EP2470681B1 - Acier inoxydable martensique - Google Patents

Acier inoxydable martensique Download PDF

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Publication number
EP2470681B1
EP2470681B1 EP10751807.8A EP10751807A EP2470681B1 EP 2470681 B1 EP2470681 B1 EP 2470681B1 EP 10751807 A EP10751807 A EP 10751807A EP 2470681 B1 EP2470681 B1 EP 2470681B1
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Prior art keywords
chromium steel
steel according
chromium
steel
tungsten
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German (de)
English (en)
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EP2470681A1 (fr
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Gisbert Kloss-Ulitzka
Oskar Pacher
Günter Schnabel
Vera Zeitz
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Zapp Precision Metals GmbH
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Stahlwerk Ergste Westig GmbH
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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
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten

Definitions

  • the invention relates to a stainless martensitic chromium steel and its use.
  • Such steels are known in large numbers and are suitable depending on their composition for a very different range of uses.
  • German patent specification describes 100 27 049 B4 a martensitic chromium steel with 0.4 to 0.75% carbon, up to 0.7% silicon, up to 0.2% nickel, 0.4 to 1.6% manganese, 0.02 to 0.15% sulfur, 12 to 19% chromium, 0.5 to 1.5% molybdenum, up to 1.5% tungsten, up to 0.1% nitrogen and 0.05 to 0.3% vanadium, titanium and niobium singly or side by side and up to 0.008% boron.
  • This steel has good processability, corrosion resistance and low plastic deformability and high wear and abrasion resistance; it is therefore suitable without a galvanic coating as a material for industrial needles and in particular allows a high sewing speed.
  • the material is not very suitable for use, the characteristic feature of which is a sliding contact metal / metal in the presence of a lubricant film.
  • Crucial here is especially in the case of systems for conveying or compressing fuels or in piston rings and wiper seals and dosing or valve needles for chemical or pharmaceutical mixtures, the stability and the adhesion of the wear-reducing surface layer.
  • stabilization is not possible in various systems, such as with new methanol and ethanol containing fuels.
  • the invention is therefore based on the problem of finding a stainless martensitic chromium steel, which has better wettability due to its chemical affinity and strong adhesion forces and forms a stable lubricant film, which is much more difficult to disturb or displace than conventional steels of this type and consequently causes less wear.
  • the solution to this problem consists in a martensitic chromium steel with 0.40 up to 0.80% carbon 0.20 up to 1.50% silicon 0.15 up to 1.00% nickel 0.30 up to 1.00% manganese 0,015 up to 0.035% sulfur 16 up to 18% Chrome, 1.25 up to 1.50% molybdenum up to 0.8% tungsten 0.04 up to 0.08% nitrogen 0.15 up to 0.20% vanadium, up to 0.05% titanium up to 0.05% niobium 0.001 up to 0.03% aluminum 0.02 up to 0.5% copper up to 0.5% cobalt up to 0.004% Boron, Remaining iron, including impurities caused by melting.
  • the steel contains each individually or side by side 0.55 up to 0.75% Carbon, up to 0.65% Silicon, up to 0.8% manganese at least 0.001% Tungsten.
  • the carbon is austenite and therefore stabilizes the austenitic crystal lattice.
  • carbon together with the carbide formers, also contributes to carbide precipitations, which increase the hardness and abrasion resistance of the steel.
  • carbide precipitations which increase the hardness and abrasion resistance of the steel.
  • the steel therefore contains 0.40 to 0.80%, preferably 0.55 to 0.75% carbon.
  • Silicon serves as a deoxidizer. However, higher contents can lead to the formation of intermetallic phases. On the other hand, silicon is also a ferrite former. The steel therefore contains 0.2 to 1.5% silicon, preferably up to 0.65% silicon.
  • Nickel belongs to the austenite blidners, but the austenite part in the microstructure carries the risk of a deterioration of the wear properties. On the other hand, nickel is also an advantage as part of the crystal lattice with its influence on the c / a ratio of the martensite. The steel therefore contains 0.15 to 1% nickel.
  • Manganese stabilizes the austenite and advantageously shifts the martensite formation to lower temperatures.
  • the maximum level of manganese is therefore 1%, but a minimum content of 0.30% should not be undercut, because manganese simultaneously alters the c / a ratio of the newly formed martensite and advantageously influences the precipitation behavior of the fine precipitates in the austenitic region.
  • the sulfur content is limited to a maximum of 0.035%, since at higher sulfur levels, troublesome sulfidic precipitates may occur.
  • Chromium is required to ensure the corrosion resistance of the steel in combination with its molybdenum content of 1.25 to 1.50%, in particular adequate resistance to pitting corrosion.
  • the chromium content is therefore at least 16%.
  • its content is limited to 18%.
  • the steel contains from 0.001 to 0.8% tungsten, preferably at least 0.001% tungsten, which together with the iron and molybdenum forms mixed carbides, which contribute significantly to the hot strength of the steel and lead to secondary carbide secondary precipitation during tempering.
  • the nitrogen together with the carbon forms carbonitrides, but also worsens the wettability of the steel to hydrocarbon lubricants; the upper content limit for nitrogen is therefore 0.08%.
  • the steel contains vanadium, niobium and titanium as carbide formers with the advantage that they form nucleation nuclei for the formation of chromium carbides even at very high temperatures in view of their high affinity for carbon.
  • the vanadium content is therefore 0.15 to 0.20% at titanium and niobium contents of up to 0.05%.
  • the steel also contains 0.001 to 0.03% aluminum as a deoxidizer, but not more, because higher aluminum contents have an embrittling effect.
  • the maximum copper content is 0.5% and, especially during tempering, leads to fine-grained secondary precipitations, which together with other precipitates improve the wettability of the steel for oils or hydrocarbons.
  • cobalt promotes the formation of ⁇ -carbides and other fine precipitates; it improves the hot strength of the steel in this way. For cost reasons, however, a cobalt content of 0.5% should not be exceeded.
  • the cooling rate should not exceed 50 ° C / sec (heat treatment A), so as not to affect the carbide formation and to prevent part of the reactants from remaining metastable at interstitial sites when the carbides are formed.
  • martensite spontaneously forms below the MS temperature from the cubic body-centered crystal lattice, with the result that the previously formed carbides are incorporated in the martensite, but the stress state of the matrix is lower, the more finely distributed the carbides are. This condition greatly enhances the lubricant or oil wetting of the surface of the steel.
  • the martensite from the austenite transformation has a tetragonal distorted crystal lattice with a ratio of the crystal axes a / c over 1.
  • the martensite formed during the conversion can be influenced by a heat treatment in the temperature range below 550 ° C. following martensite formation in such a way that the martensite Crystal axis ratio s / c reduced, which has an extremely beneficial effect on the material properties.
  • the nucleation is less favorable, so that the chromium carbide can be subject to crystallization inhibition and crystallized later. Associated with this is a coarser grained chromium carbide with an unfavorable distribution in the matrix.
  • coarse MC carbides of niobium, titanium and vanadium may be formed instead of fine primary carbides. Thus, the effect of the aforementioned elements is lost as carbide crystallization nuclei for the chromium carbides.
  • the heat treatment B consists in a starter annealing at 100 to 550 ° C, preferably at least 200 ° C instead and leads to the formation of fine precipitates in the stabilized in the previous heat treatment A in the temperature range of 1100 to 900 ° C martensite.
  • Table I below shows the analyzes of five conventional comparative steels V1 to V5 and three steels E1 to E3 which fall under the invention.
  • Table I shows the analyzes of five conventional comparative steels V1 to V5 and three steels E1 to E3 which fall under the invention.
  • Table I shows the analyzes of five conventional comparative steels V1 to V5 and three steels E1 to E3 which fall under the invention.
  • Table I shows the analyzes of five conventional comparative steels V1 to V5 and three steels E1 to E3 which fall under the invention.
  • Table I shows the analyzes of five conventional comparative steels V1 to V5 and three steels E1 to E3 which fall under the invention.
  • Table I shows the analyzes of five conventional comparative steels V1 to V5 and three steels E1 to E3 which fall under the invention.
  • Table I shows the analyzes of five conventional comparative steels V1 to V5 and three steels E1 to E3 which fall under the invention.
  • Table I shows the analyzes of five
  • Table II below shows the cumulative values for K1 to K3 resulting from the analyzes. ⁇ b> Table II ⁇ / b> K1 K2 K3 0.12 1.35 0.18 0.10 0.93 0.18 0.18 6.96 1.46 0.13 3.80 0.36 0.36 8.53 0.25 0.19 0.32 0.59 0.17 0.17 0.82 0.19 0.43 1.35
  • Austenitizing annealing indicated by A in Table III took place at 1020 ° C or 1050 ° C, followed by rapid cooling at a cooling rate of at least 50 ° C / sec to 800 ° C followed by cooling within 5 min. to 300 ° C and a slow cooling to room temperature.
  • the samples were finally heated according to the test series B to a temperature of 100 to 530 ° C and cooled at a rate of 100 ° C / h to room temperature.
  • the samples were then ground and polished, cleaned in an aqueous ultrasonic bath at 50 ° C, with hot distilled water under the action of ultrasound for another 20 min. freed of detergent residues and then dried.
  • 10 ⁇ l of paraffin oil were then applied to each sample by means of microdosing, and the oil droplets then forming were measured with respect to their width B, as shown schematically in FIG Fig. 1 results.
  • the measurement results found are recorded together with the respective austenitizing temperature in the following Table III. ⁇ b> Table III ⁇ / b> Verse no. Leg.
  • the abrasion and wear resistance was determined by means of a modified "pin on disk” test *, whereby the cylindrical samples were first ground flat, then cleaned, clamped in a holder and then correspondingly Fig. 2 Under a rotating steel shaft with an eccentric carbide ball under load and spring preload dynamically loaded. During the experiment, the contact zone between the sliding hard metal ball and the sample surface was steadily lubricated by the dripping of lubricating oil. At the end of the test period, the average width R of the sliding or wear track was then measured under a microscope at four points offset by ninety degrees from each other, and from these four measured values in each case the mean value R (see Table IV). Fig. 3 ) educated. In this case, a wide wear track or a large R value indicates that the steel ball has penetrated deeper and accordingly with greater width into the samples and that the sample material accordingly has a lower seal strength than those samples with a small wear track width R.
  • the result of a salt spray test can serve as an indicator of the size and distribution of the chromium carbide precipitates.
  • the samples were therefore subjected to 120 hours of corrosion testing as part of a modified salt spray test with a 3% NaCl solution and 5% alcohol.
  • test results are listed in column 7 of Table III .
  • the results of the salt spray test are an indicator of the size and distribution of chromium carbide precipitates.
  • the test results show that the wetting behavior of the inventive martensitic chromium steels for lubricants is significantly better than that of the comparative steels.
  • the good wettability results in less adhesive wear in the presence of lubrication.
  • Not only the chemical composition of the steel is of crucial importance.
  • a significant influence on the wettability is also exerted by a heat treatment of the samples. This is shown by the larger C values and the smaller R values of the samples according to the invention of experiments 9 to 17.
  • the factors K1 and K3 also show that the favorable test results are based on a more favorable precipitation of the carbides and other phases as well as the basic structure.

Claims (13)

  1. Acier inoxydable martensitique comprenant : de 0,4 à 0,8 % de carbone, de 0,2 à 1,5 % de silicium, de 0,15 à 1,0 % de nickel, de 0,3 à 1,00 % de manganèse, de 0,015 à 0,035 % de soufre, de 16 à 18 % de chrome, de 1,25 à 1,50 % de molybdène, jusqu'à 0,8 % de tungstène, de 0,04 % à 0,08 % d'azote, de 0,15 à 0,20 % de vanadium, jusqu'à 0,05 % de titane, jusqu'à 0,05 % de niobium, de 0,001 à 0,03 % d'aluminium, de 0,02 à 0,5 % de cuivre, jusqu'à 0,5 % de cobalt, jusqu'à 0,040 % de bore, le reste étant du fer II avec des impuretés consécutives à la production d'acier.
  2. Acier selon la revendication 1, qui comprend à l'état élémentaire ou combiné de 0,55 à 0,75 % de carbone, jusqu'à 0,65 % de silicium, jusqu'à 0,8 % de manganèse, au moins 0,001 % de tungstène.
  3. Acier selon la revendication 1 ou 2, comprenant une teneur totale en chrome, molybdène et tungstène de % Cr + 3 % Mo + % W = de 19 , 7 à 23 , 3 % .
    Figure imgb0014
  4. Acier selon l'une des revendications 1 à 3, qui respecte le réglage K ⁢ 1 = % Nb + % Ti + % V = d ⁢ e 0 , 15 à 0 , 25 % .
    Figure imgb0015
  5. Acier selon l'une des revendications 1 à 4, caractérisé en ce qu'il respecte le réglage K ⁢ 2 = 100 x % N - 0 , 03 % x % ⁢ N / % C = de 0 , 053 à 0 , 730 % .
    Figure imgb0016
  6. Acier selon l'une des revendications 1 à 5, caractérisé en ce qu'il respecte le réglage K ⁢ 3 = % Ni + % Co / % Mn = de 0 , 40 à 3 , 33 % .
    Figure imgb0017
  7. Acier selon l'une des revendications 1 à 6, caractérisé en ce qu'il subit une calcination en passant de 1 020 à 1 050°C pour passer à la phase austénitique, puis est rapidement refroidi selon une vitesse de refroidissement d'au moins 50 °C/s jusqu'à atteindre une température 800 °C, puis est refroidi en cinq minutes jusqu'à atteindre une température 300 °C à l'aide flux d'air à la température ambiante.
  8. Acier selon la revendication 7, qui est à nouveau chauffé de 100 à 530 °C puis est refroidi lentement jusqu'à atteindre la température ambiante selon une vitesse de refroidissement de 100 °C/h.
  9. Utilisation d'un acier selon l'une des revendications 1 à 8, en tant que matière première résistant aux piqûres de corrosion.
  10. Utilisation d'un acier selon l'une des revendications 1 à 8, en tant que matière première résistant à l'usure par frottement.
  11. Utilisation selon la revendication 9 ou 10 avec un film intermédiaire lubrifiant.
  12. Utilisation selon la revendication 11 dans un contact à frottement métal/métal avec une interface intermédiaire lubrifiante.
  13. Utilisation d'un acier selon l'une des revendications 1 à 7 en tant matière première pour un fabricant de tiges de soupape, d'aiguilles de commande et de dosage, de
    douilles de guidage, de composants fonctionnels de systèmes d'injection de carburant, de segments de piston pour organes plongeurs et moteurs ainsi que de bagues d'étanchéité et de segments racleurs pour compresseurs.
EP10751807.8A 2009-08-24 2010-08-18 Acier inoxydable martensique Active EP2470681B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL10751807T PL2470681T3 (pl) 2009-08-24 2010-08-18 Nierdzewna martenzytyczna stal chromowa

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009038382A DE102009038382A1 (de) 2009-08-24 2009-08-24 Rostfreier martensitischer Chromstahl
PCT/EP2010/005067 WO2011023326A1 (fr) 2009-08-24 2010-08-18 Acier chromé martensitique inoxydable

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EP2470681B1 true EP2470681B1 (fr) 2013-11-20

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EP (1) EP2470681B1 (fr)
DE (1) DE102009038382A1 (fr)
ES (1) ES2446716T3 (fr)
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WO (1) WO2011023326A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011102293A1 (de) 2011-02-24 2012-08-30 Stahlwerk Ergste Westig Gmbh Verwendung eines Chromstahls mit martensitischem Gefüge und karbidischen Einschlüssen
DE102017003965B4 (de) * 2017-04-25 2019-12-12 Zapp Precision Metals Gmbh Martensitischer Chromstahl, Stahlfolie, perforierte und/oder gelochte Komponente aus einer Stahlfolie, Verfahren zum Herstellen einer Stahlfolie
CN115109891B (zh) * 2022-07-14 2022-12-20 中北大学 一种高碳高铬含氮马氏体不锈钢及其碳化物细化方法

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Publication number Priority date Publication date Assignee Title
SE404029B (sv) * 1968-05-31 1978-09-18 Uddeholms Ab Forfarande for framstellning av emnen for tunna eggverktyg av herdat stal
US3990892A (en) * 1972-03-28 1976-11-09 Kabushiki Kaisha Fujikoshi Wear resistant and heat resistant alloy steels
AT401387B (de) * 1994-06-29 1996-08-26 Boehler Ybbstalwerke Korrosionsbeständige legierung und verfahren zur herstellung korrosionsbeständiger schneidwaren
DE19808276C2 (de) * 1998-02-27 2003-12-24 Stahlwerk Ergste Westig Gmbh Stahllegierung für Gleitelemente
JP2000337389A (ja) * 1999-03-19 2000-12-05 Nsk Ltd 転がり軸受
DE10027049B4 (de) 2000-01-17 2004-09-16 Stahlwerk Ergste Westig Gmbh Verwendung einer Chrom-Stahllegierung
DE102004051629B4 (de) * 2004-10-23 2006-08-24 Stahlwerk Ergste Westig Gmbh Rostfreier martensitischer Chromstahl
JP2008291307A (ja) * 2007-05-24 2008-12-04 Daido Steel Co Ltd 金型の製造方法、金型用鋼材の製造方法、及び、金型用鋼材を用いた金型の製造方法
DE102007025758A1 (de) * 2007-06-01 2008-12-04 Mahle International Gmbh Dichtring

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PL2470681T3 (pl) 2014-05-30
EP2470681A1 (fr) 2012-07-04
WO2011023326A1 (fr) 2011-03-03
DE102009038382A1 (de) 2011-03-03
ES2446716T3 (es) 2014-03-10
DE102009038382A8 (de) 2011-06-01

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