DE19643752A1 - Corrosion- and oxidation-resistant material, used as heat exchanger material - Google Patents
Corrosion- and oxidation-resistant material, used as heat exchanger materialInfo
- Publication number
- DE19643752A1 DE19643752A1 DE1996143752 DE19643752A DE19643752A1 DE 19643752 A1 DE19643752 A1 DE 19643752A1 DE 1996143752 DE1996143752 DE 1996143752 DE 19643752 A DE19643752 A DE 19643752A DE 19643752 A1 DE19643752 A1 DE 19643752A1
- Authority
- DE
- Germany
- Prior art keywords
- ppm
- ferritic
- corrosion
- sintering
- hours
- 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.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 47
- 230000003647 oxidation Effects 0.000 title claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 11
- 238000005260 corrosion Methods 0.000 claims abstract description 10
- 230000007797 corrosion Effects 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 239000010955 niobium Substances 0.000 claims abstract description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 2
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/081—Heat exchange elements made from metals or metal alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
- C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
-
- 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
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B37/00—Component parts or details of steam boilers
- F22B37/02—Component parts or details of steam boilers applicable to more than one kind or type of steam boiler
- F22B37/04—Component parts or details of steam boilers applicable to more than one kind or type of steam boiler and characterised by material, e.g. use of special steel alloy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
Description
Die Erfindung bezieht sich auf ein Verfahren zur Herstellung eines korrosions- und oxidationsbeständigen Werkstoffs gemäß dem Oberbegriff des Patentanspruchs 1.The invention relates to a method for producing a corrosion and Oxidation-resistant material according to the preamble of claim 1.
Solche Werkstoffe sind für die Herstellung von Wärmetauschern, insbesondere von Überhitzern von Wärmekraftanlagen vorgesehen, da sie den Einwirkungen von Tem peraturen standhalten, die mehr als 600°C betragen. Bis jetzt ist es üblich hierfür austenitische Edelstähle zu verwenden, die mindestens 18% Chrom enthalten. Bei Bauelementen, die aus diesem Werkstoff gefertigt sind, bildet sich auf den Oberflä chen eine schützende Oxidschicht aus Chrom aus. Hierdurch sind solche Bauele mente beispielsweise gegen die korrosiven Einwirkungen von Wasserdampf ge schützt, der mehr als 600°C heiß ist. Diese austenitischen Werkstoffe sind wegen ih res hohen Chromgehalts sehr teuer, was die Fertigungskosten für Wärmetaucher be achtlich erhöht.Such materials are for the manufacture of heat exchangers, in particular Overheating of thermal power plants provided, since they are exposed to the effects of Tem withstand temperatures that exceed 600 ° C. So far it has been common for this to use austenitic stainless steels that contain at least 18% chromium. At Components that are made of this material form on the surface remove a protective oxide layer made of chrome. This makes such components For example, against the corrosive effects of water vapor protects that is more than 600 ° C hot. These austenitic materials are because of them res high chromium content very expensive, which be the manufacturing costs for heat exchangers increased by eight.
Herkömmliche ferritische Werkstoffe, die 9 bis 12% Chrom enthalten und deshalb wesentlich preisgünstiger sind, können für die Herstellung der oben genannten Wär metauscher nicht verwendet werden, da sie eine unzureichende Korrosions- und Oxi dationsbeständigkeit gegenüber Wasserdampf bei Temperaturen von mehr als 600°C aufweisen. Auf den Oberflächen von Bauelementen, die aus einem der bekannten ferritischen Werkstoff hergestellt sind, bilden sich nur Schichten aus Mischphasen in Form von Eisen- und Chromoxiden wie Spinelle oder Magnetite aus. Diese Schichten sind sehr porös und platzten zudem unter der Einwirkung von Wasserdampf sehr schnell ab.Conventional ferritic materials that contain 9 to 12% chromium and therefore are much cheaper, can be used to manufacture the above-mentioned heat Meters are not used because they have insufficient corrosion and oxi dation resistance to water vapor at temperatures above 600 ° C exhibit. On the surfaces of components made from one of the known are made of ferritic material, only layers of mixed phases are formed in Form of iron and chromium oxides such as spinels or magnetites. These layers are very porous and also burst under the influence of water vapor quickly.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren aufzuzeigen, mit dem ein ferritischer Werkstoff so hergestellt werden kann, daß er einen dauerhaften Schutz gegen Korrosion und Oxidation aufweist.The invention has for its object to show a method with which ferritic material can be manufactured so that it provides permanent protection against corrosion and oxidation.
Diese Aufgabe wird durch die Merkmale des Patentanspruchs 1 gelöst.This object is achieved by the features of patent claim 1.
Weitere erfinderische Merkmale sind in den abhängigen Ansprüchen gekennzeichnet.Further inventive features are characterized in the dependent claims.
Die Herstellung des erfindungsgemäßen Werkstoffs wird an Hand der nachfolgenden Zeichnungen näher erläutert.The production of the material according to the invention is illustrated in the following Drawings explained in more detail.
Es zeigen:Show it:
Fig. 1 ein aus dem erfindungsgemäßen Werkstoff gefertigtes Bauelement, Fig. 1 a fabricated from the inventive material component,
Fig. 2 ein Diagramm, welches das Korrosionsverhalten des erfindungsgemäßen Werkstoffs veranschaulich. Fig. 2 is a diagram illustrating the corrosion behavior of the material according to the invention.
Fig. 1 zeigt ein zylinderförmiges Bauelement 10, das aus dem erfindungsgemäßen ferritischen Werkstoff 1 gefertigt ist. Für die Herstellung des Werkstoffs wird von ei nem Basismaterial ausgegangen, das Kohlenstoff, Chrom, Molybdän, Vanadium und Niob enthält. Der Anteil an Chrom und Molybdän wird hierbei so groß gewählt, daß der ferritische Werkstoff 1 nach dem Sintern 9% bis 12% Chrom und 0,5% bis 1% Molybdän aufweist. Bevorzugt wird die Herstellung eines ferritischen Werkstoffs 1 mit der Bezeichnung T 91, der folgende Strukturformel hat: X10CrMoVNb91. X steht da bei stellvertretend für Kohlenstoff. Der Werkstoff 1 wird nach dem Sintern zu Bauele menten weiterverarbeitet. Das in Fig. 1 dargestellte Bauelement 10 ist aus X10CrMoVNb91 gefertigt. Nach der Formgebung des Bauelements 10 wird dieses derart weiterbehandelt, daß der Werkstoff 1 dabei voroxidiert wird. Das Voroxidieren geschieht in einer reduzierenden Atmosphäre, in der ein Sauerstoffpartialdruck von höchstens 100 ppm bis 1000 ppm herrscht. Das Bauelement 10 wird zum Voroxidie ren des ferritischen Werkstoffs 1 zunächst vollständig in Kohlenstoff eingebettet. Anschließend wird es für mindestens 120 Stunden bei einer Temperatur von 800°C einem Gasstrom ausgesetzt, der als wesentlichen Bestandteil Stickstoff und nur 100 ppm bis 1000 ppm Sauerstoff aufweist. Fig. 1 shows a cylindrical component 10 which is made from the inventive ferritic material 1. A basic material containing carbon, chromium, molybdenum, vanadium and niobium is assumed for the production of the material. The proportion of chromium and molybdenum is chosen so large that the ferritic material 1 has 9% to 12% chromium and 0.5% to 1% molybdenum after sintering. It is preferred to produce a ferritic material 1 with the designation T 91, which has the following structural formula: X10CrMoVNb91. X stands for carbon. Material 1 is further processed into components after sintering. The component 10 shown in FIG. 1 is made of X10CrMoVNb91. After the component 10 has been shaped, it is further treated in such a way that the material 1 is preoxidized. The pre-oxidation takes place in a reducing atmosphere in which there is an oxygen partial pressure of at most 100 ppm to 1000 ppm. The component 10 is first completely embedded in carbon for the preoxidation of the ferritic material 1 . It is then exposed to a gas stream which contains nitrogen and only 100 ppm to 1000 ppm oxygen as an essential component at a temperature of 800 ° C for at least 120 hours.
Erfindungsgemäß kann der Werkstoff auch so voroxidiert werden, daß das Bauele ment 10 für wenigstens 120 Stunden einer Temperatur von 800°C ausgesetzt wird. Gleichzeitig wird das Bauelement 10 einem Gasstrom ausgesetzt, der durch ein re duzierendes Gas gebildet wird. Dieser Gasstrom besteht aus Wasserstoff mit einem Anteil von 100 ppm bis 1000 ppm Sauerstoff.According to the invention, the material can also be pre-oxidized so that the component 10 is exposed to a temperature of 800 ° C. for at least 120 hours. At the same time, the component 10 is exposed to a gas flow which is formed by a re-reducing gas. This gas stream consists of hydrogen with a proportion of 100 ppm to 1000 ppm oxygen.
Gleichgültig welche der beiden Möglichkeiten zur Voroxidation angewendet werden, immer bildet sich dabei auf den Innen- und Außenflächen des Bauelements 10 eine Deckschicht 11 aus Chromoxid selbsttätig aus. Diese Deckschicht 11 weist eine Dic ke von 2 µm bis 10 µm auf.Regardless of which of the two options for preoxidation are used, a cover layer 11 made of chromium oxide always forms automatically on the inner and outer surfaces of the component 10 . This cover layer 11 has a thickness of 2 μm to 10 μm.
Wird das Bauelement 10 anschließend beispielsweise in einen Wärmetauscher ein gebaut, wo es einen direkten Kontakt mit Wasserdampf hat, der eine Temperatur von 650°C und mehr aufweisen kann, zeigt der voroxidierte Werkstoff 1 im Vergleich zum einem ferritischen Werkstoff (hier nicht dargestellt) mit der gleichen Zusammen setzung, der jedoch nicht voroxidiert ist, eine deutlich geringere Korrosionsrate. Mes sen läßt sich diese Korrosionsrate, dadurch daß, die Zunahme des Gewichts in mg/cm2 ermittelt wird, die der Werkstoff 1 erfährt. Diese Gewichtszunahme ist in ei nem Diagramm in Fig. 2 für einen voroxidierten und einen unbehandelten ferritischen Werkstoff dargestellt, die beide Wasserdampf von 650°C ausgesetzt sind. Wie das Diagramm zeigt erfolgt die Oxidation bei dem voroxidierten Werkstoff wesentlich langsamer als das bei einem unbehandelten ferritischen Werkstoff der Fall ist.If the component 10 is subsequently built, for example, in a heat exchanger where it has direct contact with water vapor, which can have a temperature of 650 ° C. and more, the pre-oxidized material 1 shows in comparison to a ferritic material (not shown here) the same composition, but which is not pre-oxidized, has a significantly lower corrosion rate. This rate of corrosion can be measured by determining the increase in weight in mg / cm 2 experienced by material 1 . This increase in weight is shown in a diagram in FIG. 2 for a pre-oxidized and an untreated ferritic material, both of which are exposed to water vapor at 650 ° C. As the diagram shows, the oxidation of the pre-oxidized material is much slower than that of an untreated ferritic material.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1996143752 DE19643752A1 (en) | 1996-10-23 | 1996-10-23 | Corrosion- and oxidation-resistant material, used as heat exchanger material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1996143752 DE19643752A1 (en) | 1996-10-23 | 1996-10-23 | Corrosion- and oxidation-resistant material, used as heat exchanger material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19643752A1 true DE19643752A1 (en) | 1998-04-30 |
Family
ID=7809566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1996143752 Withdrawn DE19643752A1 (en) | 1996-10-23 | 1996-10-23 | Corrosion- and oxidation-resistant material, used as heat exchanger material |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE19643752A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE559681C (en) * | 1928-03-29 | 1932-09-22 | Ternstedt Mfg Company | Process for the production of chrome coatings by electrolytic means |
| DE2016920A1 (en) * | 1969-04-10 | 1970-10-01 | ||
| DE2042394A1 (en) * | 1969-08-27 | 1971-03-25 | Nippon Kokan Kk | Heat-resistant alloy steel |
| EP0332875A2 (en) * | 1988-03-14 | 1989-09-20 | Westinghouse Electric Corporation | More creep resistant turbine rotor, and procedures for repair welding of low alloy ferrous turbine components |
| DE3442250C2 (en) * | 1983-11-19 | 1993-04-15 | Alain James Johannesburg Transvaal Za Duggan | |
| WO1995020683A1 (en) * | 1994-01-26 | 1995-08-03 | Kawasaki Steel Corporation | Method of manufacturing stainless steel sheet of high corrosion resistance |
-
1996
- 1996-10-23 DE DE1996143752 patent/DE19643752A1/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE559681C (en) * | 1928-03-29 | 1932-09-22 | Ternstedt Mfg Company | Process for the production of chrome coatings by electrolytic means |
| DE2016920A1 (en) * | 1969-04-10 | 1970-10-01 | ||
| DE2042394A1 (en) * | 1969-08-27 | 1971-03-25 | Nippon Kokan Kk | Heat-resistant alloy steel |
| DE3442250C2 (en) * | 1983-11-19 | 1993-04-15 | Alain James Johannesburg Transvaal Za Duggan | |
| EP0332875A2 (en) * | 1988-03-14 | 1989-09-20 | Westinghouse Electric Corporation | More creep resistant turbine rotor, and procedures for repair welding of low alloy ferrous turbine components |
| WO1995020683A1 (en) * | 1994-01-26 | 1995-08-03 | Kawasaki Steel Corporation | Method of manufacturing stainless steel sheet of high corrosion resistance |
| EP0691412A1 (en) * | 1994-01-26 | 1996-01-10 | Kawasaki Steel Corporation | Method of manufacturing stainless steel sheet of high corrosion resistance |
Non-Patent Citations (2)
| Title |
|---|
| BETTZIECHE,P.: Hochwarmfeste ferritische Stähle. In: Mitteilungen der VGB, H. 57, Dez. 1985, S.393-397 * |
| MATOUSCHEK,Josef: Derzeitiger Stand bei den hitzebeständigen Stählen. In: technica, Nr. 22, Okt. 1959, S.1223-1226 * |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OM8 | Search report available as to paragraph 43 lit. 1 sentence 1 patent law | ||
| 8120 | Willingness to grant licenses paragraph 23 | ||
| 8127 | New person/name/address of the applicant |
Owner name: ABB PATENT GMBH, 68526 LADENBURG, DE |
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| 8139 | Disposal/non-payment of the annual fee |