxide scale varies in accordance with conditions such as the heating temperature, the heating time, and the partial pressure of oxygen in the atmosphere. The composition of the oxide scale is determined primarily by the steel composition of the base metal.
  • Si-based oxide scale (B) having an Si content of at least 50% is formed, it is preferably present between the Cu-enriched layer and oxide scale (A).
  • Oxide scale (B) serves to promote the uniform formation of oxide scale (A), and when damage such as cracking or spalling of oxide scale (A) occurs, it assists in healing of the damaged portion.
  • Oxide scale (B) comprising predominantly Si can be formed between the Cu-enriched layer and oxide scale (A) by heating a metal tube in a gas having a partial pressure of oxygen which is at least the dissociation pressure of oxides comprising predominantly Cr.
  • the dissociation pressure of oxides comprising predominantly Si is smaller than that of oxides comprising predominantly Cr. Therefore, oxide scale (B) on the inner side and oxide scale (A) on the outer side can be formed at the same time.
  • the thickness of each oxide scale varies in accordance with the heating temperature and heating time.
  • Formation of oxide scale (B) can be facilitated by increasing the Si content in the base metal alloy (to at least 0.4%, for example).
  • the thickness of an oxide scale can be measured by observation with an optical microscope of a sectional specimen for microscopic observation.
  • the content of elements in oxide scale (A) and oxide scale (B) can be measured using an EDX (energy dispersive X-ray) spectrometer. Measurement is usually carried out with a sectional specimen for microscopy having vapor deposition of C on its surface formed before it is subjected to EDX spectroscoy for quantitative analysis of elements. From the results of elemental analysis for each scale layer, the content of Cr, Al, and Si can be found when the total content of metallic elements is made 100%.
  • the inner and/or outer surface of a metal tube according to the present invention may be a surface with an irregular shape, such as one having bosses or one having differing dimensions.
  • a surface having such an irregular cross-section easily undergoes attack by carburizing gas, and as a result, damage such as spalling of an oxide scale formed thereon easily takes place.
  • the inner surface and/or the outer surface of a metal tube has high resistance to carburization, and an oxide film formed thereon has an improved ability to heal itself, so the effects of the present invention are particularly marked with a metal tube having an inner surface and/or an outer surface with an irregular cross-section.
  • a metal material (base metal) constituting a metal tube according to the present invention is preferably an alloy having the following composition (except for the Cu concentration of the Cu-enriched layer, which is expressed as atomic percent, the composition being expressed as mass percent, and the remainder is Fe and impurities).
  • the C content is at least 0.0 1 % in order to provide high-temperature strength. If the C content exceeds 0.6%, the toughness of the alloy becomes extremely poor.
  • a preferred range for the C content is 0.01 - 0.45%, and a more preferred range is 0.01 - 0.3%.
  • Si has a strong affinity for oxygen and facilitates the formation of Cr-based oxide scale (A) uniformly. This effect is exhibited when the Si content is at least 0.01 %. However, if the Si content exceeds 5%, weldability worsens, and the structure of the alloy becomes unstable. A preferred range for the Si content is 0.1 - 3%, and a more preferred range is 0.3 - 2.5%.
  • the upper limit on the Si content is preferably made 1%.
  • a more preferred range for the Si content in this case is 0.05 - 0.6%.
  • Mn is added in an amount of at least 0.01% for the purpose of deoxidation and improving workability. Since Mn is an austenite-forming element, it is possible to replace a portion ofNi by Mn. However, excessive addition of Mn impedes the formation of an oxide scale comprising predominantly Cr, so the upper limit of the Mn content is made 10%. A preferred range for the Mn content is 0.1 - 5%, and a more preferred range is 0.1 - 2%.
  • P and S segregate at grain boundaries and cause hot workability to deteriorate. Therefore, it is preferred that they be reduced as much as possible.
  • P is made at most 0.08%
  • S is made at most 0.05%.
  • P is at most 0.05% and S is at most 0.03%, and more preferably, P is at most 0.04% and S is at most 0.015%.
  • Cr is an important element in the present invention. It is necessary for the Cr content to be at least 15% in order to stably form an oxide scale comprising predominantly Cr. When the alloy contains at least 1.5% Al, an oxide scale comprising predominantly Cr and Al is formed which is denser and has higher protective properties. However, addition of an excessive amount of Cr deteriorates workability as well as stability in structure. Thus, the upper limit of Cr content is made 35%. A preferred range for the Cr content is 20 - 33%, and a more preferred range is 22 - 32%.
  • Ni is present in an amount of 30 - 75% since it is an element which acts to form a stable austenite structure depending on the Cr content. In addition, Ni also acts to reduce the speed of penetration of C when C penetrates into steel. However, an Ni content which is higher than necessary leads to cost increases and difficulty in manufacture. A preferred range for the Ni content is 35 - 70%, and a more preferred range is 40 - 65%.
  • Cu is one of the most important elements in the present invention.
  • Cu has a very strong effect on suppressing adsorption of a carburizing gas by a metal surface.
  • addition of Cu in excess of 10% causes hot workability to markedly decrease.
  • a preferred range for the Cu content is 0.03 - 5%, and a more preferred range is 0.1 - 3%.
  • N is an element which is effective at improving high-temperature strength. In order to obtain this effect, at least 0.001% of N is contained. Since excessive addition of N greatly impairs workability, the upper limit of the N content is 0.25%. A preferred range for the N content is 0.001 - 0.2%.
  • the N content is preferably at most 0.1% since Al and N form compounds which results in a decrease in creep strength.
  • a more preferred range for the N content in this case is 0.001 - 0.05%.
  • Al is an element which is effective even in minute amounts at improving hot workability.
  • at least 0.001 % of Al is added, and preferably at least 0.01% is added.
  • Al contributes to the formation of a dense oxide scale comprising predominantly Cr and Al and having good protective properties. Even when an oxide scale is not previously formed, in the environment of use, an oxide scale comprising predominantly Cr and Al is formed, thereby making it possible to greatly increase the resistance to metal dusting and resistance to carburization of a metal tube.
  • Al is present in an amount exceeding 10%, precipitation of hardening precipitates occurs in the alloy, resulting in a marked decrease in toughness and creep elongation of the alloy.
  • a preferred range for the A1 content when forming an oxide scale comprising predominantly Cr and Al is 2 - 8%, a more preferred range is 2 - 4%, and the most preferred range is 2.2 - 3.5%.
  • the Al content is preferably less than 1.5%.
  • a more preferred range for the Al content in this case is 0.01 - 1.2%, and the most preferred range is 0.01 - 0.5%.
  • Oxygen is present as an impurity. If the oxygen content exceeds 0.02%, a large amount of oxide inclusions are present in the alloy, and they cause workability to decrease and flaws to form on the surface of a metal tube. Thus, the upper limit on the oxygen content is made 0.02%.
  • Co has the effect of stabilizing an austenite phase, and a portion of Ni may be replaced by at least 0.01% of Co . However, if Co is added in excess of 5%, the hot workability of the alloy is markedly decreased. A preferred range for the Co content is 0.01 - 3%.
  • Mo and W are both solid-solution strengthening elements and are effective at increasing the high-temperature strength of an alloy. In order to exhibit this effect, at least 0.01 % of either one can be added. However, excessive addition of these elements worsens workability and impairs the stability of alloy structure, and hence the content of Mo and W are both made at most 10%.
  • a preferred range for each of Mo and W is 0.01 - 8% and a more preferred range is 0.1 - 5%.
  • Ti or Nb has a great effect on improving high-temperature strength, ductility, and toughness. However, these effects are not obtained with addition of less than 0.01% of each, while addition of over 2% causes a decrease in workability and weldability.
  • a preferred range for either Ti or Nb is 0.01 - 1.5% and a more preferred range is 0.02 - 1.2%.
  • B 0.001 - 0.1%
  • Zr 0.001 - 0.1%
  • Hf 0.001 - 0.5%
  • Each of B, Zr, and Hf is an element which strengthens grain boundaries and is effective at improving hot workability and high-temperature strength.
  • these effects cannot be obtained by addition of less than 0.001%, while excessive addition (greater than 0.1% for B and Zr, and greater than 0.5% for Hf) worsens weldability.
  • Mg 0.0005 - 0.1%
  • Ca 0.0005 - 0.1%
  • Each of Mg and Ca is an element which is effective at improving hot workability. This effect is marked with addition of at least 0.0005% for each. However, excessive addition of these elements worsens weldability, so the upper limit for each is made 0.1 %.
  • One or more of Y, La, Ce, and Nd 0.0005 - 0.15% each
  • Y, La, Ce, and Nd are elements which are effective at improving resistance to oxidation, but this effect is not obtained with addition of less than 0.0005% for each, while excessive addition worsens workability, so the upper limit is made 0.15% for each.
  • a preferred lower limit for each of these elements is 0.005%.
  • a metal tube according to the present invention having the ability to protect against a carburizing gas can be formed into a required tube shape such as a seamless tube or a welded tube by a combination of methods selected from melting, casting, hot working, cold working, welding, and the like.
  • a required tube shape can be formed by techniques such as powder metallurgy and centrifugal casting.
  • the surface of a metal tube which has undergone final heat treatment may be subjected to surface treatment such as pickling, shot blasting, machining, grinding, or electrolytic polishing. It is possible to apply a plurality of these techniques sequentially.
  • a Cu-enriched layer is then formed by the above-described method or methods.
  • Oxide scale (A) and oxide scale (B) may be formed at the time of final heat treatment, or they may be formed by carrying out heat treatment after surface treatment or after treatment to form the Cu-enriched layer.
  • a metal tube according to the present invention may have one or more bosses formed on the inner surface and/or the outer surface of the tube without in any way damaging the ability to protect against a carburizing gas. Examples of such bosses can be seen in finned tubes and the like used in tubes for pyrolysis furnaces for ethylene production. The bosses may be formed at the time of hot working or by welding, for example.
  • This example illustrates the case in which the Al content of a base metal is less than 1.5%, and an oxide scale comprising predominantly Cr is formed when forming an oxide scale.
  • Each of the metal materials having the chemical compositions shown in Table 1 was melted in a high frequency heating vacuum furnace and formed into a billet. From the billet, a metal tube having an outer diameter of 56 mm and a wall thickness of 6 mm was prepared by hot forging and cold rolling. Each metal tube was subjected to solid-solution heat treatment at 1200° C in air for 10 minutes.
  • the metal tube was cut into circular pieces approximately 30 mm long, and some of the cut metal tubes were subjected to surface processing treatment selected from shot blasting (outer surface only) (abbreviated as SB), pickling (abbreviated as Pic), pickling descaling (abbreviated as PiD), machining (outer surface only) (abbreviated as Mac), grinding (abbreviated as Grd), and combinations thereof.
  • surface processing treatment selected from shot blasting (outer surface only) (abbreviated as SB), pickling (abbreviated as Pic), pickling descaling (abbreviated as PiD), machining (outer surface only) (abbreviated as Mac), grinding (abbreviated as Grd), and combinations thereof.
  • each cut metal tube was subjected to alternating current electrolysis (abbreviated as ACEl) or controlled atmospheric heat treatment (abbreviated as ACHT) to form a Cu-enriched layer on the inner and outer surfaces of the tube.
  • ACEl alternating current electrolysis
  • ACHT controlled atmospheric
  • oxide scale (A) comprising predominantly Cr and oxide scale (B) comprising predominantly Si were formed at the time of controlled atmospheric heat treatment.
  • oxide layers were formed, and at the same time, a Cu-enriched layer was also formed on the inner side of the oxide layers.
  • surface processing treatment and alternating current electrolysis were not applied to those metal tubes which were subjected to this heat treatment.
  • Alternating current electrolysis was carried out in a sulfuric acid bath with a pH of 3 by repeated alternating application of a noble potential of +1.1 volts and a base potential of -0.6 volts (each vs SCE) for 0.15 seconds each. The application of these alternating potentials were continued for a total of 120 seconds.
  • the noble potential was changed to -0.25 volts.
  • the atmospheric heat treatment was carried out in a low oxygen atmosphere with an oxygen partial pressure of 10 -1 - 10 -8 MPa (remainder was hydrogen gas and water vapor) at 1120 - 1220° C for 3 minutes.
  • a square test piece measuring 20 mm on a side was cut from each of the above-described metal tubes, and the Cu concentration at the surface of the test piece was measured in the depth direction by AES to determine the presence of a Cu-enriched layer based on the Cu content of the base metal as well as the thickness and Cu concentration of the Cu-enriched layer.
  • the metal tubes which underwent controlled atmospheric heat treatment were subjected to measurement of an oxide scale formed on its surface in the following manner, in addition to the above-described measurement of the Cu-enriched layer by AES.
  • a sectional specimen for microscopic observation was prepared, and the thickness of each surface oxide scale was measured by observation under a microscope.
  • the Cr content of oxide scale (A) comprising predominantly Cr and the Si content of oxide scale (B) comprising predominantly Si were measured by EDX analysis. These contents were measured at three locations selected at random for each scale layer.
  • the contents of Cr, Al, and Si were determined relative to the total amount of metal elements, and the average values thereof were calculated.
  • test piece measuring 20 mm wide x 25 mm long was cut from the above-described metal tubes.
  • the test piece was kept at 650° C for 1000 hours in a carburizing gas atmosphere containing, in volume percent, 60% CO-26% H 2- 11.5% CO 2 -2.5% H 2 O. During this period, the test piece was removed at prescribed intervals, its surface was visually observed for the presence or absence of pitting, and the time until the occurrence of pitting was recorded.
  • Table 2 a time until the occurrence of pitting of 1000 hours, for example, means that pitting occurred when 1000 hours had elapsed.
  • test piece measuring 20 mm wide x 30 mm long was cut from the above-described metal tubes.
  • the test piece was kept for 300 hours at 1050° C in a carburizing gas atmosphere containing, in volume percent, 15% CH 4 -3% CO 2- 82% H 2 , and the amount of C (mass percent) which penetrated into the base metal was measured in the following manner.
  • the metal tube of Alloy No. 33 for which the chemical composition did not meet the conditions prescribed for the present invention was inferior in resistance to metal dusting as indicated by the short time until the occurrence of pitting which was less than 100 hours.
  • the metal tube was also inferior with respect to resistance to carburization as indicated by the large penetrated amount of C which was 1.9%.
  • the tested metal tubes for which the Cu concentration and thickness of the Cu-enriched layer satisfied the conditions prescribed by the present invention had a long time until the occurrence of pitting indicating that their resistance to metal dusting was excellent, and the amount of penetrated C was less than 1 % indicating that they had improved resistance to carburization.
  • the tested metal tubes for which at least one of the Cu concentration and the thickness of the Cu-enriched layer did not satisfy the conditions prescribed by the present invention had a short time until the occurrence of pitting, so their resistance to metal dusting was inferior, and they had a large amount of penetration of C, so their resistance to carburization was also inferior.
  • This example illustrates the case in which the Al content of the base metal is at least 1.5% so that when an oxide scale is formed, an oxide scale comprising predominantly Cr and Al is formed.
  • the Si content of the base metal was made at most 1% for the reason described above.
  • metal tubes for testing were prepared in the same manner as described in Example 1 except that in Comparative Examples 2-B and 6-C of Table 4, the noble potential was changed to -0.25 volts during alternating current electrolysis.
  • the metal tubes which were prepared were measured for the composition of the oxide scale and the thickness and Cu concentration (atomic percent) of the Cu-enriched layer and tested to evaluate resistance to metal dusting and resistance to carburization in the same manner as in Example 1.
  • the metal tubes prepared in this example had a high Al content of at least 1.5%, they were superior with respect to resistance to metal dusting and resistance to carburization to the metal tubes prepared in Example 1. Therefore, the test conditions were made more severe by lengthening the test time from the 1000 hours of Example 1 to 3000 hours in the test for evaluating resistance to metal dusting, and by increasing the test temperature from 1050° C to 1100° C in the test for evaluating resistance to carburization.
  • oxide scale (A) which was formed by controlled atmospheric heat treatment (ACHT) comprised predominantly Cr and Al. Therefore, the total content of Cr + Al in that layer was measured by EDX analysis.
  • Each of the tested metal tubes on which controlled atmospheric heat treatment was carried out had an Si content of less than 0.3%, and oxide scale (B) comprising predominantly Si did not form as a continuous layer, so measurement of oxide scale (B) was not performed.
  • the metal tube of Alloy No. 36 for which the chemical composition did not satisfy the conditions prescribed by the present invention had a time until the occurrence of pitting which was a low value of 200 hours, so it was inferior with respect to resistance to metal dusting.
  • the amount of penetrated C in this metal tube was a large value of 2.0%, so it was inferior with respect to resistance to carburization.
  • test metal tubes of Alloys Nos. 1 - 35 and 37 which had a chemical composition which satisfied the conditions prescribed by present invention the tested metal tubes for which the Cu concentration and the thickness of the Cu-enriched layer satisfied the conditions prescribed by the present invention had a long time until the occurrence of pitting and were superior with respect to resistance to metal dusting, and the amount of penetrated C was less than 1%, so they were superior with respect to resistance to carburization.

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EP05709298.3A 2004-02-12 2005-01-25 Metallrohr zur verwendung in aufkohlungsgasatmosphäre Expired - Fee Related EP1717330B1 (de)

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Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1780295A1 (de) * 2004-08-02 2007-05-02 Sumitomo Metal Industries, Ltd. Schweissverbindung und schweissmaterial davon
WO2010097300A1 (de) 2009-02-26 2010-09-02 Basf Se Schutzbeschichtung für metallische oberflächen und ihre herstellung
DE102009022203B3 (de) * 2009-05-20 2011-03-24 Thyssenkrupp Vdm Gmbh Metallfolie
EP1975267A4 (de) * 2006-01-11 2012-04-25 Sumitomo Metal Ind Metallmaterial mit hervorragender metal-dusting-beständigkeit
DE102010049781A1 (de) * 2010-10-29 2012-05-03 Thyssenkrupp Vdm Gmbh Ni-Fe-Cr-Mo-Legierung
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US20130287623A1 (en) * 2012-04-30 2013-10-31 Haynes International, Inc. Acid and alkali resistant nickel-chromium-molybdenum-copper alloys
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US20140044587A1 (en) * 2012-04-30 2014-02-13 Haynes International, Inc. Acid and Alkali Resistant Ni-Cr-Mo-Cu Alloys with Critical Contents of Chromium and Copper
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US10053758B2 (en) 2010-01-22 2018-08-21 Ati Properties Llc Production of high strength titanium
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JP7415144B2 (ja) 2019-12-04 2024-01-17 日本製鉄株式会社 オーステナイト系ステンレス鋼
CN117987691B (zh) * 2024-04-07 2024-06-18 上海核工程研究设计院股份有限公司 一种耐磨耐腐蚀镍基合金及其制造方法与应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5938365A (ja) * 1982-08-28 1984-03-02 Kubota Ltd 耐熱鋳鋼
EP0727503A1 (de) * 1993-10-20 1996-08-21 Sumitomo Metal Industries, Ltd. Rostfreier stahl für hochreines gas
US20020155306A1 (en) * 2000-08-11 2002-10-24 Sumitomo Metal Ind Nickel-base alloy product and method of producing the same
JP2003254916A (ja) * 2002-02-27 2003-09-10 Babcock Hitachi Kk オーステナイト鋼伝熱管材の損傷推定方法
EP1498508A1 (de) * 2003-07-17 2005-01-19 Sumitomo Metal Industries, Ltd. Rostfreier Stahl und rostfreies Stahlrohr beständig gegen Aufkohlung

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0729129B2 (ja) * 1990-04-13 1995-04-05 新日本製鐵株式会社 耐サワー性に優れたオーステナイト系高合金継目無鋼管の延伸圧延方法
DE4342188C2 (de) * 1993-12-10 1998-06-04 Bayer Ag Austenitische Legierungen und deren Verwendung
JPH11302796A (ja) * 1998-04-20 1999-11-02 Nippon Steel Corp 耐食性に優れた建築構造用ステンレス熱延鋼帯とその製造方法
JP3952861B2 (ja) * 2001-06-19 2007-08-01 住友金属工業株式会社 耐メタルダスティング性を有する金属材料

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5938365A (ja) * 1982-08-28 1984-03-02 Kubota Ltd 耐熱鋳鋼
EP0727503A1 (de) * 1993-10-20 1996-08-21 Sumitomo Metal Industries, Ltd. Rostfreier stahl für hochreines gas
US20020155306A1 (en) * 2000-08-11 2002-10-24 Sumitomo Metal Ind Nickel-base alloy product and method of producing the same
JP2003254916A (ja) * 2002-02-27 2003-09-10 Babcock Hitachi Kk オーステナイト鋼伝熱管材の損傷推定方法
EP1498508A1 (de) * 2003-07-17 2005-01-19 Sumitomo Metal Industries, Ltd. Rostfreier Stahl und rostfreies Stahlrohr beständig gegen Aufkohlung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2005078148A1 *

Cited By (61)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9796005B2 (en) 2003-05-09 2017-10-24 Ati Properties Llc Processing of titanium-aluminum-vanadium alloys and products made thereby
US10422027B2 (en) 2004-05-21 2019-09-24 Ati Properties Llc Metastable beta-titanium alloys and methods of processing the same by direct aging
US9523137B2 (en) 2004-05-21 2016-12-20 Ati Properties Llc Metastable β-titanium alloys and methods of processing the same by direct aging
EP1780295A1 (de) * 2004-08-02 2007-05-02 Sumitomo Metal Industries, Ltd. Schweissverbindung und schweissmaterial davon
EP1780295A4 (de) * 2004-08-02 2012-04-04 Sumitomo Metal Ind Schweissverbindung und schweissmaterial davon
EP1975267A4 (de) * 2006-01-11 2012-04-25 Sumitomo Metal Ind Metallmaterial mit hervorragender metal-dusting-beständigkeit
US9249482B2 (en) 2008-10-13 2016-02-02 Schmidt + Clemens Gmbh + Co. Kg Nickel-chromium-alloy
US10053756B2 (en) 2008-10-13 2018-08-21 Schmidt + Clemens Gmbh + Co. Kg Nickel chromium alloy
WO2010097300A1 (de) 2009-02-26 2010-09-02 Basf Se Schutzbeschichtung für metallische oberflächen und ihre herstellung
DE102009012003A1 (de) 2009-02-26 2010-09-02 Basf Se Schutzbeschichtung für metallische Oberflächen und ihre Herstellung
DE102009022203B3 (de) * 2009-05-20 2011-03-24 Thyssenkrupp Vdm Gmbh Metallfolie
EP2479300A1 (de) * 2009-09-16 2012-07-25 Sumitomo Metal Industries, Ltd. Legierungsprodukt auf nickelbasis und herstellungsverfahren dafür
EP2479300A4 (de) * 2009-09-16 2013-11-27 Nippon Steel & Sumitomo Metal Corp Legierungsprodukt auf nickelbasis und herstellungsverfahren dafür
US8801876B2 (en) 2009-09-16 2014-08-12 Nippon Steel & Sumitomo Metal Corporation Ni-based alloy product and producing method thereof
US8858875B2 (en) 2009-09-18 2014-10-14 Nippon Steel & Sumitomo Metal Corporation Nickel based alloy material
US10053758B2 (en) 2010-01-22 2018-08-21 Ati Properties Llc Production of high strength titanium
US9765420B2 (en) 2010-07-19 2017-09-19 Ati Properties Llc Processing of α/β titanium alloys
US10144999B2 (en) 2010-07-19 2018-12-04 Ati Properties Llc Processing of alpha/beta titanium alloys
US10435775B2 (en) 2010-09-15 2019-10-08 Ati Properties Llc Processing routes for titanium and titanium alloys
US9206497B2 (en) 2010-09-15 2015-12-08 Ati Properties, Inc. Methods for processing titanium alloys
US9624567B2 (en) 2010-09-15 2017-04-18 Ati Properties Llc Methods for processing titanium alloys
US10513755B2 (en) 2010-09-23 2019-12-24 Ati Properties Llc High strength alpha/beta titanium alloy fasteners and fastener stock
US9228250B2 (en) 2010-10-29 2016-01-05 VDM Metals GmbH Ni—Fe—Cr—Mo alloy
DE102010049781A1 (de) * 2010-10-29 2012-05-03 Thyssenkrupp Vdm Gmbh Ni-Fe-Cr-Mo-Legierung
US10287655B2 (en) 2011-06-01 2019-05-14 Ati Properties Llc Nickel-base alloy and articles
US9616480B2 (en) 2011-06-01 2017-04-11 Ati Properties Llc Thermo-mechanical processing of nickel-base alloys
US9938609B2 (en) 2012-04-30 2018-04-10 Haynes International, Inc. Acid and alkali resistant Ni—Cr—Mo—Cu alloys with critical contents of chromium and copper
US9394591B2 (en) * 2012-04-30 2016-07-19 Haynes International, Inc. Acid and alkali resistant nickel-chromium-molybdenum-copper alloys
US20140044587A1 (en) * 2012-04-30 2014-02-13 Haynes International, Inc. Acid and Alkali Resistant Ni-Cr-Mo-Cu Alloys with Critical Contents of Chromium and Copper
TWI588268B (zh) * 2012-04-30 2017-06-21 海尼斯國際公司 抗酸鹼之鎳－鉻－鉬－銅合金
US9399807B2 (en) * 2012-04-30 2016-07-26 Haynes International, Inc. Acid and alkali resistant Ni—Cr—Mo—Cu alloys with critical contents of chromium and copper
US20130287624A1 (en) * 2012-04-30 2013-10-31 Haynes International, Inc. STABILIZED ACID AND ALKALI RESISTANT Ni-Cr-Mo-Co ALLOYS
US20130287623A1 (en) * 2012-04-30 2013-10-31 Haynes International, Inc. Acid and alkali resistant nickel-chromium-molybdenum-copper alloys
WO2014023274A1 (de) * 2012-08-10 2014-02-13 Outokumpu Vdm Gmbh Verwendung einer nickel-chrom-eisen-aluminium-legierung mit guter verarbeitbarkeit
CN103882264A (zh) * 2012-12-19 2014-06-25 海恩斯国际公司 耐受酸和碱的具有临界铬和铜含量的Ni-Cr-Mo-Cu合金
US20140238552A1 (en) * 2013-02-26 2014-08-28 Ati Properties, Inc. Methods for processing alloys
US9869003B2 (en) * 2013-02-26 2018-01-16 Ati Properties Llc Methods for processing alloys
KR20150120929A (ko) * 2013-02-26 2015-10-28 에이티아이 프로퍼티즈, 인코퍼레이티드 합금을 가공하기 위한 방법
CN104838020A (zh) * 2013-02-26 2015-08-12 Ati资产公司 用于处理合金的方法
US10570469B2 (en) 2013-02-26 2020-02-25 Ati Properties Llc Methods for processing alloys
AU2014221415B2 (en) * 2013-02-26 2018-08-23 Ati Properties Llc Methods for processing alloys
CN104838020B (zh) * 2013-02-26 2018-10-09 冶联科技地产有限责任公司 用于处理合金的方法
US9192981B2 (en) 2013-03-11 2015-11-24 Ati Properties, Inc. Thermomechanical processing of high strength non-magnetic corrosion resistant material
US10337093B2 (en) 2013-03-11 2019-07-02 Ati Properties Llc Non-magnetic alloy forgings
US9777361B2 (en) 2013-03-15 2017-10-03 Ati Properties Llc Thermomechanical processing of alpha-beta titanium alloys
US10370751B2 (en) 2013-03-15 2019-08-06 Ati Properties Llc Thermomechanical processing of alpha-beta titanium alloys
US11111552B2 (en) 2013-11-12 2021-09-07 Ati Properties Llc Methods for processing metal alloys
EP3239311A4 (de) * 2014-12-26 2018-06-20 Kubota Corporation Hitzebeständiges rohr mit aluminiumsperrschicht
US10094003B2 (en) 2015-01-12 2018-10-09 Ati Properties Llc Titanium alloy
US10619226B2 (en) 2015-01-12 2020-04-14 Ati Properties Llc Titanium alloy
US10808298B2 (en) 2015-01-12 2020-10-20 Ati Properties Llc Titanium alloy
US11319616B2 (en) 2015-01-12 2022-05-03 Ati Properties Llc Titanium alloy
US11851734B2 (en) 2015-01-12 2023-12-26 Ati Properties Llc Titanium alloy
RU2578277C1 (ru) * 2015-05-18 2016-03-27 Байдуганов Александр Меркурьевич Жаропрочный сплав
US10502252B2 (en) 2015-11-23 2019-12-10 Ati Properties Llc Processing of alpha-beta titanium alloys
RU2632497C2 (ru) * 2016-02-10 2017-10-05 Байдуганов Александр Меркурьевич Жаропрочный сплав
RU2635411C2 (ru) * 2016-04-11 2017-11-13 Байдуганов Александр Меркурьевич Жаропрочный сплав
US11162151B2 (en) 2016-11-09 2021-11-02 Kubota Corporation Tube body that is to be used in high-temperature atmosphere and method for forming metal oxide layer on inner surface of tube body
US11215356B2 (en) 2017-06-08 2022-01-04 Nippon Steel Corporation Ni-based alloy pipe for nuclear power
RU2653376C1 (ru) * 2017-12-05 2018-05-08 Юлия Алексеевна Щепочкина Коррозионностойкий сплав
US11846006B2 (en) 2019-10-03 2023-12-19 Tokyo Metropolitan Public University Corporation Heat-resistant alloy, heat-resistant alloy powder, heat-resistant alloy structural component, and manufacturing method of the same

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EP1717330B1 (de) 2018-06-13
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