EP1213363B1 - Verfahren zur Erzeugung verschleissbeständiger Randschichten an Bauteilen aus ausscheidungshärtbaren metallischem Werkstoff - Google Patents
Verfahren zur Erzeugung verschleissbeständiger Randschichten an Bauteilen aus ausscheidungshärtbaren metallischem Werkstoff Download PDFInfo
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- EP1213363B1 EP1213363B1 EP00126449A EP00126449A EP1213363B1 EP 1213363 B1 EP1213363 B1 EP 1213363B1 EP 00126449 A EP00126449 A EP 00126449A EP 00126449 A EP00126449 A EP 00126449A EP 1213363 B1 EP1213363 B1 EP 1213363B1
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- spa
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Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/06—Surface hardening
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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
- C21D6/02—Hardening by precipitation
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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
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/34—Methods of heating
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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
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
- C21D7/04—Modifying the physical properties of iron or steel by deformation by cold working of the surface
- C21D7/06—Modifying the physical properties of iron or steel by deformation by cold working of the surface by shot-peening or the like
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S148/00—Metal treatment
- Y10S148/902—Metal treatment having portions of differing metallurgical properties or characteristics
Definitions
- the invention relates to the surface hardening of machine components.
- the invention for increasing the wear resistance of components made of stainless, precipitation-hardenable martensitic steels, such. Turbine blades, pump shafts, heavy-duty bolts from the aerospace industry, parts from the shipbuilding industry or special ones Tools usable.
- Another field of application are wear-stressed components high-strength, precipitation-hardenable metallic materials, which in the presence of high Toughness requirements can not be used in the fully cured state.
- Edge zones of wear-resistant but also fatigue-stressed components are subject during their use significantly different loads than the component core. This fact is known accounted for in the marginal zone by thermal, physical, chemical, mechanical, thermochemical or thermomechanical processes a harder, wear-resistant or fatigue-resistant structure is produced as in the core, its structure so is adjusted that it primarily the present strength and toughness requirements enough.
- Blades of low pressure stages in steam turbines are subject during their use extremely high quasi-static (centrifugal force, blade twisting), cyclic (periodic Vapor pressure, blade vibrations) and tribological (drop impact) Stresses.
- quasi-static centrifugal force, blade twisting
- cyclic periodic Vapor pressure, blade vibrations
- tribological drop impact
- Martensithärtende 13% chromium steels are able to meet these complex requirements.
- This will be the blade material in the tempered, highly tempered condition (fulfillment of the requirements of Toughness, stress corrosion cracking resistance, vibration crack corrosion resistance, sufficient static and cyclic load capacity; Hardness about 250-350 HV) and the Environment of the leading edge z.
- the heat treatment usually comprises at least one solution annealing at 1030-1080 ° C. (annealing time about 1 h) and the actual aging treatment in the temperature range between 480 ° C. and 620 ° C. (time 1-4 h).
- the achievable mechanical properties hardness, yield value R p0.2 and tensile strength R m reach their maximum at the lower limit of the conventionally possible tempering temperature of 480 ° C and decrease sharply with increasing aging temperature (see also drawing 1). So falls z.
- the hardness of 425 HV to 285 HV the hardness of 1170 to 750 MPa and the tensile strength of 1310 to 930 MPa.
- the aging temperature must be set so high that the 0.2% flow limit and the tensile strength fall below values of about 1040 and 1000 MPa, respectively. This means that the high hardness-supplying lower range of possible tempering temperatures can not be used (see drawing 1).
- the shortcoming of this conventional heat treatment process is therefore that the resistance to drop impact wear is too low.
- the cause lies in that the hardness at 340 - 370 HV near the surface is too small.
- a treatment method comprising only the surface layer for the separate microstructure adjustment in the edge layer and the component core of precipitation hardenable steels by a Surface layer heat treatment is given in SU-A-1447878.
- the steel sheet is a conventional treatment cycle consisting of hardening, cold forming and Precipitation hardening subjected.
- the structure consists mainly of precipitation-hardened martensite and minor proportions of austenite.
- by a very short-term laser edge-layer annealing allows partial re-conversion of the martensite soft and ductile austenite erzi via. This soft, mostly austenitic surface layer has a reduced risk of cracking in the spring load.
- the object of the invention is to provide a new and effective heat treatment process, which allows components of precipitation-hardenable materials with much more wear-resistant To provide edge layers without a deterioration of the remaining mechanical Use properties of the component to accept.
- the invention has for its object to provide a heat treatment process, it regardless of structure and the mechanical properties of the component interior and without influence, higher surface hardening up to one of the tribological load to get dependent, sufficiently large depth with sufficient toughness, that too mold complicate parts can be used and in which the aging temperature Hardening possibilities of conventionalzeitanssglimmed state better uses.
- the above object is achieved with a method for producing wear-resistant edge layers of precipitation-hardenable materials such as in Claims 1 to 14 shown solved.
- the method is based on a function optimization by a separate adjustment of the structure in the component interior and the edge layer.
- a thorough solution annealing and precipitation heat treatment are carried out in such a way that the structural state in the component interior and the resulting core strength and toughness best correspond to the later mechanical and, in particular, cyclic loading conditions.
- the surface layer solution annealing according to the invention then takes place in a strongly inhomogeneous temperature field, followed by an inventively modified aging treatment of the entire component in a homogeneous or nearly homogeneous temperature field.
- the requirements for depth, width, position and course of the wear protection zone resulting from the analysis of the tribological and / or cyclic load distribution correspond to the desired geometry of the solution annealing zone.
- the solution annealing zone is produced by a boundary layer heating method with sufficient power density.
- the depth t H of the target solution annealing zone is set by the local absorbed energy density and the local energy exposure time. The energy density and the duration of energy action also determine the resulting heating rate and the temperature gradient
- the cooling rate according to the invention prevents grain coarsening during cooling and uncontrolled
- Precipitation hardening The specification of an unusually high value for the maximum peak temperature T max s sa makes use of the knowledge that the hardness of the surface layer, as the primary, the wear resistance of the relevant types of wear determining characteristic increases or only slightly decreases with the peak temperature. As a result, a dissolution state of the precipitates can be achieved even at greater depths of the short-time solution annealing zone, which guarantees a greater hardening depth or a shallower hardness drop. Particularly high resistance to abrasion can be achieved if, as stated in claim 3, the parameters of the final aging heat treatment are selected so that the peak hardness of the precipitation hardness is achieved.
- a specific embodiment of the invention for the class of martensitic precipitation hardenable steels provides claim 4. By selecting the values according to the invention for the peak temperature T max s sa, the temperature T spa and the time ⁇ t spa a significantly higher surface layer hardness is achieved.
- An advantage of the method embodiment according to claim 10 is that thus the residual stress state the precipitation hardened surface layer can be improved and a larger one Number of germs for the formation of fine precipitates is present.
- the execution of the mechanical deformation as a shot peening treatment, as in claim 13 can be particularly advantageous for the optimization of the edge layer properties of very complicated shaped or very locally treated components, such.
- the heat treatment according to the invention can be applied to precipitation-hardenable steels various applications (stainless and acid-resistant steels, special steels, maraging steels) deploy.
- Such steels are z.
- a drop impact loaded end runner made of steel N700 should be provided with a wear-resistant leading edge.
- the expected erosion zone width is 11 mm.
- the erosion intensity is greatest at the leading edge and decreases rapidly within the erosion zone width in the direction of the blade leading edge.
- the maximum hardening depth t H of the edge layer in the vicinity of the leading edge 1.3 mm is desired, wherein the hardening depth can decrease in accordance with the decrease in erosion intensity with increasing distance to the leading edge.
- the material N700 has the following chemical composition: carbon ⁇ 0.04%; Silicon: 0.25%; Manganese: 0.40%; Chromium: 15.40%; Nickel: 4.40%; Copper: 3.30%; Niobium: 0.30% (in each case in percent by weight).
- the following mechanical properties are set by a conventional heat treatment: 0.2% flow limit R p0.2 : 930 - 1000 MPa, tensile strength R m ⁇ 1040 MPa (see dashed lines in Fig. 1).
- the cooling takes place in air.
- the resulting microhardness is 353 HV 0.05 and is the same in the component core as in the surface layer. This level of hardness is not sufficient for the required drop impact wear resistance, but has sufficient toughness for very high cyclic loads.
- the heat treatment according to the invention for producing wear-resistant surface layers is done as follows:
- T csa2 and holding times ⁇ t csa2 of the conventional reference solution annealing treatment would have been T csa2 ⁇ 1050 ° C and ⁇ t csa2 ⁇ 1 h.
- T csa 2 + 300 K T max ssa .
- the heating takes place in a conventional heat treatment furnace with nitrogen as protective gas.
- Fig. 2 shows the achieved surface hardness HV 0.05 and the hardness-depth curve.
- the surface hardness reaches 477 HV 0.05 . That is a hardness increase of 124 HV 0.05 .
- the hardening depth up to the ultimate hardness 353 HV is 1.5 mm.
- the achieved compressive residual stress state in the hardened zone reduces the stress and vibration cracking susceptibility of the cured structure.
- the dependence of the microhardness HV 0.05 of the edge layer according to the invention on the removal temperature is shown in FIG. 1 in a comparative manner. It can be seen that the microhardness values in the aging temperature range 460 ° C. ⁇ T spa ⁇ 510 ° C. are significantly higher than those of the conventional heat treatment.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Articles (AREA)
- Coating By Spraying Or Casting (AREA)
- Heat Treatments In General, Especially Conveying And Cooling (AREA)
Description
- Laserstrahlleistung am Auftreffort der Laserstrahlung: 2,75 kW;
- absorbierte Laserstrahlleistung: 2,2 kW;
- Vorschubgeschwindigkeit: 1000 mm/min ;
- Strahlfleckdurchmesser: 11,9 mm;
- resultierende mittlere Laserleistungsdichte: 2,0 kW/cm2.
- Aufheizgeschwindigkeit
- Temperaturgradient beim Aufheizen (in größerem Abstand zur Schaufelspitze)
- Spitzentemperatur Tmax s sa ≈ 1350 °C;
- Haltezeit des Kurzzeit-Lösungsglühens Δts sa ≈ 0,7 s;
- Abkühlgeschwindigkeit
- Auslagerungstemperatur Tspa ≈ 465 °C,
- Auslagerungszeit Δtspa ≈ 4 h.
Somit gilt: Tspa + 15 K = Tcpa2; Δtspa = 4 * Δtcpa2.
Die Erwärmung erfolgt durchgreifend in einem konventionellen Wärmebehandlungsofen mit Stickstoff als Schutzgas.
Die Abhängigkeit der Mikrohärte HV0,05 der erfindungsgemäß hergestellten Randschicht von derAuslagerungstemperatur ist in Fig. 1 vergleichend dargestellt. Es ist zu erkennen, dass die Mikrohärtewerte im Auslagerungstemperaturbereich 460 °C ≤ Tspa ≤ 510 °C deutlich über denen der konventionellen Wärmebehandlung liegen.
Claims (14)
- Verfahren zur Erzeugung von verschleißbeständigen Randschichten an Bauteilen aus ausscheidungshärtbaren metallischen Werkstoffen durch ein Kurzzeitlösungsglühen und eine nachfolgende Auslagerungswärmebehandlung, wobei das Bauteila) durchgreifend bei einer Temperatur Tcsa1 lösungsgeglüht wird,b) bei einer Temperatur Tcpa1 durchgreifend einer Auslagerungswärmebehandlung unterworfen wird, wobei die Temperatur Tcpa1 und die Haltezeit Δ tcpa1 der Auslagerungswärmebehandlung so eingestellt werden, dass ein überalterter Zustand entsteht, der hinsichtlich seiner mechanischen Kennwerte 0,2% Fließgrenze, Zugfestigkeit, Zähigkeit und Härte auf die mechanische Bauteilbelastung angepasst ist,c) anschließend einer erneuten, nur die Randschicht des Bauteils erfassenden Kurzzeitlösungsglühung bei einer Temperatur Tssa > Tcsa1 und einer Haltezeit des Kurzzeit-Lösungsglühens Δttssa < 12 s unterworfen wird undd) anschließend einer weiteren, sowohl das Bauteilinnere als auch die Randschicht gleichermaßen umfassende Auslagerungswärmebehandlung bei einer Temperatur Tspa < Tcpa1 ausgesetzt wird.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dassa) die Randschicht des Bauteiles bis zu einer Tiefe t H, die der angestrebten Einhärtungstiefe entspricht, durch eine kurzzeitige und von der Bauteiloberfläche ausgehende Energieeinwirkung lösungsgeglüht wird,b) die kurzzeitige und von der Bauteiloberfläche ausgehende Energieeinwirkung durch ein hochenergetisches Randschichterwärmungsverfahren realisiert wird,e) für die Spitzentemperatur Tmax ssa der Kurzzeit-Lösungsglühbehandlung
Tcsa2 + 50 K ≤ T max ssa ≤ Tcsa2 +400 K gilt, wobei Tcsa2 die konventionelle Lösungsglühtemperatur des entsprechenden Werkstoffes ist,f) die Haltezeit des Kurzzeit-Lösungsglühens Δ t ssa in dem Temperaturbereich, in dem eine merkliche Auflösung der Ausscheidungen stattfindet, im Bereich 10 -1 s ≤ Δ t ssa ≤ 12 s liegt,h) die Auslagerungswärmebehandlung mit einer im Vergleich zur Kurzzeit-Lösungsglühbehandlung längeren Haltezeit Δ tspa, Δ tspa > Δ tssh und einem deutlich geringeren Temperaturgradienten durchgeführt wird,i) für die Temperatur Tspa der Auslagerungswärmebehandlung Tspa ≤ Tcpa2 ≤ Tspa + 80 K gilt, wobei Tcpa2 die Untergrenze des konventionellen Auslagerungstemperaturbereiches darstellt,j) die Haltezeit der Auslagerungswärmebehandlung Δ tspa eineinhalb bis sechzehnmal so groß gewählt wird, wie die Haltezeit Δ t cpa2 der konventionellen Auslagerungswärmebehandlung. - Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die abschließende Auslagerungswärmebehandlung bei einer Temperatur Tspa und einer Haltezeit Δ tspa durchgeführt werden, die die gewünschte Härte ergibt.
- Verfahren nach mindestens einem der Ansprüche von 1 bis 3, dadurch gekennzeichnet, dass die Randschichtveredlung von ausscheidungshärtbaren martensitischen Stählen mit Kohlenstoffgehalten von 0,03 bis 0,08 Gew. %, Chromgehalten von 10 bis 19 Gew. %, Nickelgehalten von 3,0 bis 11,0 Gew. %, Kupfergehalten von 1,0 bis 5,0 Gew. % und Niobgehalten von 0,15 bis 0,45 Gew. % so durchgeführt wird, dassa) die Tiefe t H der lösungsgeglühten Randschicht 0,1 mm ≤ t H < 7 mm beträgt,b) für die Spitzentemperatur Tmax ssa der Kurzzeit-Lösungsglühbehandlung 1080 °C ≤ Tmax ssa ≤ 1350 °C gilt,c) die Temperatur Tspa der Auslagerungswärmebehandlung im Bereich 445 °C ≤ Tspa ≤ 500 °C gewählt wird,d) die Haltezeit der Auslagerungswärmebehandlung Δ tspa im Bereich 1 h ≤ Δ tspa ≤ 8 h eingestellt wird.
- Verfahren nach einem der Ansprüche von 1 bis 4, dadurch gekennzeichnet, dass das hochenergetische Randschichterwärmungsverfahren eine Laserstrahlerwärmung ist.
- Verfahren nach einem der Ansprüche von 1 bis 4, dadurch gekennzeichnet, dass als hochenergetisches Randschichterwärmungsverfahren eine Elektronenstrahlerwärmung gewählt wird.
- Verfahren nach einem der Ansprüche von 1 bis 4, dadurch gekennzeichnet, dass als hochenergetisches Randschichterwärmungsverfahren eine induktive Randschichterwärmung dient.
- Verfahren nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass nach der Kurzzeit-Lösungsglühbehandlung und vor der Auslagerungswärmebehandlung eine mechanische Verformung der Randschicht vorgenommen wird.
- Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass das Bauteil ein Halbzeug ist und das Halbzeug seine endgültige Form durch eine Umformung erhält.
- Verfahren nach Anspruch 10 und 11, dadurch gekennzeichnet, dass die Kurzzeit-Lösungsglühbehandlung, die Umformung und die Auslagerungswärmebehandlung im Durchlaufverfahren durchgeführt werden.
- Verfahren nach mindestens einem der Ansprüche von 10 bis 12, dadurch gekennzeichnet, dass die mechanische Verformung der Randschicht durch eine Kugelstrahlbehandlung vorgenommen wird.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10030433A DE10030433C2 (de) | 1999-06-23 | 2000-06-21 | Verfahren zur Erzeugung verschleißbeständiger Randschichten an ausscheidungshärtbaren Werkstoffen |
EP00126449A EP1213363B1 (de) | 1999-06-23 | 2000-12-07 | Verfahren zur Erzeugung verschleissbeständiger Randschichten an Bauteilen aus ausscheidungshärtbaren metallischem Werkstoff |
DE50010769T DE50010769D1 (de) | 1999-06-23 | 2000-12-07 | Verfahren zur Erzeugung verschleissbeständiger Randschichten an Bauteilen aus ausscheidungshärtbaren metallischem Werkstoff |
AT00126449T ATE299954T1 (de) | 1999-06-23 | 2000-12-07 | Verfahren zur erzeugung verschleissbeständiger randschichten an bauteilen aus ausscheidungshärtbaren metallischem werkstoff |
ES00126449T ES2249224T3 (es) | 1999-06-23 | 2000-12-07 | Procedimiento para la produccion de capas marginales resistentes al desgaste en componentes de materiales metalicos templables por precipitacion. |
US09/736,443 US6511559B2 (en) | 1999-06-23 | 2000-12-15 | Process for producing wear-resistant edge layers in precipitation-hardenable materials |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19928773 | 1999-06-23 | ||
DE10030433A DE10030433C2 (de) | 1999-06-23 | 2000-06-21 | Verfahren zur Erzeugung verschleißbeständiger Randschichten an ausscheidungshärtbaren Werkstoffen |
EP00126449A EP1213363B1 (de) | 1999-06-23 | 2000-12-07 | Verfahren zur Erzeugung verschleissbeständiger Randschichten an Bauteilen aus ausscheidungshärtbaren metallischem Werkstoff |
US09/736,443 US6511559B2 (en) | 1999-06-23 | 2000-12-15 | Process for producing wear-resistant edge layers in precipitation-hardenable materials |
Publications (2)
Publication Number | Publication Date |
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EP1213363A1 EP1213363A1 (de) | 2002-06-12 |
EP1213363B1 true EP1213363B1 (de) | 2005-07-20 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP00126449A Expired - Lifetime EP1213363B1 (de) | 1999-06-23 | 2000-12-07 | Verfahren zur Erzeugung verschleissbeständiger Randschichten an Bauteilen aus ausscheidungshärtbaren metallischem Werkstoff |
Country Status (5)
Country | Link |
---|---|
US (1) | US6511559B2 (de) |
EP (1) | EP1213363B1 (de) |
AT (1) | ATE299954T1 (de) |
DE (2) | DE10030433C2 (de) |
ES (1) | ES2249224T3 (de) |
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DE102006050799A1 (de) * | 2006-10-27 | 2008-05-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren und Vorrichtung zum Randschichthärten formkomplizierter Bauteile |
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FR2921448A1 (fr) | 2007-09-24 | 2009-03-27 | Snecma Sa | Procede de formation de reliefs pertubateurs de couche limite |
US9248579B2 (en) * | 2008-07-16 | 2016-02-02 | The Gillette Company | Razors and razor cartridges |
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DE102012018551A1 (de) * | 2012-09-20 | 2014-03-20 | Wika Alexander Wiegand Se & Co. Kg | Edelstahlrohr mit Randhärtung |
WO2015077185A1 (en) | 2013-11-25 | 2015-05-28 | Magna International Inc. | Structural component including a tempered transition zone |
US20150217414A1 (en) * | 2014-02-04 | 2015-08-06 | Caterpillar Inc. | Method of remanufacturing a component |
DE102017209881A1 (de) * | 2017-06-12 | 2018-12-13 | Audi Ag | Verfahren zur Fertigung eines gehärteten Getriebebauteils und hierfür verwendbares Umformwerkzeug mit gekühltem Gesenk |
CN108977626A (zh) * | 2018-08-22 | 2018-12-11 | 哈尔滨工程大学 | 蒸汽轮机叶片表面的激光淬火与时效处理复合强化方法 |
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US5238510A (en) * | 1990-08-10 | 1993-08-24 | Bethlehem Steel Corporation | Metal sheet and method for producing the same |
DE29706372U1 (de) * | 1997-04-10 | 1997-10-30 | Biller Rudi | Harte Edelstahlbohrschraube |
DE29914269U1 (de) * | 1999-08-19 | 1999-11-25 | Friederich Heinrich | Hochfester korrosionsbeständiger Edelstahl-Stab |
-
2000
- 2000-06-21 DE DE10030433A patent/DE10030433C2/de not_active Expired - Lifetime
- 2000-12-07 EP EP00126449A patent/EP1213363B1/de not_active Expired - Lifetime
- 2000-12-07 AT AT00126449T patent/ATE299954T1/de active
- 2000-12-07 DE DE50010769T patent/DE50010769D1/de not_active Expired - Lifetime
- 2000-12-07 ES ES00126449T patent/ES2249224T3/es not_active Expired - Lifetime
- 2000-12-15 US US09/736,443 patent/US6511559B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DE10030433C2 (de) | 2002-06-06 |
US6511559B2 (en) | 2003-01-28 |
ATE299954T1 (de) | 2005-08-15 |
ES2249224T3 (es) | 2006-04-01 |
DE50010769D1 (de) | 2005-08-25 |
EP1213363A1 (de) | 2002-06-12 |
US20020074066A1 (en) | 2002-06-20 |
DE10030433A1 (de) | 2001-05-03 |
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