EP1069202A1 - A paramagnetic, corrosion resistant austenitic steel with high elasticity, strength and toughness and a process for its manufacture - Google Patents
A paramagnetic, corrosion resistant austenitic steel with high elasticity, strength and toughness and a process for its manufacture Download PDFInfo
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- EP1069202A1 EP1069202A1 EP00890207A EP00890207A EP1069202A1 EP 1069202 A1 EP1069202 A1 EP 1069202A1 EP 00890207 A EP00890207 A EP 00890207A EP 00890207 A EP00890207 A EP 00890207A EP 1069202 A1 EP1069202 A1 EP 1069202A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
- C21D8/1222—Hot rolling
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
- C21D8/1227—Warm rolling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
Definitions
- the invention relates to a method for producing a paramagnetic, in particular in media with a high chloride concentration, corrosion-resistant material with a high yield strength, strength and toughness consisting of in% by weight Max. 0.1 carbon 0.21 to 0.6 silicon 17.0 to 24.0 chromium as well as manganese and nitrogen up to 2.5 nickel up to 1.9 molybdenum Max. 0.3 copper up to 0.002 boron up to 0.8 elements of groups 4 and 5 of the periodic table Remainder iron, melting-related accompanying elements and impurities.
- the invention further relates to an austenitic, paramagnetic material good corrosion resistance, especially in media with high Chloride concentration, and high yield strength, strength and toughness made of carbon, manganese, silicon, chromium and nitrogen, and optionally Nickel, molybdenum, copper, boron, carbide-forming elements, remainder iron, Melting-related accompanying elements and impurities.
- the invention includes the use of one at the beginning mentioned method manufactured material.
- High-strength materials that are paramagnetic and corrosion-resistant economic reasons mainly from chromium-manganese-iron alloys exist for chemical apparatus engineering, for facilities for electrical power generation and especially for components in the Oilfield technology used. Both the corrosion chemical and the mechanical properties of such materials are described in increasingly higher demands.
- Iron-manganese-chromium alloys were also used for economic reasons developed that without pressure melting and the like casting process, so at Atmospheric pressure can be produced (WO 98/48070), whereby alloying measures a desired property profile of the Material should be achieved. Alloys of this type point to Improvement in corrosion resistance to a molybdenum content of over 2%, which brings advantages in particular with hole and crevice corrosion behavior.
- molybdenum is a ferrite former and can be found in segregation areas lead to unfavorable magnetic properties of the material. Increased Nickel contents stabilize the austenite, but may also contribute higher copper concentrations worsening the mechanical Properties and intensify the crack initiation.
- the invention aims to provide a method which Exhaustion of alloying measures includes deformation and synergistically a manufacture of a highly magnetic paramagnetic, in Media with a high chloride concentration are corrosion-resistant, ferrite-free Material with high yield strength, strength and toughness indicates.
- Another object of the invention is a fully austenitic paramagnetic Material with good corrosion resistance and high mechanical values create.
- the advantages achieved by the invention are essentially to be seen in that with high efficiency regarding the material costs and Manufacturing process by an alloy-technical optimization largest Corrosion resistance and a desired paramagnetic behavior of the Material can be achieved, whereby its high mechanical characteristics, especially the yield strength, without adversely affecting the above properties mentioned by a targeted cold forming increased temperature experienced a further significant improvement.
- the carbon content of the alloy is max. 0.1% by weight, because higher levels result in both pitting and stress corrosion cracking chloride-containing media as well as intercrystalline corrosion from it manufactured parts. Compliance with this upper limit, with levels of Max. 0.06 and 0.05% by weight is preferred, as mentioned above, from Corrosion-chemical reasons important, although carbon increases the yield strength and has a strong austenite-forming effect.
- Silicon is said to be a deoxidation metal with a concentration of at least 0.21 % By weight is present in the metal, an upper limit of 0.6% by weight being provided. Higher silicon levels lead to nitride formation and deterioration of the Resistance to stress corrosion cracking of the material. Because silicon is also strong Magnetic permeability can also have a ferrite-forming effect due to higher contents be adversely affected. A maximum content of 0.48 is advantageous % By weight effective.
- Corrosion behavior especially resistance to Stress corrosion cracking and pitting corrosion is caused by the chromium content of the Alloy determined. It is important that a largely homogeneous Chromium distribution in the material is present; in other words, the so-called Weak spots in the passive layer due to segregation and inclusions avoided are. To be largely secured, a desired corrosion resistance too chromium contents of more than 17% by weight, preferably of more than 19% by weight required.
- Chromium increases the solubility of the alloy for Nitrogen, however, has a ferrite-forming effect and is therefore unfavorable with regard to the desired one non-magnetic or paramagnetic behavior of the material, so that the highest chromium concentration is 24.0% by weight, preferably 22.0% by weight.
- Nickel can increase the mechanical properties of the alloy and the stability the austenitic structure can be improved for sufficiently good ones Corrosion properties of the material, especially the Regarding stress corrosion cracking, nickel contents are less than 2.5% by weight. better, but less than 0.96 wt .-% required. Due to low nickel contents From 0.21% by weight up to the above maximum values it is possible without disadvantages in the corrosion behavior of the desired alloy, an increase in To reach yield strength.
- the alloy element molybdenum improves the durability of the material against corrosion, especially against chloride-induced crevice and pitting corrosion.
- this element is a strong ferrite former and the like
- Carbide formers and formers of socialized phases are the Molybdenum caps at 1.9% by weight, but better at 1.5% by weight.
- Low Levels from 0.28 wt .-% molybdenum up to the above limits can Precipitation-free austenite structure of the micro-chemical structure Advantages bring.
- the element copper which is often effective against corrosion attack, has been used in the
- the alloy according to the invention was found to have a disadvantageous effect the copper contents less than 0.3% by weight, but better less than 0.25% by weight to achieve resistance to corrosion.
- Boron can be used to improve the hot forming behavior of the material an amount of up to 0.002% by weight, preferably up to 0.0012% by weight. Higher amounts of boron lead to grain boundary deposits, Signs of embrittlement and undesirable structures.
- elements of group 4 and group 5 of the periodic table are particularly important for preventing stress cracking and pitting corrosion low levels of elements of group 4 and group 5 of the periodic table.
- These elements Ti, Zr, Hg, V, Nb, Ta
- These elements are extremely strong carbide and nitride or Carbonitride formers and have values of less than 0.8 in total % By weight, better of less than 0.48% by weight. Higher concentrations cause excretions and thereby weak points in the passive layer on the Workpiece surface, which affects the corrosion resistance.
- the element nitrogen is a strong austenite former.
- the yield strength and the resistance of the material to perforations and crevice corrosion increased by nitrogen.
- Nitrogen is in iron based alloys however, only soluble to a limited extent, with increasing chromium and manganese contents Solubility limit is increased.
- the chromium-manganese and Nitrogen concentrations of the alloy synergistically for the invention To see material or for its properties.
- Preferred nitrogen concentration ranges are: 0.64 to 1.3 wt .-%, in particular 0.72 to 1.2 wt .-% N.
- this or this diffusion annealing which is a homogenization of the Serves microstructure or a compensation of micro segregations become.
- This annealing can be carried out, for example, at a temperature of around 1200 ° C up to 60 hours.
- the hot forming of the casting which represents the first deformation step, mostly done by forging, whereby the forming temperature is higher than 850 ° C, to ensure a correspondingly favorable recrystallization of the mixed structure.
- the forging shaped in this way is, as a rule, from the forging heat cooled down at increased speed.
- This cooling the avoidance of Excretions, especially at the grain boundaries, can be in one Water basin or with a continuous cooling section.
- the forging is made at a temperature below 600 ° C reshaped, a solidification of the material, in particular a desired increase in the proof stress occurs.
- a solidification of the material in particular a desired increase in the proof stress occurs.
- the material fully austenitic or ferrite-free; there is therefore no expected partial folding to form a structure with deformation martensite. It turned out to be proved favorable when the deformation of the forged casting in the second Step at elevated temperature, but safely below 600 ° C and then the deformed shaped part is allowed to cool to room temperature.
- Manufacturing technology but also in terms of improved homogeneity and Material quality can be favorable if the block uses an ESR process will be produced.
- the material quality can be further increased if the block in the first step with a degree of deformation, which is defined: output cross section through Final cross-section is at least 4 times thermoformed. This makes a fine, recrystallized, uniform ferrite-free austenite structure achieved.
- the forging in the second step in a To transform temperature in the range of 400 to 500 ° C.
- An austenitic, paramagnetic material with the composition mentioned with good Corrosion properties that are thermoformed at least 3.5 times and below the Elimination temperature of nitrides and associated phases, however is cold-formed above a temperature of 350 ° C, shows the slightest traces of ferrite, practically no ferrite content in the preferred ranges of the composition on and behaves essentially paramagnetically with a relative Permeability below 1.05, in particular below 1.016.
- the yield strength R P0.2 of the material at room temperature is higher than 700 N / mm 2 .
- the values for the impact strength at room temperature are greater than 52J and the FATT (Fracture Appearance Transition Temperature) is lower than -25 ° C.
- Table 1 shows the chemical composition of all reference materials and, additionally, the deformation data for samples 1 to 3 and A to E.
- Samples 4 to 6 come from comparative material that was available on the market.
- Table 2 summarizes the results regarding the magnetic property, the mechanical values and the corrosion behavior.
- Samples 2 and A were made from a steel which was melted in the induction furnace and cast into blocks under protective gas.
- Samples 1, 3, B to E come from ESR material.
- the materials of samples 1 and 3 have low magnetic data with good magnetic data Yield strengths and strength values.
- Good toughness and sufficient FATT and the corresponding oxalic acid test pattern show low hole potentials opposite, whereby the materials due to an insufficient Eliminate property profile for high loads. The causes of this are in the low chromium and manganese contents as well as in the consequence low nitrogen concentrations.
- the material of sample 2 does have a sufficiently high chromium content, however, low manganese and the like cause nitrogen in particular poor corrosion resistance.
- the samples A to E produced by means of the method according to the invention are significantly improved in leaps and bounds in the entirety of the use properties. Synergistically, the respective, coordinated concentrations of the alloying elements and the solidifying cold forming of the material produced without precipitation provide superior corrosion resistance with a low relative magnetic permeability and a substantial increase in the strength values of the same. This is also shown by the test results or measured values of the freely obtained alloy samples 4 to 6.
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- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Electromagnetism (AREA)
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Abstract
Description
Die Erfindung bezieht sich auf ein Verfahren zur Herstellung eines
paramagnetischen, insbesondere in Medien mit hoher Chloridkonzentration
korrosionsbeständigen Werkstoffes mit hoher Dehngrenze, Festigkeit und Zähigkeit
bestehend aus in Gew.-%
max. 0,1 Kohlenstoff
0,21 bis 0,6 Silizium
17,0 bis 24,0 Chrom sowie Mangan und Stickstoff
bis 2,5 Nickel
bis 1,9 Molybdän
max. 0,3 Kupfer
bis 0,002 Bor
bis 0,8 Elemente der Gruppe 4 und 5 des Periodensystems
Rest Eisen, erschmelzungsbedingte Begleitelemente und Verunreinigungen.The invention relates to a method for producing a paramagnetic, in particular in media with a high chloride concentration, corrosion-resistant material with a high yield strength, strength and toughness consisting of in% by weight
Max. 0.1 carbon
0.21 to 0.6 silicon
17.0 to 24.0 chromium as well as manganese and nitrogen
up to 2.5 nickel
up to 1.9 molybdenum
Max. 0.3 copper
up to 0.002 boron
up to 0.8 elements of groups 4 and 5 of the periodic table
Remainder iron, melting-related accompanying elements and impurities.
Weiters betrifft die Erfindung einen austenitischen, paramagnetischen Werkstoff mit guter Korrosionsbeständigkeit, insbesondere in Medien mit hoher Chloridkonzentration, und hoher Dehngrenze, Festigkeit und Zähigkeit bestehend aus Kohlenstoff, Mangan, Silizium, Chrom und Stickstoff sowie gegebenenfalls Nickel, Molybdän, Kupfer, Bor, karbidbildende Elemente, Rest Eisen, erschmelzungsbedingte Begleitelemente und Verunreinigungen.The invention further relates to an austenitic, paramagnetic material good corrosion resistance, especially in media with high Chloride concentration, and high yield strength, strength and toughness made of carbon, manganese, silicon, chromium and nitrogen, and optionally Nickel, molybdenum, copper, boron, carbide-forming elements, remainder iron, Melting-related accompanying elements and impurities.
Schließlich umfaßt die Erfindung die Verwendung eines nach dem eingangs genannten Verfahren hergestellten Werkstoffes.Finally, the invention includes the use of one at the beginning mentioned method manufactured material.
Hochfeste Werkstoffe, die paramagnetisch und korrosionsbeständig sind und aus wirtschaftlichen Gründen im wesentlichen aus Chrom- Mangan- Eisen- Legierungen bestehen, werden für den chemischen Apparatebau, bei Einrichtungen für die elektrische Energieerzeugung und insbesondere für Komponenten in der Ölfeldtechnik verwendet. Sowohl an die korrosionschemischen also auch an die mechanischen Eigenschaften derartig einzusetzender Materialien werden in zunehmendem Maße höhere Forderungen gestellt.High-strength materials that are paramagnetic and corrosion-resistant economic reasons mainly from chromium-manganese-iron alloys exist for chemical apparatus engineering, for facilities for electrical power generation and especially for components in the Oilfield technology used. Both the corrosion chemical and the mechanical properties of such materials are described in increasingly higher demands.
Bei im wesentlichen allen oben angeführten Verwendungsarten ist es unabdingbar, daß sich der Werkstoff vollkommen homogen,höchst amagnetisch bzw. paramagnetisch verhält. Bei Kappenringen von Generatoren mit hoher Dehngrenze und Zähigkeit beispielsweise, muß ein gegebenenfalls geringfügiges ferromagnetisches Verhalten auch in Teilen des Werkstoffes mit höchster Sicherheit ausgeschlossen sein. Für Messungen bei der Durchführung von Bohrungen, insbesondere Explorationsbohrungen in Erdöl- oder Erdgasfeldern, sind Schwerstangen aus Werkstoffen mit magnetischen Permeabilitätswerten von unter 1,02 bzw. von weniger als 1,018 erforderlich, um eine genaue Verfolgung des Ortes der Bohrung und Abweichungen von dem vorgesehenen Kurs derselben feststellen und berichtigen zu können.For essentially all of the uses listed above, it is essential that the material is completely homogeneous, highly non-magnetic or behaves paramagnetically. For generator cap rings with a high yield strength and toughness, for example, must be a slight one ferromagnetic behavior even in parts of the material with the highest security be excluded. For measurements when drilling holes, especially exploration drilling in oil or gas fields Collars made of materials with magnetic permeability values below 1.02 or less than 1.018 required to track the location closely determine the hole and deviations from the intended course of the same and to be able to correct.
Weiters ist es auch notwendig, daß Einrichtungen der Ölfeldtechnik und Bohrstrangkomponenten eine hohe mechanische Festigkeit, insbesondere eine hohe 0,2%- Dehngrenze aufweisen, um dadurch maschinen- und anlagentechnische Vorteile und eine hohe Betriebssicherheit zu erhalten. Ebenso wichtig ist in vielen Fällen eine hohe Dauerwechselfestigkeit, weil bei einer Rotation des Teiles bzw. der Schwerstangen schwellende oder wechselnde Beanspruchungen vorliegen können.Furthermore, it is also necessary that facilities of oil field technology and Drill string components have a high mechanical strength, in particular a have a high 0.2% proof stress in order to technical advantages and high operational reliability. As well in many cases it is important to have a high fatigue strength, because with one Rotation of the part or the drill collars swelling or changing Stresses can exist.
Schließlich ist von entscheidender Bedeutung das Korrosionsverhalten des Werkstoffes in wässrigen oder ölhaltigen Medien, insbesondere mit hoher Chloridkonzentration.Finally, the corrosion behavior of the Material in aqueous or oil-containing media, especially with high Chloride concentration.
Den Anforderungen der neueren Entwicklungen in der Anlagen- und Tierfbohrtechnik zufolge werden immer strengere Maßstäbe an die Werkstoffe hinsichtlich der Kombination von paramagnetischem Verhalten, hoher Dehngrenze sowie dergleichen Festigkeit und Beständigkeit gegen chloridinduzierte Spannungsrißkorrosion sowie Lochfraßkorrosion (Lochkorrosion) und Spaltkorosion gestellt. The requirements of recent developments in plant and According to Tierfbohrtechnik, materials are subject to ever stricter standards regarding the combination of paramagnetic behavior, high yield strength and the like strength and resistance to chloride-induced Stress corrosion cracking as well as pitting corrosion (pitting corrosion) and crevice corrosion posed.
Es sind Werkstoffe aus Cr-Mn-Fe- Legierungen bekannt, die hinsichtlich der mechanischen Eigenschaften und des Korrosionsverhaltens durchaus den an diese gestellten diesbezüglichen Anforderungen genügen, allein deren magnetische Permeabilitätswerte verhindern den Einsatz für Teile, die im Zusammenhang mit magnetischen Messungen eingesetzt werden und schließen beispielsweise eine Verwendung für Schwerstangen aus. Andererseits können erforderliche amagnetische Werkstoffe mit guten Festigkeitseigenschaften den Korrosionsangriffen nicht standhalten und weitgehend paramagnetische Teile mit hohem Korrosionswiderstand besitzen oft nicht die notwendigen hohen mechanischen Werte.There are materials made of Cr-Mn-Fe alloys known with regard to mechanical properties and the corrosion behavior definitely match those the relevant requirements are met, only their magnetic Permeability values prevent use for parts related to magnetic measurements are used and include, for example Use for drill collars. On the other hand, required non-magnetic materials with good strength properties Do not withstand corrosive attack and largely use paramagnetic parts high corrosion resistance often do not have the necessary high resistance mechanical values.
Es ist bekannt, durch Stickstoffgehalte die mechanischen und korrosionschemischen Eigenschaften von im wesentlichen Cr -Mn-Fe- Legierungen zu verbessern, wobei jedoch teure metallurgische Verfahren, die mit erhöhten Drücken arbeiten, erforderlich sind.It is known that the mechanical and nitrogen contents Corrosion-chemical properties of essentially Cr -Mn-Fe alloys to improve, however, using expensive metallurgical processes involving increased Press work are required.
Aus wirtschaftlichen Gründen wurden auch Eisen-Mangan-Chrom- Legierungen entwickelt, die ohne Druckschmelz- und dergleichen Gießverfahren,also bei Atmosphärendruck, herstellbar sind ( WO 98/48070), wobei durch legierungstechnische Maßnahmen ein gewünschtes Eigenschaftsprofil des Werkstoffes erreicht werden soll. Derartige Legierungen weisen durchwegs zur Verbesserung der Korrosionsbeständigkeit einen Molybdängehalt von über 2% auf, was Vorteile insbesondere beim Loch- und Spaltkorrosionsverhalten erbringt . Molybdän ist jedoch wie Chrom ein Ferritbildner und kann in Seigerungsbereichen zu ungünstigen magnetischen Eigenschaften des Materials führen. Erhöhte Nickelgehalte stabilisieren zwar den Austenit, wirken aber gegebenenfalls mit höheren Kupferkonzentrationen verschlechternd auf die mechanischen Eigenschaften und intensivieren die Rißinitiation.Iron-manganese-chromium alloys were also used for economic reasons developed that without pressure melting and the like casting process, so at Atmospheric pressure can be produced (WO 98/48070), whereby alloying measures a desired property profile of the Material should be achieved. Alloys of this type point to Improvement in corrosion resistance to a molybdenum content of over 2%, which brings advantages in particular with hole and crevice corrosion behavior. However, like chromium, molybdenum is a ferrite former and can be found in segregation areas lead to unfavorable magnetic properties of the material. Increased Nickel contents stabilize the austenite, but may also contribute higher copper concentrations worsening the mechanical Properties and intensify the crack initiation.
Durch eine ausgewogene Konzentration der Legierungselemente wird gemäß PCT/US91/02490 versucht, eine austenitische antimagnetische rostfreie Stahllegierung zu schaffen, die bei Warmbearbeitung jedoch ohne anschließende Vergütung eine hervorragende Kombination von Eigenschaften besitzt.A balanced concentration of the alloying elements results in PCT / US91 / 02490 tried an austenitic antimagnetic stainless To create steel alloy, but with hot machining without subsequent Remuneration has an excellent combination of properties.
Um insbesondere die mechanischen Eigenschaften von amagnetischen Bohrsstrangteilen zu verbessern, wurde bereits ein Verfahren vorgeschlagen (EP-0207068 B1), bei welchem der Werkstoff einer Warm-und Kaltumformung unterworfen wird, wobei die Kaltumformung bei einer Temperatur zwischen 100°C und 700°C mit einem zumindest 5%-igen Verformungsgrad erfolgt.In particular, the mechanical properties of non-magnetic A method has already been proposed to improve drill string parts (EP-0207068 B1), in which the material is hot and cold formed is subjected to the cold forming at a temperature between 100 ° C. and 700 ° C with an at least 5% degree of deformation.
Die Erfindung setzt sich zum Ziel, ein Verfahren zu schaffen, welches bei Ausschöpfung von legierungstechnischen Maßnahmen eine Verformung einschließt und synergetisch eine Herstellung eines mit hoher Sicherheit paramagnetischen, in Medien mit hoher Chloridkonzentration korrosionsbeständigen ferritfreien Werkstoffes mit hoher Dehngrenze, Festigkeit und Zähigkeit angibt.The invention aims to provide a method which Exhaustion of alloying measures includes deformation and synergistically a manufacture of a highly magnetic paramagnetic, in Media with a high chloride concentration are corrosion-resistant, ferrite-free Material with high yield strength, strength and toughness indicates.
Weiters ist es Aufgabe der Erfindung, einen vollaustenitischen paramagnetischen Werkstoff mit guter Korrosionsbeständigkeit und hohen mechanischen Werten zu erstellen.Another object of the invention is a fully austenitic paramagnetic Material with good corrosion resistance and high mechanical values create.
Das erfindungsgemäße Ziel wird bei einem Verfahren der eingangs genannten Art
dadurch erreicht, daß eine Legierung bestehend in Gew.-%
Mangan und
Stickstoff
und mit
Manganese and
nitrogen
and with
Die durch die Erfindung erreichten Vorteile sind im wesentlichen darin zu sehen, daß bei hoher Wirtschaftlichkeit betreffend die Werkstoffkosten und das Herstellverfahren durch eine legierungstechnische Optimierung größte Korrosionsbeständigkeit und ein gewünscht paramagnetisches Verhalten des Materials erreicht werden, wobei dessen hohe mechanischen Kennwerte, insbesondere die Dehngrenze, ohne nachteilige Auswirkungen auf die oben angeführten Eigenschaften durch eine gezielt ausgerichtete Kaltumformung bei erhöhter Temperatur eine weitere wesentliche Verbesserung erfahren.The advantages achieved by the invention are essentially to be seen in that with high efficiency regarding the material costs and Manufacturing process by an alloy-technical optimization largest Corrosion resistance and a desired paramagnetic behavior of the Material can be achieved, whereby its high mechanical characteristics, especially the yield strength, without adversely affecting the above properties mentioned by a targeted cold forming increased temperature experienced a further significant improvement.
Der Kohlenstoffgehalt der Legierung ist mit max. 0,1 Gew.-% nach oben begrenzt, weil höhere Gehalte sowohl zu einer Loch- und Spannungsrißkorrosion in chloridhaltigen Medien als auch zu einer interkristallinen Korrosion von daraus gefertigten Teilen führen. Die Einhaltung dieser Obergrenze, wobei Gehalte von max. 0,06 und 0,05 Gew.-% bevorzugt sind, ist, wie oben erwähnt, aus korrosionschemischen Gründen wichtig, obwohl Kohlenstoff die Dehngrenze erhöht und stark austenitbildend wirkt.The carbon content of the alloy is max. 0.1% by weight, because higher levels result in both pitting and stress corrosion cracking chloride-containing media as well as intercrystalline corrosion from it manufactured parts. Compliance with this upper limit, with levels of Max. 0.06 and 0.05% by weight is preferred, as mentioned above, from Corrosion-chemical reasons important, although carbon increases the yield strength and has a strong austenite-forming effect.
Silizium soll als Desoxidationsmetall mit einer Konzentration von mindestens 0,21 Gew.-% im Metall vorliegen, wobei eine Obergrenze mit 0,6 Gew.-% vorgesehen ist. Höhere Gehalte an Silizium führen zu Nitridbildungen und zur Verschlechterung der Beständigkeit gegen Spannungsrißkorrosion des Materials. Weil Silizium auch stark ferritbildend wirkt, kann durch höhere Gehalte auch die magnetische Permeabilität nachteilig beeinflußt werden. In vorteilhafter Weise ist ein Höchstgehalt von 0,48 Gew.-% wirksam.Silicon is said to be a deoxidation metal with a concentration of at least 0.21 % By weight is present in the metal, an upper limit of 0.6% by weight being provided. Higher silicon levels lead to nitride formation and deterioration of the Resistance to stress corrosion cracking of the material. Because silicon is also strong Magnetic permeability can also have a ferrite-forming effect due to higher contents be adversely affected. A maximum content of 0.48 is advantageous % By weight effective.
Das Korrosionsverhalten, insbesondere eine Beständigkeit gegen Spannungsrißkorrosion und Lochkorrosion wird durch den Chromgehalt der Legierung bestimmt. Dabei ist wichtig, daß eine weitgehend homogene Chromverteilung im Werkstoff vorliegt; mit anderen Worten, daß sogenannte Schwachstellen der Passivschicht durch Seigerungen und Einschlüsse vermieden sind. Um weitgehend gesichert, eine gewünschte Korrosionsbeständigkeit zu erreichen, sind Chromgehalte von größer als 17 Gew.-%, vorzugweise von mehr als 19 Gew.-% erforderlich. Chrom erhöht zwar die Löslichkeit der Legierung für Stickstoff, wirkt jedoch ferritbildend und somit ungünstig bezüglich des gewünschten amagnetischen bzw. paramagnetischen Verhaltens des Materials, so daß die höchste Chromkonzentration 24,0 Gew.-%, bevorzugt 22,0 Gew.-% beträgt.Corrosion behavior, especially resistance to Stress corrosion cracking and pitting corrosion is caused by the chromium content of the Alloy determined. It is important that a largely homogeneous Chromium distribution in the material is present; in other words, the so-called Weak spots in the passive layer due to segregation and inclusions avoided are. To be largely secured, a desired corrosion resistance too chromium contents of more than 17% by weight, preferably of more than 19% by weight required. Chromium increases the solubility of the alloy for Nitrogen, however, has a ferrite-forming effect and is therefore unfavorable with regard to the desired one non-magnetic or paramagnetic behavior of the material, so that the highest chromium concentration is 24.0% by weight, preferably 22.0% by weight.
Durch Nickel können zwar die mechanischen Werte der Legierung und die Stabilität der austenitischen Struktur verbessert werden, für ausreichend gute Korrosionseigenschaften des Werkstoffes, insbesondere die Spannungsrißkorrosion betreffend, sind Nickelgehalte geringer als 2,5 Gew.-% besser, jedoch kleiner als 0,96 Gew.-% gefordert. Durch niedrige Nickelgehalte ab 0,21 Gew.-% aufwärts bis zu obigen Maximalwerten ist es möglich, ohne Nachteile im Korrosionsverhalten der gewünschten Legierung, eine Erhöhung der Dehngrenze zu erreichen.Nickel can increase the mechanical properties of the alloy and the stability the austenitic structure can be improved for sufficiently good ones Corrosion properties of the material, especially the Regarding stress corrosion cracking, nickel contents are less than 2.5% by weight. better, but less than 0.96 wt .-% required. Due to low nickel contents From 0.21% by weight up to the above maximum values it is possible without disadvantages in the corrosion behavior of the desired alloy, an increase in To reach yield strength.
Das Legierungselement Molybdän verbessert die Beständigkeit des Werkstoffes gegen Korrosion, insbesondere gegen chloridinduzierte Spalt- und Lochkorrosion. Weil jedoch dieses Element ein starken Ferritbildner und ein dergleichen Karbidbildner sowie Bildner von vergesellschafteten Phasen ist, liegen die Molybdänobergrenzen bei 1,9 Gew.-%, besser jedoch bei 1,5 Gew.-%. Geringe Gehalte ab 0,28 Gew.-% Molybdän aufwärts bis zu obigen Grenzwerten können ausscheidungsfreier Austenitstruktur des Gefüges korrosionschemisch Vorteile bringen.The alloy element molybdenum improves the durability of the material against corrosion, especially against chloride-induced crevice and pitting corrosion. However, because this element is a strong ferrite former and the like Carbide formers and formers of socialized phases are the Molybdenum caps at 1.9% by weight, but better at 1.5% by weight. Low Levels from 0.28 wt .-% molybdenum up to the above limits can Precipitation-free austenite structure of the micro-chemical structure Advantages bring.
Das oft gegen Korrosionsangriff effektive Element Kupfer hat sich bei der erfindungsgemäßen Legierung jeoch als nachteilig wirkend herausgestellt, wobei die Kupfergehalte kleiner als 0,3 Gew.-%, besser jedoch kleiner als 0,25 Gew.-% sind, um Resistenz gegen Korrosion zu erreichen.The element copper, which is often effective against corrosion attack, has been used in the However, the alloy according to the invention was found to have a disadvantageous effect the copper contents less than 0.3% by weight, but better less than 0.25% by weight to achieve resistance to corrosion.
Bor kann zur Verbesserung des Warmumformverhaltens des Materials diesem in einer Menge bis zu 0,002 Gew.-%, vorzugsweise bis 0,0012 Gew.-% zulegiert sein. Höhere Mengen an Bor führen zu Korngrenzenausscheidungen, Versprödungserscheinungen und unerwünschten Gefügestrukturen.Boron can be used to improve the hot forming behavior of the material an amount of up to 0.002% by weight, preferably up to 0.0012% by weight. Higher amounts of boron lead to grain boundary deposits, Signs of embrittlement and undesirable structures.
Besonders wichtig für eine Verhinderung der Spannungsriß-und Lochkorrosion sind niedrige Gehalte der Elemente der Gruppe 4 und Gruppe 5 des Periodensystems. Diese Elemente ( Ti, Zr, Hg, V, Nb, Ta) sind äußerst starke Karbid- und Nitrid- bzw. Karbonitridbildner und weisen in der Gesamtheit Werte von geringer als 0,8 Gew.-%, besser von geringer als 0,48 Gew.-% auf. Höhere Konzentrationen bewirken Ausscheidungen und dadurch Schwachstellen in der Passivschicht an der Werkstückoberfläche, wodurch die Korrosionsbeständigkeit beeinträchtigt ist.Are particularly important for preventing stress cracking and pitting corrosion low levels of elements of group 4 and group 5 of the periodic table. These elements (Ti, Zr, Hg, V, Nb, Ta) are extremely strong carbide and nitride or Carbonitride formers and have values of less than 0.8 in total % By weight, better of less than 0.48% by weight. Higher concentrations cause excretions and thereby weak points in the passive layer on the Workpiece surface, which affects the corrosion resistance.
Legierungstechnisch stellt das Element Stickstoff einen starken Austenitbildner dar. Außerdem werden die Dehngrenze und die Resistenz des Werkstoffes gegen Loch- und Spaltkorrosion durch Stickstoff erhöht. Stickstoff ist in Eisenbasislegierungen jedoch nur begrenzt löslich, wobei durch steigende Chrom- und Mangangehalte die Löslichkeitsgrenze erhöht wird. Im wesentlichen sind daher die Chrom-Mangan- und Stickstoffkonzentrationen der Legierung synergetisch für den erfindungsgemäßen Werkstoff bzw. für dessen Eigenschaften zu sehen. Einen Chromgehalt von 17,0 bis 24,0 Gew.-%, vorzugsweise von 19,0 bis 22,0 Gew.-%, besitzt, wie vorher dargelegt, der Werkstoff hauptsächlich aus Gründen der Korrosionsbeständigkeit und des paramagnetischen Verhaltens wegen. Der Mangangehalt von mehr als 20 Gew.-%, jedoch weniger als 30 Gew.-%, wobei die bevorzugten Konzentrationsbereiche zwischen 20,5 bzw. 21,5 und 29,5 bzw. 25,0 Gew.-% liegen, ist einerseits zur Erhöhung der Stickstofflöslichkeit und andererseits zur Stabilisierung der austenitischen bzw. ferritfreien Gefügestruktur vorgesehen. Schließlich dient der Stickstoffgehalt von mehr als 0,6 Gew.-%, jedoch niedriger als 1,4 Gew.-%, im wesentlichen der Erreichbarkeit von hohen Dehngrenzenwerten. In terms of alloying, the element nitrogen is a strong austenite former. In addition, the yield strength and the resistance of the material to perforations and crevice corrosion increased by nitrogen. Nitrogen is in iron based alloys however, only soluble to a limited extent, with increasing chromium and manganese contents Solubility limit is increased. The chromium-manganese and Nitrogen concentrations of the alloy synergistically for the invention To see material or for its properties. A chromium content of 17.0 to 24.0% by weight, preferably from 19.0 to 22.0% by weight, as before explained the material mainly for reasons of corrosion resistance and because of the paramagnetic behavior. The manganese content of more than 20 % By weight, but less than 30% by weight, the preferred ones Concentration ranges between 20.5 or 21.5 and 29.5 or 25.0% by weight lie on the one hand to increase nitrogen solubility and on the other hand to Stabilization of the austenitic or ferrite-free structure is provided. Finally, the nitrogen content of more than 0.6 wt .-%, but lower than 1.4% by weight, essentially the accessibility of high yield strength values.
Bevorzugte Stickstoffkonzentrationsbereiche sind:
0,64 bis 1,3 Gew.-%, insbesondere 0,72 bis 1,2 Gew.-% N. Niedrige Mangangehalte
von 20 Gew.-% und geringer sowie hohe Stickstoffkonzentrationen von 1,4 Gew.-%
und größer führen auf Grund einer sprunghaften Abnahme der Stickstofflöslichkeit
der Legierung bei der Erstarrung zu porösen bzw. undichten Gußstücken. Bei
Mangangehalten von 30 Gew.-% und mehr sowie bei Stickstoffanteilen von 0,6
Gew.-% und weniger sind erforderlich hohe Dehngrenzen nicht erreichbar und eine
Versprödung des Materials kann auftreten.Preferred nitrogen concentration ranges are:
0.64 to 1.3 wt .-%, in particular 0.72 to 1.2 wt .-% N. Low manganese contents of 20 wt .-% and lower and high nitrogen concentrations of 1.4 wt .-% and larger due to a sudden decrease in the nitrogen solubility of the alloy when it solidifies into porous or leaky castings. With manganese contents of 30% by weight or more and with nitrogen contents of 0.6% by weight or less, high yield strengths are not attainable and the material can become brittle.
Wenn, wie aus Gründen der Werkstoffgüte und der Wirtschaftlichkeit vorgesehen ist, der Gußblock oder das Gußstück unter Atmosphärendruck erstarrt ist, kann dieser bzw. dieses einer Diffusionsglühung, die einer Homogenisierung der Mikrostuktur bzw. einem Ausgleich der Mikroseigerungen dient, unterworfen werden. Diese Glühung kann beispielsweise bei einer Temperatur um 1200 °C mit einer Dauer bis 60 Stunden durchgeführt werden.If, as intended for reasons of material quality and economy is, the casting block or the casting has solidified under atmospheric pressure, can this or this diffusion annealing, which is a homogenization of the Serves microstructure or a compensation of micro segregations become. This annealing can be carried out, for example, at a temperature of around 1200 ° C up to 60 hours.
Die Warmumformung des Gußstückes, die den ersten Verformungsschritt darstellt, erfolgt meist durch Schmieden, wobei die Umformtemperatur höher als 850°C liegt, um eine entsprechend günstige Rekristallisation des Mischgefüges sicherzustellen. Das derart geformte Schmiedestück wird, in der Regel aus der Schmiedehitze, mit erhöhter Geschwindigkeit abgekühlt. Diese Abkühlung, die der Vermeidung von Ausscheidungen, insbesondere an den Korngrenzen dient, kann in einem Wasserbecken oder mit einer Durchlaufkühlstrecke vorgenommen werden. Dabei kann auch von Vorteil sein, wenn nach dem ersten Schritt der umgeformte Block einer Zwischenglühung bei einer Glühtemperatur von über 850°C und darauffolgend einer Abkühlung mit erhöhter Geschwindigkeit unterworfen wird, weil dadurch gegebenenfalls gebildete Ausscheidungen wieder in Lösung gebracht werden.The hot forming of the casting, which represents the first deformation step, mostly done by forging, whereby the forming temperature is higher than 850 ° C, to ensure a correspondingly favorable recrystallization of the mixed structure. The forging shaped in this way is, as a rule, from the forging heat cooled down at increased speed. This cooling, the avoidance of Excretions, especially at the grain boundaries, can be in one Water basin or with a continuous cooling section. there can also be advantageous if after the first step the deformed block intermediate annealing at an annealing temperature of over 850 ° C and thereafter is subjected to cooling at an increased rate because it does so any precipitates formed are brought back into solution.
Im zweiten Schritt wird das Schmiedestück bei einer Temperatur von unter 600°C umgeformt, wobei eine Verfestigung des Werkstoffes, insbesondere eine gewünschte Erhöhung der Dehngrenze eintritt. Trotz des hohen Chrom- und insbesondere Mangangehaltes bleibt in überraschender Weise der Werkstoff vollaustenitisch bzw. ferritfrei; es erfolgt also kein erwartetes teilweises Umklappen unter Ausbildung eines Gefüges mit Verformungsmartensit. Es hat sich dabei als günstig erwiesen, wenn die Verformung des geschmiedeten Gußstückes im zweiten Schritt bei erhöhter Temperatur, jedoch sicher unter 600°C erfolgt und anschließend der verformte Umformteil auf Raumtemperatur erkalten gelassen wird. Fertigungstechnisch, jedoch auch hinsichtlich einer verbesserten Homogenität und Werkstoffgüte kann es günstig sein, wenn der Block nach einem ESU-Verfahren hergestellt wird.In the second step, the forging is made at a temperature below 600 ° C reshaped, a solidification of the material, in particular a desired increase in the proof stress occurs. Despite the high chrome and Manganese content, in particular, surprisingly remains the material fully austenitic or ferrite-free; there is therefore no expected partial folding to form a structure with deformation martensite. It turned out to be proved favorable when the deformation of the forged casting in the second Step at elevated temperature, but safely below 600 ° C and then the deformed shaped part is allowed to cool to room temperature. Manufacturing technology, but also in terms of improved homogeneity and Material quality can be favorable if the block uses an ESR process will be produced.
Die Werkstoffgüte kann weiter gesteigert werden, wenn der Block im ersten Schritt mit einem Umformgrad, welcher definiert ist: Ausgangsquerschnitt durch Endquerschnitt von mindestens 4-fach warmverformt wird. Dadurch wird ein feines, rekristallisiertes, gleichmäßiges ferritfreies Austenitgefüge erreicht.The material quality can be further increased if the block in the first step with a degree of deformation, which is defined: output cross section through Final cross-section is at least 4 times thermoformed. This makes a fine, recrystallized, uniform ferrite-free austenite structure achieved.
Nach einem Abkühlen mit erhöhter Geschwindigkeit von einer Temperatur von über 850°C, was zur Verhinderung einer Ausscheidungsbildung dient, wird das Schmiedestück im zweiten Schritt mit einer Umformung in %, definiert als Ausgangsquerschnitt minus Endquerschnitt gebrochen durch Ausgangsquerschnitt mal 100 von kleiner 35 % verformt, wodurch die Dehngrenze und die Festigkeit des Materials erhöht werden. Im Sinne gleichmäßiger Erhöhung der mechanischen Werte hat sich ein rekristallisationsfreier Verformungsbereich von 5 % bis 20 % herausgestellt.After cooling at an elevated rate from a temperature above 850 ° C, which serves to prevent the formation of excretions, it will Forging in the second step with a deformation in%, defined as Output cross-section minus final cross-section broken by output cross-section times 100 deformed by less than 35%, whereby the yield strength and the strength of the Material can be increased. In the sense of an even increase in mechanical A recrystallization-free deformation range of 5% to 20% exposed.
Sowohl für eine Durchführung der Kaltumformung als auch für eine wirkungsvolle tiefgreifende und versprödungsfreie Verbesserung der Werkstoffeigenschaften und eine sichere Vermeidung des Auftretens von Verformungsmartensit hat es sich als besonders vorteilhaft herausgestellt, das Schmiedestück im zweiten Schritt bei einer Temperatur im Bereich von 400 bis 500°C umzuformen.Both for performing cold forming as well as for an effective one profound and embrittlement-free improvement of the material properties and a safe avoidance of the occurrence of deformation martensite has proven to be particularly advantageous, the forging in the second step in a To transform temperature in the range of 400 to 500 ° C.
Ein gemäß dem vorstehenden Verfahren hergestellter austenitischer, paramagnetischer Werkstoff mit der genannten Zusammensetzung mit guten Korrosionseigenschaften, der mindestens 3,5-fach warmverformt und unterhalb der Ausscheidungstemperatur von Nitriden sowie vergesellschafteten Phasen, jedoch über einer Temperatur von 350°C kaltverformt ist, weist geringste Spuren von Ferrit, in den bevorzugten Bereichen der Zusammensetzung praktisch keinen Ferritgehalt auf und verhält sich im wesentlichen paramagnetisch mit einer relativen Permeabilität ur von unter 1,05, insbesondere von unter 1,016.An austenitic, paramagnetic material with the composition mentioned with good Corrosion properties that are thermoformed at least 3.5 times and below the Elimination temperature of nitrides and associated phases, however is cold-formed above a temperature of 350 ° C, shows the slightest traces of ferrite, practically no ferrite content in the preferred ranges of the composition on and behaves essentially paramagnetically with a relative Permeability below 1.05, in particular below 1.016.
Die Dehngrenze RP0,2 des Werkstoffes bei Raumtemperatur liegt höher als 700 N/mm2. Die Werte für die Kerbschlagzähigkeit bei Raumtemperatur sind größer als 52J und die FATT (Fracture Appearance Transition Temperature) ist tiefer als -25°C. Der erfindungsgemäße Werkstoff weist weiters eine Dauerwechselfestigkeit von größer als + 400 N/mm2 bei N = 107 Lastwechsel auf und besitzt ein Lochpotential in neutralen Lösungen (entsprechend ASTM G5/87) bei Raumtemperatur von größer als 700 mVH/1000ppm Chloride und/oder 200mVH /80000ppm Chloride.The yield strength R P0.2 of the material at room temperature is higher than 700 N / mm 2 . The values for the impact strength at room temperature are greater than 52J and the FATT (Fracture Appearance Transition Temperature) is lower than -25 ° C. The material according to the invention also has a fatigue strength of greater than + 400 N / mm 2 at N = 10 7 load changes and has a hole potential in neutral solutions (according to ASTM G5 / 87) at room temperature of greater than 700 mV H / 1000ppm chlorides and / or 200mV H / 80000ppm chlorides.
Anhand von Beispielen wird die Erfindung näher erläutert.
In Tabelle 1 sind chemische Zusammensetzung sämtlicher Vergleichswerkstoffe
und von den Proben 1 bis 3 sowie A bis E zusätzlich die Verformungsdaten
angegeben. Die Proben 4 bis 6 stammen aus Vergleichsmaterial, das am Markt
verfügbar war.
In Tabelle 2 sind die Ergebnisse betreffend die magnetische Eigenschaft, die
mechanischen Werte und das Korrosionsverhalten zusammengestellt.The invention is explained in more detail with the aid of examples.
Table 1 shows the chemical composition of all reference materials and, additionally, the deformation data for samples 1 to 3 and A to E. Samples 4 to 6 come from comparative material that was available on the market.
Table 2 summarizes the results regarding the magnetic property, the mechanical values and the corrosion behavior.
Die Proben 2 und A wurden aus einem Stahl, der im Induktionsofen erschmolzen
wurde und unter Schutzgas zu Blöcken gegossen wurde, hergestellt.
Die Proben 1,3, B bis E stammen aus ESU-Material.Samples 2 and A were made from a steel which was melted in the induction furnace and cast into blocks under protective gas.
Samples 1, 3, B to E come from ESR material.
Die Werkstoffe der Proben 1 und 3 weisen bei guten magnetischen Daten niedrige Dehngrenzen und Festigkeitswerte auf. Guter Zähigkeit und ausreichender FATT sowie entsprechendem Oxalsäuretestbild stehen niedrige Lochpotentiale gegenüber, wodurch die Werkstoffe auf Grund eines unzureichenden Eigenschaftsprofiles für hohe Beanspruchungen ausscheiden. Die Ursachen dafür liegen in den niedrigen Chrom- und Mangangehalten sowie den in der Folge niedrigen Stickstoffkonzentrationen. The materials of samples 1 and 3 have low magnetic data with good magnetic data Yield strengths and strength values. Good toughness and sufficient FATT and the corresponding oxalic acid test pattern show low hole potentials opposite, whereby the materials due to an insufficient Eliminate property profile for high loads. The causes of this are in the low chromium and manganese contents as well as in the consequence low nitrogen concentrations.
Das Material der Probe 2 weist zwar einen ausreichend hohen Chromgehalt auf, niedrige Mangan- und dergleichen Stickstoffwerte bewirken jedoch insbesondere schlechte Korrosionsbeständigkeit.The material of sample 2 does have a sufficiently high chromium content, however, low manganese and the like cause nitrogen in particular poor corrosion resistance.
Die mittels des erfindungsgemäßen Verfahrens hergestellten Proben A bis E sind in
der Gesamtheit der Gebrauchseigenschaften deutlich sprunghaft verbessert.
Synergetisch erbringen die jeweiligen, aufeinander abgestimmten Konzentrationen
der Legierungselemente und die verfestigende Kaltumformung des
ausscheidungsfrei erstellten Werkstoffes eine überlegene Korrosionsbeständigkeit
bei einer geringen relativen magnetischen Permeabilität und eine wesentliche
Erhöhung der Festigkeitswerte desselben. Dies wird auch durch die
Untersuchungsergebnisse bzw. Meßwerte der frei erhaltenen Legierungsproben 4
bis 6 gezeigt.
Claims (24)
max. 0,1 Kohlenstoff
0,21 bis 0,6 Silizium
17,0 bis 24,0 Chrom sowie
Mangan und
Stickstoff
bis 2,5 Nickel
bis 1,9 Molybdän
max 0,3 Kupfer
bis 0,002 Bor
bis 0,8 Elemente der Gruppe 4 und 5 des Periodensystems
Rest Eisen, erschmelzungsbedingte Begleitelemente und Verunreinigungen,
dadurch gekennzeichnet, daß eine Legierung mit vorstehender Konzentration der Elemente und mit
mehr als 20 Gew.-%, jedoch weniger als 30 Gew.-% Mangan
und mit
mehr als 0,6 Gew.-%, jedoch weniger als 1,4 Gew.-% Stickstoff
erschmolzen, unter Atmosphärendruck zu einem Block oder Gußstück erstarren gelassen und der gebildete Block bzw. das Gußstück in einem ersten Schritt einer Warmumformung bei einer Umformtemperatur von höher als 850°C unterworfen und darauffolgend mit erhöhter Geschwindigkeit abgekühlt wird, wonach in einem zweiten Schritt eine weitere Umformung des Schmiedestückes bei einer Temperatur von unter 600°C erfolgt und danach der Umformteil auf Raumtemperatur erkalten gelassen wird.Process for the production of a paramagnetic, especially in media with high chloride concentration, corrosion-resistant material with high yield strength, strength and toughness, consisting of in% by weight
Max. 0.1 carbon
0.21 to 0.6 silicon
17.0 to 24.0 chrome as well
Manganese and
nitrogen
up to 2.5 nickel
up to 1.9 molybdenum
max 0.3 copper
up to 0.002 boron
up to 0.8 elements of groups 4 and 5 of the periodic table
Remainder iron, melting-related accompanying elements and impurities,
characterized in that an alloy with the above concentration of the elements and with
more than 20% by weight, but less than 30% by weight of manganese
and with
more than 0.6% by weight but less than 1.4% by weight nitrogen
melted, solidified under atmospheric pressure to form a block or casting and the block or casting formed in a first step is subjected to hot forming at a forming temperature of more than 850 ° C and then cooled at an increased speed, after which a further step is carried out in a second step Forming of the forging takes place at a temperature of below 600 ° C and then the forming part is allowed to cool to room temperature.
max.0,06, vorzugsweise max. 0,05 Kohlenstoff
0,21 bis 0,48 Silizium
19,0 bis 22,0 Chrom sowie
20,5 bis 29,5 Mangan
0,64 bis 1,3 Stickstoff
0,21 bis 0,96 Nickel
0,28 bis 1,5 Molybdän
max. 0,25 Kupfer
bis 0,0012 Bor
bis 0,48 karbidbildende Elemente
Rest Eisen, erschmelzungsbedingte Begleitelemente und Verunreinigungen erschmolzen und verarbeitet wird.A method according to claim 1, characterized in that an alloy consisting of in wt .-%
max.0.06, preferably max. 0.05 carbon
0.21 to 0.48 silicon
19.0 to 22.0 chromium as well
20.5 to 29.5 manganese
0.64 to 1.3 nitrogen
0.21 to 0.96 nickel
0.28 to 1.5 molybdenum
Max. 0.25 copper
up to 0.0012 boron
up to 0.48 carbide-forming elements
Remainder iron, melting-related accompanying elements and impurities are melted and processed.
max. 0,10 Kohlenstoff
0,21 bis 0,6 Silizium
mehr als 20,0 bis weniger als 30,0 Mangan
mehr als 0,6 bis weniger als 1,4 Stickstoff
17,0 bis 24,0 Chrom,
bis 2,5 Nickel
bis 1,9 Molybdän
max. 0,3 Kupfer
bis 0,002 Bor
bis 0,8 karbidbildende Elemente
Rest im wesentlichen Eisen gebildet, mit einem Umformgrad von mindestens 3,5-fach warmverformt und unterhalb der Ausscheidungstemperatur von Nitriden sowie von vergesellschafteten Phasen, jedoch bei erhöhter Temperatur, insbesondere über einer Temperatur von 350 °C kaltverformt ist und praktisch keinen Ferritgehalt aufweist.Austenitic, paramagnetic material with good corrosion resistance, especially in media with a high chloride concentration and high yield strength, strength and toughness, consisting of carbon, manganese, silicon, chromium and nitrogen as well as possibly nickel, molybdenum, copper, boron, carbide-forming elements, remainder iron, melting-related Accompanying elements and impurities, characterized in that the alloy consists of in% by weight
Max. 0.10 carbon
0.21 to 0.6 silicon
more than 20.0 to less than 30.0 manganese
more than 0.6 to less than 1.4 nitrogen
17.0 to 24.0 chrome,
up to 2.5 nickel
up to 1.9 molybdenum
Max. 0.3 copper
up to 0.002 boron
up to 0.8 carbide-forming elements
The remainder is essentially iron, is thermoformed with a degree of deformation of at least 3.5 times and is cold-formed below the precipitation temperature of nitrides and of associated phases, but at elevated temperature, in particular above a temperature of 350 ° C., and has practically no ferrite content.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0123299A AT407882B (en) | 1999-07-15 | 1999-07-15 | METHOD FOR PRODUCING A PARAMAGNETIC, CORROSION-RESISTANT MATERIAL AND THE LIKE MATERIALS WITH A HIGH STRETCH LIMIT, STRENGTH AND TENSITY |
| AT123299 | 1999-07-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1069202A1 true EP1069202A1 (en) | 2001-01-17 |
| EP1069202B1 EP1069202B1 (en) | 2002-12-11 |
Family
ID=3509471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00890207A Expired - Lifetime EP1069202B1 (en) | 1999-07-15 | 2000-06-29 | A paramagnetic, corrosion resistant austenitic steel with high elasticity, strength and toughness and a process for its manufacture |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US6454879B1 (en) |
| EP (1) | EP1069202B1 (en) |
| AT (2) | AT407882B (en) |
| CA (1) | CA2313975C (en) |
| DE (1) | DE50000903D1 (en) |
| ES (1) | ES2187434T3 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6454879B1 (en) | 1999-07-15 | 2002-09-24 | Schoeller-Bleckman Oilfield Technology Gmbh & Co. Kg | Process for producing a paramagnetic, corrosion-resistant material and like materials with high yield strength, strength, and ductility |
| EP2924131A1 (en) * | 2014-03-28 | 2015-09-30 | Outokumpu Oyj | Austenitic stainless steel |
| WO2020127789A1 (en) | 2018-12-20 | 2020-06-25 | Voestalpine Böhler Edelstahl Gmbh & Co Kg | Superaustenitic material |
| DE102018133251A1 (en) | 2018-12-20 | 2020-06-25 | Schoeller-Bleckmann Oilfield Technology Gmbh | Drill string component with high corrosion resistance and process for their manufacture |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060065327A1 (en) * | 2003-02-07 | 2006-03-30 | Advance Steel Technology | Fine-grained martensitic stainless steel and method thereof |
| AT412727B (en) * | 2003-12-03 | 2005-06-27 | Boehler Edelstahl | CORROSION RESISTANT, AUSTENITIC STEEL ALLOY |
| DE602007008420D1 (en) * | 2006-06-23 | 2010-09-23 | Jorgensen Forge Corp | AUSTENITIAN PARAMAGNETIC CORROSION-FREE STEEL |
| US7658883B2 (en) * | 2006-12-18 | 2010-02-09 | Schlumberger Technology Corporation | Interstitially strengthened high carbon and high nitrogen austenitic alloys, oilfield apparatus comprising same, and methods of making and using same |
| US9347121B2 (en) | 2011-12-20 | 2016-05-24 | Ati Properties, Inc. | High strength, corrosion resistant austenitic alloys |
| JP6451545B2 (en) * | 2015-08-05 | 2019-01-16 | 新日鐵住金株式会社 | High Mn steel for high-pressure hydrogen gas, method for producing the same, and piping, container, valve and joint made of the steel |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3847599A (en) * | 1973-10-04 | 1974-11-12 | Allegheny Ludlum Ind Inc | Corrosion resistant austenitic steel |
| US3907551A (en) * | 1973-04-30 | 1975-09-23 | Allegheny Ludlum Ind Inc | Corrosion resistant austenitic steel |
| US4217136A (en) * | 1974-05-01 | 1980-08-12 | Allegheny Ludlum Steel Corporation | Corrosion resistant austenitic stainless steel |
| DE3143096A1 (en) * | 1980-11-05 | 1982-05-19 | General Electric Co., Schenectady, N.Y. | Iron-based alloy, process for producing it, and articles manufactured with it |
| EP0432434A1 (en) * | 1989-12-07 | 1991-06-19 | Vereinigte Schmiedewerke Gmbh | Process for manufacturing joining structural parts from a fully austenitic Cr-Mn steel. |
| US5094812A (en) * | 1990-04-12 | 1992-03-10 | Carpenter Technology Corporation | Austenitic, non-magnetic, stainless steel alloy |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3936297A (en) * | 1972-05-08 | 1976-02-03 | Allegheny Ludlum Industries, Inc. | Method of producing austenitic stainless steel |
| US3938990A (en) * | 1973-11-28 | 1976-02-17 | Allegheny Ludlum Industries, Inc. | Method of making corrosion resistant austenitic steel |
| CA1205659A (en) * | 1981-03-20 | 1986-06-10 | Masao Yamamoto | Corrosion-resistant non-magnetic steel and retaining ring for a generator made of it |
| AT381658B (en) * | 1985-06-25 | 1986-11-10 | Ver Edelstahlwerke Ag | METHOD FOR PRODUCING AMAGNETIC DRILL STRING PARTS |
| JPH089113B2 (en) * | 1987-07-16 | 1996-01-31 | 三菱マテリアル株式会社 | Fe-based overlay alloy with excellent corrosion and wear resistance |
| US4935027A (en) | 1989-08-21 | 1990-06-19 | Inbae Yoon | Surgical suture instrument with remotely controllable suture material advancement |
| FR2672904B1 (en) * | 1991-02-14 | 1993-05-07 | Aubert & Duval Acieries | NON-MAGNETIC STAINLESS STEEL BASED ON MANGANESE-CHROME RESISTANT TO CORROSION UNDER STRESS, METHOD OF MANUFACTURING A LONG-LENGTH NON-MAGNETIC STEEL BAR. |
| DE19758613C2 (en) | 1997-04-22 | 2000-12-07 | Krupp Vdm Gmbh | High-strength and corrosion-resistant iron-manganese-chrome alloy |
| AT407882B (en) | 1999-07-15 | 2001-07-25 | Schoeller Bleckmann Oilfield T | METHOD FOR PRODUCING A PARAMAGNETIC, CORROSION-RESISTANT MATERIAL AND THE LIKE MATERIALS WITH A HIGH STRETCH LIMIT, STRENGTH AND TENSITY |
-
1999
- 1999-07-15 AT AT0123299A patent/AT407882B/en not_active IP Right Cessation
-
2000
- 2000-06-29 AT AT00890207T patent/ATE229575T1/en active
- 2000-06-29 DE DE50000903T patent/DE50000903D1/en not_active Expired - Lifetime
- 2000-06-29 ES ES00890207T patent/ES2187434T3/en not_active Expired - Lifetime
- 2000-06-29 EP EP00890207A patent/EP1069202B1/en not_active Expired - Lifetime
- 2000-07-14 US US09/617,541 patent/US6454879B1/en not_active Expired - Lifetime
- 2000-07-14 CA CA002313975A patent/CA2313975C/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907551A (en) * | 1973-04-30 | 1975-09-23 | Allegheny Ludlum Ind Inc | Corrosion resistant austenitic steel |
| US3847599A (en) * | 1973-10-04 | 1974-11-12 | Allegheny Ludlum Ind Inc | Corrosion resistant austenitic steel |
| US4217136A (en) * | 1974-05-01 | 1980-08-12 | Allegheny Ludlum Steel Corporation | Corrosion resistant austenitic stainless steel |
| DE3143096A1 (en) * | 1980-11-05 | 1982-05-19 | General Electric Co., Schenectady, N.Y. | Iron-based alloy, process for producing it, and articles manufactured with it |
| EP0432434A1 (en) * | 1989-12-07 | 1991-06-19 | Vereinigte Schmiedewerke Gmbh | Process for manufacturing joining structural parts from a fully austenitic Cr-Mn steel. |
| US5094812A (en) * | 1990-04-12 | 1992-03-10 | Carpenter Technology Corporation | Austenitic, non-magnetic, stainless steel alloy |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 013, no. 249 (C - 605) 9 June 1989 (1989-06-09) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6454879B1 (en) | 1999-07-15 | 2002-09-24 | Schoeller-Bleckman Oilfield Technology Gmbh & Co. Kg | Process for producing a paramagnetic, corrosion-resistant material and like materials with high yield strength, strength, and ductility |
| EP2924131A1 (en) * | 2014-03-28 | 2015-09-30 | Outokumpu Oyj | Austenitic stainless steel |
| WO2015144896A3 (en) * | 2014-03-28 | 2016-03-17 | Outokumpu Oyj | Austenitic stainless steel |
| WO2020127789A1 (en) | 2018-12-20 | 2020-06-25 | Voestalpine Böhler Edelstahl Gmbh & Co Kg | Superaustenitic material |
| DE102018133255A1 (en) | 2018-12-20 | 2020-06-25 | Voestalpine Böhler Edelstahl Gmbh & Co Kg | Super austenitic material |
| WO2020127788A1 (en) | 2018-12-20 | 2020-06-25 | Voestalpine Böhler Edelstahl Gmbh Co. | Superaustenitic material |
| DE102018133251A1 (en) | 2018-12-20 | 2020-06-25 | Schoeller-Bleckmann Oilfield Technology Gmbh | Drill string component with high corrosion resistance and process for their manufacture |
| WO2020127786A1 (en) | 2018-12-20 | 2020-06-25 | Voestalpine Böhler Edelstahl Gmbh Co. | Drill string component with high corosion resistance, and method for the production of same |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1069202B1 (en) | 2002-12-11 |
| ATA123299A (en) | 2000-11-15 |
| DE50000903D1 (en) | 2003-01-23 |
| CA2313975C (en) | 2005-06-28 |
| ES2187434T3 (en) | 2003-06-16 |
| ATE229575T1 (en) | 2002-12-15 |
| US6454879B1 (en) | 2002-09-24 |
| CA2313975A1 (en) | 2001-01-15 |
| AT407882B (en) | 2001-07-25 |
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