US20050126661A1 - Precipitation hardenable austenitic steel - Google Patents

Precipitation hardenable austenitic steel Download PDF

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US20050126661A1
US20050126661A1 US10/496,491 US49649105A US2005126661A1 US 20050126661 A1 US20050126661 A1 US 20050126661A1 US 49649105 A US49649105 A US 49649105A US 2005126661 A1 US2005126661 A1 US 2005126661A1
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weight
product
alloy
strength
heat treatment
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Gustaf Zetterholm
Hakan Holmberg
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Sandvik Intellectual Property AB
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Assigned to SANDVIK AB reassignment SANDVIK AB ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HOLMBERG, HAKAN, ZETTERHOLM, GUSTAF
Assigned to SANDVIK INTELLECTUAL PROPERTY HB reassignment SANDVIK INTELLECTUAL PROPERTY HB ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SANDVIK AB
Publication of US20050126661A1 publication Critical patent/US20050126661A1/en
Assigned to SANDVIK INTELLECTUAL PROPERTY AKTIEBOLAG reassignment SANDVIK INTELLECTUAL PROPERTY AKTIEBOLAG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SANDVIK INTELLECTUAL PROPERTY HB
Priority to US11/487,442 priority Critical patent/US20070041863A1/en
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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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • 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
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • 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
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper

Definitions

  • the present invention relates to an austenitic stainless steel alloy, more precisely a high-strength precipitation hardenable austenitic stainless steel alloy containing a well balanced aluminium content and a high silicon content, a product which is reduced by cold working, especially drawing, without intermediate heat treatment, the strength of which increases through final heat treatment at 300° C. to 500° C. by not less than 14%, which shows a M d30 -value of between ⁇ 55 and ⁇ 100, a loss of force that is lower than 3.0% at 1400 N during 24 hours and which is very suitable for use in spring applications, such as springs of round wire and strip steel and in medical applications, such as surgical and dental instruments.
  • the cold-Worked austenitic stainless springsteels of type AISI 302 assume a dominating position. This is based on a combination of relatively good corrosion resistance and a possibility to cold-work the material to a considerable strength, which is a prerequisite for a good spring material. Based on the cold-worked state, the mechanical properties may be increased additionally by means of a simple heat treatment. Steel of the type AISI 631 is alloyed with aluminium in order to additionally enhance the increase of strength at heat treatment. During cold-working, a transformation takes place from the annealed structure's principal constituent of austenite to deformation martensite, which is harder than the phase from which it is formed.
  • These steels are higher alloyed and have a lower carbon content than steels of the type AISI 302 and AISI 631. This entails that a higher rate of reduction can be allowed in this type of steel.
  • the disadvantage of these steels is that the resulting product properties that are essential for a good spring function frequently are worse than for steels of AISI 302 and AISI 631.
  • One example of such a property is the resistance to relaxation, which describes the ability of a spring to retain spring strength over time.
  • the alloy according to U.S. Pat. No. 6,048,416 contains no precipitation-hardening element.
  • a high-strength, precipitation hardenable, austenitic stainless steel alloy which contains (in weight-%): C more than 0 to 0.07 Si 0.5-3.0 N >0-0.1 Cr 15.0-20.0 Ni 7.0-12.0 Al 0.25-1.5 Cu 0 ⁇ Cu ⁇ 4.0 Mn >0-3.0 Mo >0-2.0 Ti >0-1.0 Balance Fe and normally occurring impurities and additives.
  • FIG. 1 shows the loss of force of the springs after 24 hours of materials according to the invention compared with AISI 302 and charge no. 150725.
  • FIG. 2 shows the ultimate tensile strength of materials according to the invention compared with AISI 302* (* —with intermediate heat treatment) and charge no. 150725.
  • FIG. 3 shows the ultimate tensile strength as a logarithmic function of the cumulative reduction rate of materials according to the invention compared with charge no. 150725.
  • FIG. 4 shows schematically a segment of a possible embodiment of an expanding ring in a side view.
  • FIG. 5 shows in FIG. 5 a the ring seen from above. The ends are pressed against each other by the force F, in FIG. 5 b the ring is shown seen from the side, the ends being pressed against each other by the force F and in FIG. 5 c a part of the expanding ring is shown that constitutes a flat spring element and how this is influenced by the force F.
  • FIG. 6 shows different embodiments for strip springs.
  • Carbon (C) has a high propensity to combine with chromium which means that chromium carbides is precipitated in the crystal grain boundaries, whereby the surrounding the bulk is depleted of chromium.
  • the corrosion properties of the material deteriorate, problems also arise with embrittlement that foremost causes problem when the wire is shaped to springs. Therefore, the carbon content should be held at as low a level as possible, being more than 0.0 weight-% , but maximum 0.07 weight-% , preferably 0.05 weight-% , most preferably maximum 0.035 weight-%.
  • Silicon (Si) has a ferrite-stabilising effect, which entails that too a high silicon content produces a two-phase structure. Therefore, the silicon content should not exceed 3.0 weight-% .
  • silicon is also favourable in that it contributes to a greater increase of strength at heat treatment of the cold-worked product. Therefore, the silicon content should not be lower than 0,5 weight-% and should be in the range of 0.5 to 3.0 weight-% , preferably. between 0.5 and 2.5 weight-% , most preferably 0.5 to 1.5 weight-%.
  • Nitrogen (N) is an alloying element that together with aluminium forms non-disirable brittle slags in the form of aluminium nitrides. Further, nitrogen increases the deformation-hardening at cold-working, which is a disadvantage in the present invention. Therefore, it is of highest importance that the nitrogen content is held on as low a level as possible, maximum 0.1 weight-% , preferably 0.05 weight-%.
  • Chromium (Cr) is a very important alloying element what concerns the corrosion resistance of the material. This is due to the ability of chromium to form a passive layer of Cr 2 O 3 on the surface of the steel. In order for that passive layer to form, it is required that the chromium content exceeds approximately 12.0 weight-% , in addition, the corrosion resistance increases with added chromium content. Another advantage of chromium is that the austenitic structure of the material is stabilized against transition to martensite at cold-working. However, chromium is ferrite-stabilising, and therefore the content should not be too high. Therefore, in the alloy according to the present invention the chromium content should not be lower than 15.0 weight-% and not be higher than 20.0 weight-% , preferably be in the range of 16.0 to 19.0 weight-%.
  • Nickel (Ni) is an alloying element that in a sufficient amount guarantees that the material gets an austenitic structure at room temperature. Furthermore, the ductility is improved with an increased nickel content. However, nickel is an expensive alloying element and high contents entail a slow deformation-hardening, which in its turn entails difficulties to attain a sufficient strength. Therefore, the nickel content should be within the range of 7.0 till2.0 weight-% , preferably between 8.0 till I.0 weight-% , most preferably within the range of 9.0 to 10.0 weight-%.
  • Aluminium is a central alloying element in the present invention. Aluminium is added as a precipitation hardening element in order to increase the strength, which in turn influences the relaxation resistance. During precipitation-hardening at 350-500° C. of the cold-worked wire, precipitations in the form of ⁇ -NiAL are formed, which improves the mechanical properties unlike materials known until now. This effect is of highest importance when the wire is to be used as springs, the relaxation resistance of which has to meet very high requirements.
  • a disadvantage of aluminium is that it is ferrite-stabilizing, for what reason the aluminium content should be limited to maximum 1.5 weight-%. However, in the light of the above-mentioned, the aluminium content should be at least 0.25 weight-% and preferably be in the range of 0.41.0 weight-%.
  • Copper (Cu) is an alloying element that has two important properties. Firstly, copper is an austenite-stabilizing element and secondly copper decreases the deformation-hardening of the material and entails improved ductility. Since the material has to withstand extreme reductions without intermediate annealings, the copper content has to be as high as possible. However, with an increasing copper content, the risk of unwanted precipitations increases, which decreases the ductility of the material. Therefore, the copper content should be in the range of 0 ⁇ Cu ⁇ 4.0 weight-% , preferably between 2.0 to 3.5 weight-% , most preferably between 2.4 to 3.0 weight-%.
  • Manganese (Mn) has similar effect as nickel, both with regard to forming austenite at setting as well as stabilizing the same against transformation into martensite at cold-working. However, manganese increases the deformation-hardening, which nickel does not. This results in a faster deformation-hardening and diminishes the greatest possible reduction rate between the annealings.
  • the manganese content should be more than 0.0 weight-% , but being limited to maximum 3.0 weight-% , preferably to maximum 1.0 weight-%.
  • Molybdenum (Mo) is a ferrite-stabilizing element that has a strongly favourable effect on the corrosion resistance in chloride environments.
  • Established PRE (Pitting Resistance Equivalent) formulas allocate molybdenum a factor of ⁇ 3 in comparison with the effect of chromium.
  • a high molybdenum content stabilises the ferrite phase in the steel.
  • the molybdenum content should be more than 0.0 weight-% , but limited upwards to 2.0 weight-%.
  • Titanium (Ti) is, like aluminium, a precipitation-hardening element that is added in order to increase the strength, which in turn influences the relaxation resistance. Furthermore, titanium together with silicon gives a strong heat treatment effect already at low contents of titanium. However, titanium is strongly ferrite-stabilizing, for what reason the content should not be too high. Therefore, the titanium content should be more than 0.0 weight-% , but being limited up to 1.0 weight-% , preferably maximum 0.75 weight-%.
  • test materials were produced by melting in a high frequency furnace. Subsequently, all test ingots were fully ground before they were forged. Forging was performed on the ingot to 103 ⁇ 103 mm length in stock. The heating temperature was in the range between 1240° C. and 1260° C. The holding time at full temperature was 1 h. At the subsequent blank treatment, the blanks were fully ground and ultrasonically tested.
  • the wire rod in the dimension range of ⁇ 5.50 mm- ⁇ 5.60 mm was produced by warming the blanks to 1200° C.-1240° C., whereupon they were rolled to final dimension and then cooled by water quenching. The hot-rolled wires were then cold-worked by drawing in a conventional drawing machine.
  • M d30 /Nohara shows the temperature where at a rate of cold reduction of 30% , 50% of the austenite in the steel is transformed to transformation-martensite. A higher value for the temperature indicates, that the structure is more stable (more disposed to form martensite) and leeds to a higher rate of cold-deformation in the steel.
  • Table 4 shows the results for the test charges 1 to 7. It has surprisingly shown that a steel with the composition according to the present invention attains the best heat treatment effect at M d30 -valus of between ⁇ 55 and ⁇ 100 and the highest increase in ultimate tensile strength after solely cold working without intermediate heat treatment.
  • the steel according to the present invention is subjected to a strong cold deformation. It can be shaped to different cross-section geometries, for example, oval wire, profiles of different cross-sections, for example, rectangular, triangular or more complicated embodiments and geometries. Round wire may even be flat-rolled.
  • springs of wire made from the alloy according to invention are wound. These springs have good spring properties in the form of relaxation, i.e. the retention of spring force under a long period and are advantageously used in typical spring applications, such as, for instance, springs in locking applications, i.e. mechanical parts in the locking device, springs in aerosol containers, pens, especially ball point pens, pump springs, springs in industrial looms, springs in the vehicle industry, electronics, computers and fine mechanics.
  • springs in locking applications i.e. mechanical parts in the locking device
  • a so-called reverse winding may be accomplished.
  • the spring is preformed by being wound in a direction opposite the working direction. Then a heat treatment of the spring takes place, after which it is wound-in in the opposite direction in the spring housing.
  • the strip is formed on a tack, after which heat treatment takes place. Then the spring is wound in the opposite direction into the spring housing.
  • An expander is a bit of wire, which is corrugated and shaped to a flat spring connected in series. This spring is used, for instance, in order to regulate the pressure of the oil scraper rings against the cylinder wall in an internal combustion engine.
  • a typical expander for car motors is seen as the corrugated wire between two piston rings.
  • a possible embodiment of such a corrugated ring is shown schematically in FIG. 4 .
  • a drawback of motor-driven vehicles today is the great energy consumption that is necessary in order to give the vehicle the desired performance thereof.
  • the easiest ways to achieve a reduced energy consumption is, among other things, to diminish the internal friction of the drive and to reduce the total mass of the vehicle.
  • the piston core accounts for more than half of the friction of a motor. Therefore, it is a continuous aim to improve the material and precision of the rings, pistons and cylinder walls with the purpose of reducing tare weights and bearing pressure.
  • the expander is the spring that regulates the pressure of the oil scraper rings against the cylinder wall and thereby also oil consumption and part of the internal friction of a motor.
  • the load of the expander wire consists of the force F, as shown in FIGS. 5 a to 5 c.
  • Expression (3) shows that the wire thickness that is required for a given property depends on the design of the expander. If the allowed tension of the material is increased, a smaller bending radius can be allowed, which is of great interest since rings of smaller types can be manufactured. The possibility of being able to manufacture smaller rings becomes more and more important since the demand for small motors increases as the environmental requirements are raised.
  • Expression (4) shows that a certain elastic energy for given modulus of elasticity is a function of the specific volume, material use and allowed maximum tension. An increased maximal allowed tension increases as a rule the material-use constant, which in combination gives a major impact on the required specific volume. Thus, it is possible to diminish the material volume increased allowed tension for retained level of elastic energy.
  • the material may be formed in a relatively soft state so as to later be heat treated in the finished form, whereupon the desired spring properties are obtained by precipitation hardening.
  • This embodiment according to the present invention is used especially in applications that make great demands on the relaxation properties of the steel, since it should resist a force without being preformed.
  • Wire, manufactured from the alloy according to invention may even be used in medical applications, for instance, in the form of dental instruments as files, such as root canal files, nerve extractor and the like, as well as surgical needles.
  • Flat-rolled wire of the steel according to invention may advantageously be used for the production of dental and surgical instruments.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Heat Treatment Of Steel (AREA)
  • Materials For Medical Uses (AREA)
  • Dental Preparations (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Heat Treatment Of Articles (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)
  • Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
  • Springs (AREA)
US10/496,491 2001-12-11 2002-12-11 Precipitation hardenable austenitic steel Abandoned US20050126661A1 (en)

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SE0104192A SE526881C2 (sv) 2001-12-11 2001-12-11 Utskiljningshärdbar austenitisk legering, användning av legeringen samt framställning av en produkt av legeringen
SE0104192-0 2001-12-11
PCT/SE2002/002300 WO2003056053A1 (en) 2001-12-11 2002-12-11 Precipitation hardenable austenitic steel

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EP (1) EP1472383B1 (enrdf_load_stackoverflow)
JP (1) JP4327601B2 (enrdf_load_stackoverflow)
KR (1) KR100966068B1 (enrdf_load_stackoverflow)
AT (1) ATE360104T1 (enrdf_load_stackoverflow)
AU (2) AU2002360028A1 (enrdf_load_stackoverflow)
BR (1) BR0214816B1 (enrdf_load_stackoverflow)
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US20060266439A1 (en) * 2002-07-15 2006-11-30 Maziasz Philip J Heat and corrosion resistant cast austenitic stainless steel alloy with improved high temperature strength
US20080199345A1 (en) * 2005-05-23 2008-08-21 Piotr R. Scheller Austenitic Lightweight Steel and Use Thereof
CN102597545A (zh) * 2009-10-05 2012-07-18 嘉利股份公司 自锁定螺母
US8382411B2 (en) * 2008-06-16 2013-02-26 Gally S.P.A. Self-locking nut
AT516464A1 (de) * 2014-11-03 2016-05-15 Berndorf Band Gmbh Metallische Bänder und deren Herstellungsverfahren
AT516453A1 (de) * 2014-11-03 2016-05-15 Berndorf Band Gmbh Metallische Bänder und deren Herstellungsverfahren
CN112941423A (zh) * 2019-11-26 2021-06-11 上海微创医疗器械（集团）有限公司 医用合金及支架

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JP6259579B2 (ja) * 2012-03-29 2018-01-10 新日鐵住金ステンレス株式会社 耐熱へたり性に優れた高強度ステンレス鋼線、高強度ばね並びにその製造方法
KR101420782B1 (ko) * 2013-12-30 2014-07-17 광일토건환경 주식회사 흙막이 가시설 시공방법
WO2016031958A1 (ja) * 2014-08-28 2016-03-03 国立大学法人豊橋技術科学大学 金属材料および加工処理方法
CN105483502A (zh) * 2015-12-03 2016-04-13 浙江腾龙精线有限公司 一种弹簧线的生产方法
JP6782601B2 (ja) * 2016-10-05 2020-11-11 日鉄ステンレス株式会社 耐温間リラクセーション特性に優れる高強度ステンレス鋼線およびその製造方法、ならびにばね部品
CN108977727A (zh) * 2018-06-29 2018-12-11 柳州市横阳机械有限公司 不锈钢丝的制备方法
CN114959423B (zh) * 2022-06-07 2023-04-14 甘肃酒钢集团宏兴钢铁股份有限公司 一种高硅含钛奥氏体不锈钢的冶炼方法

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US20070041863A1 (en) 2007-02-22
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DE60219693D1 (de) 2007-05-31
EP1472383A2 (en) 2004-11-03
DE60219693T2 (de) 2007-12-27
WO2003056053A1 (en) 2003-07-10
JP4327601B2 (ja) 2009-09-09
BR0214816B1 (pt) 2011-02-08
JP2005513273A (ja) 2005-05-12
AU2002360028A1 (en) 2003-07-15
BR0214816A (pt) 2004-08-31
KR100966068B1 (ko) 2010-06-28
ATE360104T1 (de) 2007-05-15
EP1472383B1 (en) 2007-04-18
AU2002358375A1 (en) 2003-07-15
KR20040061028A (ko) 2004-07-06
SE526881C2 (sv) 2005-11-15
WO2003056053B1 (en) 2004-04-08
WO2003056052A1 (en) 2003-07-10

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