EP2855723B1 - Nickel-chrom-aluminium-legierung mit guter verarbeitbarkeit, kriechfestigkeit und korrosionsbeständigkeit - Google Patents

Nickel-chrom-aluminium-legierung mit guter verarbeitbarkeit, kriechfestigkeit und korrosionsbeständigkeit Download PDF

Info

Publication number
EP2855723B1
EP2855723B1 EP13731273.2A EP13731273A EP2855723B1 EP 2855723 B1 EP2855723 B1 EP 2855723B1 EP 13731273 A EP13731273 A EP 13731273A EP 2855723 B1 EP2855723 B1 EP 2855723B1
Authority
EP
European Patent Office
Prior art keywords
alloy
content
alloy according
max
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP13731273.2A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2855723A1 (de
Inventor
Heike Hattendorf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
VDM Metals International GmbH
Original Assignee
VDM Metals International GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by VDM Metals International GmbH filed Critical VDM Metals International GmbH
Publication of EP2855723A1 publication Critical patent/EP2855723A1/de
Application granted granted Critical
Publication of EP2855723B1 publication Critical patent/EP2855723B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/007Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/053Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon

Definitions

  • the invention relates to a nickel-chromium-aluminum alloy having excellent high temperature corrosion resistance, creep resistance and improved processability.
  • Austenitic nickel-chromium-aluminum alloys with different nickel, chromium and aluminum contents have long been used in furnace construction and in the chemical and petrochemical industries. For this application, a good high-temperature corrosion resistance is required even in carburizing atmospheres and a good heat resistance / creep resistance.
  • the high temperature corrosion resistance of the alloys listed in Table 1 increases with increasing chromium content. All these alloys form a chromium oxide layer (Cr 2 O 3 ) with an underlying, more or less closed, Al 2 O 3 layer. Small additions of strongly oxygen-affinitive elements such as Y or Ce improve the oxidation resistance. The content of chromium is slowly consumed in the course of use in the application area for the formation of the protective layer. Therefore, a higher chromium content increases the life of the material, since a higher content of the protective layer-forming element chromium retards the time at which the Cr content is below the critical limit and forms oxides other than Cr 2 O 3 , eg ferrous and nickel containing oxides are. A further increase in high temperature corrosion resistance can be achieved by adding aluminum and silicon. From a certain minimum content, these elements form a closed layer below the chromium oxide layer and thus reduce the consumption of chromium.
  • High resistance to carburization is achieved by materials with low solubility for carbon and low diffusion rate of carbon.
  • Nickel alloys are therefore generally more resistant to carburization than iron-base alloys because both carbon diffusion and carbon solubility in nickel are lower than in iron.
  • Increasing the chromium content results in a higher carburization resistance by forming a protective chromium oxide layer, unless the oxygen partial pressure in the gas is insufficient to form this protective chromium oxide layer.
  • materials can be used which form a layer of silicon oxide or the even more stable alumina, both of which can form protective oxide layers even at significantly lower oxygen contents.
  • Typical conditions for the occurrence of metal dusting are strongly carburizing CO, H 2 or CH 4 gas mixtures, as they occur in ammonia synthesis, in methanol plants, in metallurgical processes, but also in hardening furnaces.
  • the resistance to metal dusting tends to increase with increasing nickel content of the alloy ( Grabke, HJ, Krajak, R., Müller-Lorenz, EM, Strauss, S .: Materials and Corrosion 47 (1996), p. 495 ), however, nickel alloys are not generally resistant to metal dusting.
  • the chromium and aluminum content has a significant influence on the corrosion resistance under metal dusting conditions (see Figure 1).
  • Low chromium nickel alloys (such as alloy Alloy 600, see Table 1) show comparatively high corrosion rates under metal dusting conditions.
  • the nickel alloy Alloy 602 CA (N06025) with a chromium content of 25% and an aluminum content of 2.3% as well as Alloy 690 (N06690) with a chromium content of 30% is significantly more resistant ( Hermse, CGM and van Wortel, JC: Metal Dusting: relationship between alloy composition and degradation rate. Corrosion Engineering, Science and Technology 44 (2009), p. 182 - 185 ). Resistance to metal dusting increases with the sum Cr + AL.
  • the heat resistance or creep resistance at the specified temperatures is u. a. improved by a high carbon content.
  • high contents of solid solution hardening elements such as chromium, aluminum, silicon, molybdenum and tungsten also improve the heat resistance.
  • additions of aluminum, titanium and / or niobium can improve the strength by excretion of the y'- and / or ⁇ "-phase.
  • Alloys such as Alloy 602 CA (N06025), Alloy 693 (N06693) or Alloy 603 (N06603) are superior in their corrosion resistance compared to Alloy 600 (N06600) or Alloy 601 (N06601) due to the high aluminum content of more than 1.8 % known.
  • Alloy 602 CA (N06025), Alloy 693 (N06693), Alloy 603 (N06603) and Alloy 690 (N06690) show excellent carburization resistance or metal dusting resistance due to their high chromium and / or aluminum content.
  • alloys such as Alloy 602 CA (N06025), Alloy 693 (N06693) or Alloy 603 are shown (N06603), because of the high carbon and aluminum contents, excellent hot strength or creep resistance occurs in the temperature range in the metal dusting.
  • Alloy 602 CA (N06025) and Alloy 603 (N06603) have excellent heat resistance and creep resistance even at temperatures above 1000 ° C.
  • z For example, the high aluminum content impairs processability, and the higher the aluminum content, the stronger the deterioration (for example, for Alloy 693 - N06693).
  • Alloy 602 CA (N06025) or Alloy 603 (N06603) in particular the cold workability is limited by a high proportion of primary carbides.
  • the US 6,623,869B1 discloses a metallic material consisting of not more than 0.2% C, 0.01-4% Si, 0.05-2.0% Mn, not more than 0.04% P, not more than 0.015% S, 10 - 35% Cr, 30 - 78% Ni, 0.005 - ⁇ 4.5% Al, 0.005 - 0.2% N, and at least one of the elements 0.015 - 3% Cu and 0.015 - 3% Co, with the balance consists of 100% iron.
  • the value of 40Si + Ni + 5Al + 40N + 10 (Cu + Co) is not less than 50, the symbols of the elements meaning the content of the corresponding elements.
  • the material has excellent corrosion resistance in an environment where metal dusting can take place and therefore can be used for stovepipes, piping systems, heat exchanger tubes and the like. ⁇ . Used in petroleum refineries or petrochemical plants and can significantly improve the life and safety of the plant.
  • the EP 0 508 058 A1 discloses an austenitic nickel-chromium-iron alloy consisting of (in weight%) C 0.12-0.3%, Cr 23-30%, Fe 8-11%, Al 1.8 2.4% , Y 0.01 - 0.15%, Ti 0.01 - 1.0%, Nb 0.01 - 1.0%, Zr 0.01 - 0.2%, Mg 0.001 - 0.015%, Ca 0.001 - 0.01%, N max. 0.03%, Si max. 0.5%, Mn max. 0.25%, P max. 0.02%, S max. 0.01%, Ni remainder, including unavoidable melt contaminants.
  • the US 4,882,125 B1 discloses a chromium-containing nickel alloy which, with excellent resistance to desulfurization and oxidation at temperatures greater than 1093 ° C, has excellent creep resistance of more than 200 hours at temperatures above 983 ° C and a tension of 2000 PSI, good tensile strength and good Elongation, both at room temperature and elevated temperatures, consisting of (in% by weight) 27-35% Cr, 2.5-5% Al, 2.5-6% Fe, 0.5-2.5% Nb, up to 0.1% C, up to 1% each of Ti and Zr, up to 0.05% Ce, up to 0.05% Y, up to 1% Si, up to 1% Mn and Ni remainder.
  • the EP 0 549 286 B1 discloses a high temperature resistant Ni-Cr alloy including 55-65% Ni, 19-25% Cr1-4.5% Al, 0.045-0.3% Y, 0.15-1% Ti, 0.005-0.5 % C, 0.1-1.5% Si, 0-1% Mn and at least 0.005%, at least one of the elements of the group containing Mg, Ca, Ce, ⁇ 0.5% in total Mg + Ca, ⁇ 1 % Ce, 0.0001 - 0.1% B, 0 - 0.5% Zr, 0.0001 - 0.2% N, 0 - 10% Co, 0 - 0.5% Cu, 0 - 0.5 % Mo, 0-0.3% Nb, 0-0.1% V, 0-0.1% W, balance iron and impurities.
  • a heat-resistant nickel-based alloy comprising ⁇ 0.1% C, 0.01-2% Si, ⁇ 2% Mn, ⁇ 0.005% S, 10-25% Cr, 2.1- ⁇ 4.5% Al, ⁇ 0.055% N, in total 0.001-1% of at least one of the elements B, Zr, Hf, wherein said elements may be present in the following contents: B ⁇ 0.03%, Zr ⁇ 0.2%, Hf ⁇ 0.8 %.
  • Mo and W the following formula must be fulfilled: 2 . 5 ⁇ Not a word + W ⁇ 15
  • Nickel-chromium-aluminum alloy with (in% by weight) 24 to 33% chromium, 1.8 to ⁇ 3.0% aluminum, 0.10 to ⁇ 2.5% iron, 0.001 to 0.50% Silicon, 0.005 to 2.0% manganese, 0.00 to 0.60% titanium, each 0.0002 to 0.05% magnesium and / or calcium, 0.005 to 0.12% carbon, 0.001 to 0.050% nitrogen, 0 , 0001 - 0.020% oxygen, 0.001 to 0.030% phosphorus, max. 0.010% sulfur, max. 2.0% molybdenum, max.
  • the alloy further contains oxygen in amounts between 0.0001 and 0.020%, in particular 0.0001 to 0.010%.
  • Preferred ranges can be set with: fp ⁇ 38 . 4 fp ⁇ 36 . 6
  • Nb is present in the alloy
  • the alloy may also contain from 0.001 to 0.60% tantalum.
  • a maximum of 0.5% Cu may be contained in the alloy.
  • a maximum of 0.5% vanadium may be present in the alloy.
  • impurities may still contain the elements lead, zinc and tin in amounts as follows: pb Max. 0.002% Zn Max. 0.002% sn Max. 0.002%.
  • Preferred ranges can be set with: fa ⁇ 54
  • Preferred ranges can be set with: Fk ⁇ 49 Fk ⁇ 53
  • the alloy of the invention is preferably melted open, followed by treatment in a VOD or VLF plant. But also a melting and pouring in a vacuum is possible. Thereafter, the alloy is poured in blocks or as a continuous casting. If necessary, the block is then at temperatures between Annealed 900 ° C and 1270 ° C for 0.1 h to 70 h. Furthermore, it is possible to remelt the alloy additionally with ESU and / or VAR. Thereafter, the alloy is brought into the desired semifinished product.
  • the surface of the material may optionally (also several times) be removed chemically and / or mechanically in between and / or at the end for cleaning.
  • After the end of the hot forming can optionally be a cold forming with degrees of deformation up to 98% in the desired semi-finished mold, possibly with intermediate anneals between 700 ° C and 1250 ° C for 0.1 min to 70 h, possibly under inert gas such.
  • the alloy according to the invention can be produced and used well in the product forms strip, sheet metal, rod wire, longitudinally welded tube and seamless tube.
  • These product forms are produced with an average particle size of 5 ⁇ m to 600 ⁇ m.
  • the preferred range is between 20 ⁇ m and 200 ⁇ m.
  • the alloy according to the invention should preferably be used in areas in which carburizing conditions prevail, such as. As in components, especially pipes in the petrochemical industry. In addition, it is also suitable for furnace construction.
  • the occurring phases in equilibrium were calculated for the different alloy variants with the program JMatPro from Thermotech.
  • the database used for the calculations was the TTNI7 nickel base alloy database from Thermotech.
  • the formability is determined in a tensile test according to DIN EN ISO 6892-1 at room temperature.
  • the yield strength R p0.2 , the tensile strength R m and the elongation A are determined until the fracture.
  • the experiments were carried out on round samples with a diameter of 6 mm in the measuring range and a measuring length L 0 of 30 mm.
  • the sampling took place transversely to the forming direction of the semifinished product.
  • the forming speed was 10 MPa / s at R p0.2 and 40% / min at R m 6.7 10 -3 .
  • the amount of elongation A in the tensile test at room temperature can be taken as a measure of the deformability.
  • a good workable material should have an elongation of at least 50%.
  • the hot strength is determined in a hot tensile test according to DIN EN ISO 6892-2.
  • the yield strength R p0.2 , the tensile strength R m and the Elongation A until break determined analogously to the tensile test at room temperature (DIN EN ISO 6892-1).
  • the experiments were carried out on round samples with a diameter of 6 mm in the measuring range and an initial measuring length L 0 of 30 mm. The sampling took place transversely to the forming direction of the semifinished product.
  • the forming speed at R p0.2 was 8.33 10 -5 1 / s (0.5% / min) and at R m was 8.33 10 -4 1 / s (5% / min).
  • the respective sample is installed at room temperature in a tensile testing machine and heated to a desired temperature without load with a tensile force. After reaching the test temperature, the sample is held without load for one hour (600 ° C) or two hours (700 ° C to 1100 ° C) for temperature compensation. Thereafter, the sample is loaded with a tensile force to maintain the desired strain rates, and the test begins.
  • the creep resistance of a material improves with increasing heat resistance. Therefore, the hot strength is also used to evaluate the creep resistance of the various materials.
  • the corrosion resistance at higher temperatures was determined in an oxidation test at 1000 ° C in air, the test was interrupted every 96 hours and the mass changes of the samples was determined by the oxidation.
  • the samples were placed in the ceramic crucible in the experiment, so that possibly spalling oxide was collected and by weighing the crucible containing the oxides, the mass of the chipped oxide can be determined.
  • the sum of the mass of the chipped oxide and the mass change of the samples corresponds to the gross mass change of the sample.
  • the specific mass change is the mass change related to the surface of the samples. These are m net for the specific net mass change, m gross for the specific gross mass change, m spall for the following designates specific mass change of the chipped oxides.
  • the experiments were carried out on samples with about 5 mm thickness. 3 samples were removed from each batch, the values given are the mean values of these 3 samples.
  • batch 111389 for N06690 shows computationally the formation of ⁇ -chromium with a low content of Ni and / or Fe (BCC phase in Figure 2) below 720 ° C (T s BCC ) large proportions.
  • this phase is difficult to form because it is very different analytically from the basic material.
  • T s BCC of this phase is very high, then it may well occur, as z.
  • the formation temperature T s BCC should be less than or equal to 939 ° C. - the lowest formation temperature T s BCC under the examples of Alloy 693 in Table 2 (out US 4,88,125 Table 1).
  • An alloy can be hardened by several mechanisms so that it has a high heat resistance or creep resistance.
  • the alloying of another element causes a greater or lesser increase in strength (solid solution hardening).
  • Far more effective is an increase in strength through fine particles or precipitates (particle hardening).
  • This can be z. B. by the ⁇ '-phase, which form with additions of Al and other elements, such as Ti, to a nickel alloy or by carbides which form by the addition of carbon to a chromium-containing nickel alloy ( see eg Ralf Bürgel, Handbuch der Hochtemperaturtechnik, 3rd edition, Vieweg Verlag, Wiesbaden, 2006, pages 358 - 369 ).
  • strains A5 in the tensile test at room temperature of ⁇ 50%, but at least ⁇ 45%, are aimed for.
  • the yield strength, or the tensile strength, at higher temperatures should at least reach the values of Alloy 601 (see Table 4).
  • 600 ° C Yield point R p 0 . 2 > 150 MPA ;
  • Tensile strength R m > 500 MPA 800 ° C Yield point R p 0 . 2 > 130 MPA ;
  • the yield strength or tensile strength prefferably in the range of Alloy602 CA (see Table 4). At least 3 of the 4 following relations should be fulfilled: 600 ° C : Yield point R p 0 . 2 > 230 MPA ; Tensile strength R m > 550 MPA 800 ° C : Yield point R p 0 . 2 > 180 MPA ; Tensile strength R m > 190 MPA
  • Tables 3a and 3b show the analyzes of laboratory-scale molten batches along with some prior art large scale molten batches of Alloy 602CA (N06025) used for comparison. Alloy 690 (N06690), Alloy 601 (N06601). The prior art batches are marked with a T, those of the invention with an E. The batches marked on the laboratory scale are marked with an L, the large-scale blown batches with a G.
  • the blocks of laboratory-scale molten alloys in Tables 3a and b were annealed between 900 ° C and 1270 ° C for 8 hours and hot rolled and further intermediate anneals between 900 ° C and 1270 ° C for 0.1 to 1 hour Final thickness of 13 mm or 6 mm hot rolled.
  • the sheets produced in this way were solution-annealed between 900 ° C. and 1270 ° C. for 1 h. From these sheets, the samples required for the measurements were produced.
  • All alloy variants typically had a particle size of 70 to 300 ⁇ m.
  • Table 4 shows the yield strength R p0.2 , the tensile strength R m and the elongation A 5 for room temperature (RT) and for 600 ° C, furthermore the tensile strength R m for 800 ° C.
  • the values for Fa and Fk are entered.
  • Example batches 156817 and 160483 of the prior art alloy Alloy 602 CA have in Table 4 a relatively low elongation A5 at room temperature of 36 and 42%, respectively, which are below the requirements for good formability.
  • Fa is> 60, which is above the range that indicates good formability.
  • All inventive alloys (E) show an elongation> 50%. They thus fulfill the requirements.
  • Fa is ⁇ 60 for all alloys according to the invention. They are therefore in the range of good formability. The elongation is particularly high when Fa is comparatively small.
  • Example Example 156658 of the prior art Alloy 601 in Table 4 is an example of the minimum requirements for yield strength and tensile strength at 600 ° C and 800 ° C, respectively.
  • Example lots 156817 and 160483 of the prior art Alloy 602 CA alloy on the other hand are examples of very good values of yield strength and tensile strength at 600 ° C and 800 ° C, respectively.
  • Alloy 601 represents a material that meets the minimum requirements Creep resistance described in Relation 9a to 9d shows Alloy 602 CA a material exhibiting excellent creep strength described in Relation 10a to 10d.
  • the value for Fk is significantly greater for both alloys than 45 and for Alloy 602 CA additionally significantly higher than the value of Alloy 601, reflecting the increased strength values of Alloy 602 CA.
  • the alloys (E) according to the invention all exhibit a yield strength and tensile strength at 600 ° C. or 800 ° C. in the region or significantly above that of Alloy 601, ie they have fulfilled the relations 9a to 9d. They are in the range of the values of Alloy 602 CA and also meet the desirable requirements, ie 3 of the 4 relations 10a to 10d. Also for all alloys according to the invention in the examples in Table 4, Fk is greater than 45, and even most greater than 54, and thus in the range characterized by good heat resistance or creep resistance.
  • the batches 2297 and 2300 are an example that the relations 9a to 9d are not fulfilled and also a Fk ⁇ 45 is given.
  • Table 5 shows the specific mass changes after an oxidation test at 1100 ° C in air after 11 cycles of 96 h, for a total of 1056 h. Given in Table 5 are the specific gross mass change, the net specific mass change and the specific mass change of the chipped oxides after 1056 h.
  • the example batches of the prior art alloys Alloy 601 and Alloy 690 showed a significantly higher gross mass change than Alloy 602 CA, with that of Alloy 601 again being significantly larger than that of Alloy 690. Both form a chromium oxide layer that grows faster than an aluminum oxide layer. Alloy 601 still contains about 1.3% Al.
  • Alloy 602 CA has approx. 2.3% aluminum. This can be below the Chromoxid für form an at least partially closed aluminum oxide layer. This noticeably reduces the growth of the oxide layer and thus also the specific mass increase.
  • All alloys (E) according to the invention contain at least 2% aluminum and thus have a similarly low or lower gross mass increase than Alloy 602 CA. Also, all of the alloys of the invention, similar to the example batches of Alloy 602 CA, exhibit flaking in the area of measurement accuracy, while Alloy 601 and Alloy 690 show large flaking.
  • Si is needed in the production of the alloy. It is therefore necessary a minimum content of 0.001%. Too high levels, in turn, affect processability and phase stability, especially at high levels of aluminum and chromium. The Si content is therefore limited to 0.50%.
  • a minimum content of 0.005% Mn is required to improve processability.
  • Manganese is limited to 2.0% because this element reduces oxidation resistance.
  • Titanium increases the high-temperature strength. From 0.60%, the oxidation behavior can be degraded, which is why 0.60% is the maximum value.
  • Mg and / or Ca contents improve the processing by the setting of sulfur, whereby the occurrence of low-melting NiS Eutektika is avoided.
  • Mg and or Ca therefore, a minimum content of 0.0002% is required. If the contents are too high, intermetallic Ni-Mg phases or Ni-Ca phases may occur, which again significantly impair processability.
  • the Mg and / or Ca content is therefore limited to a maximum of 0.05%.
  • a minimum content of 0.005% C is required for good creep resistance.
  • C is limited to a maximum of 0.12%, since this element reduces the processability by the excessive formation of primary carbides from this content.
  • N A minimum content of 0.001% N is required, which improves the processability of the material. N is limited to a maximum of 0.05%, since this element reduces the processability by forming coarse carbonitrides.
  • the oxygen content must be ⁇ 0.020% to ensure the manufacturability of the alloy. Too low an oxygen content increases the costs. The oxygen content is therefore ⁇ 0.0001%.
  • the content of phosphorus should be less than or equal to 0.030%, since this surfactant affects the oxidation resistance. A too low P content increases the costs. The P content is therefore ⁇ 0.001%.
  • the levels of sulfur should be adjusted as low as possible, since this surfactant affects the oxidation resistance. It will therefore max. 0.010% S set,
  • Molybdenum is reduced to max. 2.0% limited as this element reduces oxidation resistance.
  • Tungsten is limited to max. 2.0% limited as this element also reduces oxidation resistance.
  • the oxidation resistance can be further improved. They do this by incorporating them into the oxide layer and blocking the diffusion paths of the oxygen there on the grain boundaries.
  • a minimum content of 0.01% Y is necessary to obtain the oxidation resistance-enhancing effect of Y.
  • the upper limit is set at 0.20% for cost reasons.
  • a minimum content of 0.001% La is necessary to obtain the oxidation resistance enhancing effect of La.
  • the upper limit is set at 0.20% for cost reasons.
  • a minimum content of 0.001% Ce is necessary to obtain the oxidation resistance-enhancing effect of Ce.
  • the upper limit is set at 0.20% for cost reasons.
  • cerium mischmetal A minimum content of 0.001% cerium mischmetal is necessary to obtain the oxidation resistance enhancing effect of cerium mischmetal.
  • the upper limit is set at 0.20% for cost reasons.
  • niobium can be added, as niobium also increases the high-temperature strength. Higher levels increase costs very much. The upper limit is therefore set at 1.10%.
  • the alloy may also contain tantalum, since tantalum also increases high-temperature strength. Higher levels increase costs very much.
  • the upper limit is therefore set at 0.60%.
  • a minimum level of 0.001% is required to have an effect.
  • the alloy can also be given Zr.
  • a minimum content of 0.01% Zr is necessary to obtain the high-temperature strength and oxidation resistance-enhancing effect of Zr.
  • the upper limit is set at 0.20% Zr for cost reasons.
  • Zr can be wholly or partially replaced by Hf, since this element, such as Zr, also increases high-temperature strength and oxidation resistance. Replacement is possible from 0.001%.
  • the upper limit is set at 0.20% Hf for cost reasons.
  • boron may be added to the alloy because boron improves creep resistance. Therefore, a content of at least 0.0001% should be present. At the same time, this surfactant deteriorates the oxidation resistance. It will therefore max. 0.008% Boron set.
  • Cobalt can be contained in this alloy up to 5.0%. Higher contents considerably reduce the oxidation resistance.
  • Copper is heated to max. 0.5% limited as this element reduces the oxidation resistance.
  • Vanadium is reduced to max. 0.5% limited as this element also reduces oxidation resistance.
  • Pb is set to max. 0.002% limited because this element reduces the oxidation resistance.
  • Zn and Sn are set to max. 0.002% limited because this element reduces the oxidation resistance.
  • Zn and Sn are set to max. 0.002% limited because this element reduces the oxidation resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Heat Treatment Of Steel (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Powder Metallurgy (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Fuel Cell (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Heat Treatment Of Articles (AREA)
EP13731273.2A 2012-06-05 2013-05-15 Nickel-chrom-aluminium-legierung mit guter verarbeitbarkeit, kriechfestigkeit und korrosionsbeständigkeit Active EP2855723B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012011161.4A DE102012011161B4 (de) 2012-06-05 2012-06-05 Nickel-Chrom-Aluminium-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit
PCT/DE2013/000268 WO2013182177A1 (de) 2012-06-05 2013-05-15 Nickel-chrom-aluminium-legierung mit guter verarbeitbarkeit, kriechfestigkeit und korrosionsbeständigkeit

Publications (2)

Publication Number Publication Date
EP2855723A1 EP2855723A1 (de) 2015-04-08
EP2855723B1 true EP2855723B1 (de) 2016-10-05

Family

ID=48698848

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13731273.2A Active EP2855723B1 (de) 2012-06-05 2013-05-15 Nickel-chrom-aluminium-legierung mit guter verarbeitbarkeit, kriechfestigkeit und korrosionsbeständigkeit

Country Status (11)

Country Link
US (1) US9657373B2 (ja)
EP (1) EP2855723B1 (ja)
JP (1) JP6076472B2 (ja)
KR (1) KR101668383B1 (ja)
CN (1) CN104245978B (ja)
BR (1) BR112014024761B1 (ja)
DE (1) DE102012011161B4 (ja)
ES (1) ES2605948T3 (ja)
MX (1) MX362836B (ja)
RU (1) RU2599324C2 (ja)
WO (1) WO2013182177A1 (ja)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5270043B2 (ja) * 2011-02-01 2013-08-21 三菱重工業株式会社 Ni基高Cr合金溶接ワイヤ、被覆アーク溶接棒及び被覆アーク溶着金属
CN103725924B (zh) * 2014-01-16 2016-01-20 南通波斯佳织造科技有限公司 一种镍合金及其制备方法
DE102014001328B4 (de) * 2014-02-04 2016-04-21 VDM Metals GmbH Aushärtende Nickel-Chrom-Eisen-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit
DE102014001330B4 (de) 2014-02-04 2016-05-12 VDM Metals GmbH Aushärtende Nickel-Chrom-Kobalt-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit
DE102014001329B4 (de) 2014-02-04 2016-04-28 VDM Metals GmbH Verwendung einer aushärtenden Nickel-Chrom-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit
BR112017002000A2 (pt) * 2014-08-18 2018-03-06 Gen Electric superligas à base de níquel e componentes giratórios de um motor de turbina
DE102015008322A1 (de) 2015-06-30 2017-01-05 Vdm Metals International Gmbh Verfahren zur Herstellung einer Nickel-Eisen-Chrom-Aluminium-Knetlegierung mit einer erhöhten Dehnung im Zugversuch
CN105402413A (zh) * 2015-11-26 2016-03-16 成都九十度工业产品设计有限公司 一种发动机用组合垫片
ITUA20161551A1 (it) 2016-03-10 2017-09-10 Nuovo Pignone Tecnologie Srl Lega avente elevata resistenza all’ossidazione ed applicazioni di turbine a gas che la impiegano
CN110719964B (zh) * 2017-06-08 2022-03-04 日本制铁株式会社 原子能用Ni基合金管
KR20200030035A (ko) * 2017-06-21 2020-03-19 오브쉬체스트보 에스 오그라니첸노이 오트벳스트베노스트유 “오베디넨나야 꼼파니야 루살 인제네르노-테크놀로지체스키 첸트르” 알루미늄 합금
DE102018107248A1 (de) * 2018-03-27 2019-10-02 Vdm Metals International Gmbh Verwendung einer nickel-chrom-eisen-aluminium-legierung
KR102142782B1 (ko) * 2018-11-29 2020-08-10 주식회사 포스코 크리프 강도가 우수한 크롬-몰리브덴 강판 및 그 제조방법
DE102020132193A1 (de) 2019-12-06 2021-06-10 Vdm Metals International Gmbh Verwendung einer Nickel-Chrom-Eisen-Aluminium-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit
DE102020132219A1 (de) * 2019-12-06 2021-06-10 Vdm Metals International Gmbh Verwendung einer Nickel-Chrom-Aluminium-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit
RU2748445C1 (ru) * 2020-06-09 2021-05-25 Акционерное общество "Объединенная двигателестроительная корпорация" (АО "ОДК") Жаропрочный сплав на никелевой основе и изделие, выполненное из него
RU208686U1 (ru) * 2021-10-03 2021-12-29 Антон Владимирович Новиков Блок из трех полых направляющих лопаток турбины для газотурбинных двигателей и энергетических установок
DE102022105659A1 (de) 2022-03-10 2023-09-14 Vdm Metals International Gmbh Verfahren zur Herstellung eines mit Schweißnähten versehenen Bauteils aus einer Nickel-Chrom-Aluminium-Legierung
DE102022105658A1 (de) 2022-03-10 2023-09-14 Vdm Metals International Gmbh Verfahren zur Herstellung eines Bauteils aus dem Halbzeug einer Nickel-Chrom-Aluminium-Legierung
CN114871624B (zh) * 2022-06-09 2023-04-18 上海工程技术大学 一种铁路货车车轮增材制造用药芯焊丝及其制备方法

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US488125A (en) 1892-12-13 Hub-blank for metal wheels
US4882125A (en) 1988-04-22 1989-11-21 Inco Alloys International, Inc. Sulfidation/oxidation resistant alloys
DE4111821C1 (ja) 1991-04-11 1991-11-28 Vdm Nickel-Technologie Ag, 5980 Werdohl, De
EP0549286B1 (en) 1991-12-20 1995-06-14 Inco Alloys Limited High temperature resistant Ni-Cr alloy
JPH0711366A (ja) 1993-06-24 1995-01-13 Sumitomo Metal Ind Ltd 熱間加工性および高温水中の耐食性に優れた合金
JPH07216511A (ja) 1994-01-31 1995-08-15 Sumitomo Metal Ind Ltd 高温強度に優れた高クロムオーステナイト耐熱合金
JPH08127848A (ja) 1994-11-01 1996-05-21 Sumitomo Metal Ind Ltd 高温強度に優れた高クロムオーステナイト耐熱合金
RU2125110C1 (ru) * 1996-12-17 1999-01-20 Байдуганов Александр Меркурьевич Жаропрочный сплав
US5997809A (en) 1998-12-08 1999-12-07 Inco Alloys International, Inc. Alloys for high temperature service in aggressive environments
KR100372482B1 (ko) 1999-06-30 2003-02-17 스미토모 긴조쿠 고교 가부시키가이샤 니켈 베이스 내열합금
JP3965869B2 (ja) 2000-06-14 2007-08-29 住友金属工業株式会社 Ni基耐熱合金
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
JP2003138334A (ja) 2001-11-01 2003-05-14 Hitachi Metals Ltd 高温耐酸化性及び高温延性に優れたNi基合金
DE60206464T2 (de) 2001-12-21 2006-07-13 Hitachi Metals, Ltd. Ni-Legierung mit verbesserter Oxidations- Resistenz, Warmfestigkeit and Warmbearbeitbarkeit
DE10302989B4 (de) 2003-01-25 2005-03-03 Schmidt + Clemens Gmbh & Co. Kg Verwendung einer Hitze- und korrosionsbeständigen Nickel-Chrom-Stahllegierung
JP2006274443A (ja) 2005-03-03 2006-10-12 Daido Steel Co Ltd 非磁性高硬度合金
US8568901B2 (en) 2006-11-21 2013-10-29 Huntington Alloys Corporation Filler metal composition and method for overlaying low NOx power boiler tubes
FR2910912B1 (fr) 2006-12-29 2009-02-13 Areva Np Sas Procede de traitement thermique de desensibilisation a la fissuration assistee par l'environnement d'un alliage a base nickel, et piece realisee en cet alliage ainsi traitee
JP2008214734A (ja) * 2007-03-08 2008-09-18 Sumitomo Metal Ind Ltd 耐メタルダスティング性に優れた金属材料
JP4978790B2 (ja) 2007-08-27 2012-07-18 三菱マテリアル株式会社 樹脂成形用金型部材
DE102008051014A1 (de) 2008-10-13 2010-04-22 Schmidt + Clemens Gmbh + Co. Kg Nickel-Chrom-Legierung
JP4780189B2 (ja) * 2008-12-25 2011-09-28 住友金属工業株式会社 オーステナイト系耐熱合金
JP5284252B2 (ja) 2009-12-10 2013-09-11 株式会社神戸製鋼所 耐割れ性に優れたNi−Cr−Fe合金系溶接金属

Also Published As

Publication number Publication date
MX362836B (es) 2019-02-19
RU2014153531A (ru) 2016-08-10
KR20150005706A (ko) 2015-01-14
EP2855723A1 (de) 2015-04-08
RU2599324C2 (ru) 2016-10-10
CN104245978A (zh) 2014-12-24
DE102012011161A1 (de) 2013-12-05
US20150050182A1 (en) 2015-02-19
WO2013182177A1 (de) 2013-12-12
JP2015524023A (ja) 2015-08-20
MX2014014557A (es) 2015-03-05
JP6076472B2 (ja) 2017-02-08
CN104245978B (zh) 2016-10-26
KR101668383B1 (ko) 2016-10-21
BR112014024761B1 (pt) 2019-03-26
ES2605948T3 (es) 2017-03-17
US9657373B2 (en) 2017-05-23
DE102012011161B4 (de) 2014-06-18

Similar Documents

Publication Publication Date Title
EP2855723B1 (de) Nickel-chrom-aluminium-legierung mit guter verarbeitbarkeit, kriechfestigkeit und korrosionsbeständigkeit
EP2855724B1 (de) Nickel-chrom-legierung mit guter verarbeitbarkeit, kriechfestigkeit und korrosionsbeständigkeit
EP2678458B1 (de) Nickel-chrom-eisen-aluminium-legierung mit guter verarbeitbarkeit
EP3775308B1 (de) Verwendung einer nickel-chrom-eisen-aluminium-legierung
EP3102710B1 (de) Aushärtende nickel-chrom-kobalt-titan-aluminium-legierung mit guter verschleissbeständigkeit, kriechfestigkeit, korrosionsbeständigkeit und verarbeitbarkeit
EP3102711B1 (de) Aushärtende nickel-chrom-eisen-titan-aluminium-legierung mit guter verschleissbeständigkeit, kriechfestigkeit, korrosionsbeständigkeit und verarbeitbarkeit
EP2882881B1 (de) Verwendung einer nickel-chrom-eisen-aluminium-legierung mit guter verarbeitbarkeit
WO2017000932A1 (de) Verfahren zur herstellung einer nickel-eisen-chrom-aluminium-knetlegierung mit einer erhöhten dehnung im zugversuch
EP3102712B1 (de) Aushärtende nickel-chrom-titan-aluminium-legierung mit guter verschleissbeständigkeit, kriechfestigkeit, korrosionsbeständigkeit und verarbeitbarkeit
DE2253148C3 (de) Verfahren zur Herstellung eines ferritischen, korrosionsbeständigen Stahls und dessen Verwendung
DE69106372T2 (de) Legierung mit niedrigem wärmeausdehnungskoeffizient und daraus hergestellter gegenstand.
DE102020132193A1 (de) Verwendung einer Nickel-Chrom-Eisen-Aluminium-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit
DE102022110383A1 (de) Verwendung einer Nickel-Eisen-Chrom-Legierung mit hoher Beständigkeit in aufkohlenden und sulfidierenden und chlorierenden Umgebungen und gleichzeitig guter Verarbeitbarkeit und Festigkeit
DE102022110384A1 (de) Verwendung einer Nickel-Eisen-Chrom-Legierung mit hoher Beständigkeit in hoch korrosiven Umgebungen und gleichzeitig guter Verarbeitbarkeit und Festigkeit

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20141029

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160304

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: VDM METALS INTERNATIONAL GMBH

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 834743

Country of ref document: AT

Kind code of ref document: T

Effective date: 20161015

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502013004872

Country of ref document: DE

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20161005

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2605948

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20170317

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170105

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170106

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170205

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170206

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502013004872

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170105

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170531

26N No opposition filed

Effective date: 20170706

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170531

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170515

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20170531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170515

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20130515

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161005

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230526

Year of fee payment: 11

Ref country code: FR

Payment date: 20230526

Year of fee payment: 11

Ref country code: DE

Payment date: 20230519

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20230519

Year of fee payment: 11

Ref country code: AT

Payment date: 20230522

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230524

Year of fee payment: 11

Ref country code: ES

Payment date: 20230725

Year of fee payment: 11