EP1735478B1 - Steel alloy for cutting details - Google Patents

Steel alloy for cutting details Download PDF

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Publication number
EP1735478B1
EP1735478B1 EP05728087A EP05728087A EP1735478B1 EP 1735478 B1 EP1735478 B1 EP 1735478B1 EP 05728087 A EP05728087 A EP 05728087A EP 05728087 A EP05728087 A EP 05728087A EP 1735478 B1 EP1735478 B1 EP 1735478B1
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EP
European Patent Office
Prior art keywords
steel alloy
alloy
hardness
weight
alloy according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
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EP05728087A
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German (de)
English (en)
French (fr)
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EP1735478A1 (en
Inventor
Jonas Nilsson
Andreas Rosberg
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Sandvik Intellectual Property AB
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Sandvik Intellectual Property AB
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Publication of EP1735478A1 publication Critical patent/EP1735478A1/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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • 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
    • 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
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese

Definitions

  • the present disclosure relates to a material for cutting details with high demands on, among other things, corrosion resistance and hardness. Details of the material should be possible to be made by photoetching, and in order to meet these demands, a very particular combination of properties is required according to the discussion below.
  • a factor that further drastically affects the edge durability of a material is the presence of hard particles (carbides, nitrides, and carbonitrides which henceforth are denominated jointly as carbonitrides) in the material.
  • An increasing volume fraction of carbonitrides gives a material having better edge durability.
  • there are limitations that have to be taken into consideration - the possibility again of making a truly sharp edge by mechanical machining or photoetching.
  • mechanical machining of edges having small edge angles ( ⁇ 30°) experience shows that carbonitrides (also applying to slags and inclusions), of a diameter larger than 10 ⁇ m, cause tear outs and edge damage, the initial sharpness of the edge drastically being deteriorated.
  • the demands are even greater.
  • a usual cause of large carbonitrides is alloying additives of very strong carbide formers, such as, for instance, vanadium, and therefore this type of alloying elements should preferably be avoided.
  • Another cause of large carbonitrides is poor process control when casting and hot working the materials.
  • An additional demand on the material according to the present invention is that it, in a cost-effective and quality-assured way, should be possible to harden by a continuous process (strip widths up to 1000 mm and strip thicknesses down to 15 ⁇ m) including furnace for the austenitizing, quenching for the conversion to martensite and finally a furnace for tempering.
  • a continuous process strip widths up to 1000 mm and strip thicknesses down to 15 ⁇ m
  • the austenitizing the carbonitrides in the material are dissolved to a certain extent and the contents of alloying elements increase in the matrix.
  • the production process for the material includes melting of raw materials in an electric arc furnace alternatively a high frequency furnace.
  • the content of carbon in the material can be controlled by choice of raw materials or by carbon elimination either in AOD (Argon Oxygen Decarburization), CLU (Creusot Loire Uddeholm) or another refining process.
  • the material may be remelted in a secondary metallurgical process such as VIM (Vacuum Induction Melting), VAR (Vacuum Arc Remelting), ESR (Electroslag Remelting), or the like.
  • Casting may take place in the traditional way into ingot or by continuous casting. A first strong reduction is made in the warm state, and then the material is spheroidized. Next, cold rolling is carried out in a plurality of steps including intermediate annealing operations.
  • the material may be delivered to customer either in cold-rolled, annealed, or hardened and tempered form.
  • the stainless martensitic chromium steel according to the discussion above has advantages to austenitic materials for the manufacture of details by photochemical processing. These advantages are, among other things, that the material after hardening has a very good flatness and is almost strain free. The material also allows a good productivity for this type of machining.
  • the hardness of the material in the hardened form is substantially determined by the content (carbon + nitrogen) in % by weight, and in order to be able to attain a hardness of over 56 HRC without deep freezing, with sufficient remaining volume fraction of carbonitrides for the edge durability, this sum has to be greater than 0,55 % by weight, provided that high contents of carbonitride formers such as chromium and molybdenum are present.
  • the carbon activity has to be limited for avoiding formation of primary carbides in the solidification, which is provided by keeping the content of silicon low, i.e.
  • the material is austenitized at 950-1150 °C, preferably 1000-1070 °C, and then quenched (suitably in oil, between cooling clamps or by means of compressed air) to room temperature.
  • a tempering is made at about 200 °C in order to achieve a hardness > 56 HRC. With deep freezing to -80 °C before tempering, an additional hardness enhancement of about 2 HRC can be attained.
  • Chromium has to be added to the material in a sufficient quantity in order to form a corrosion-protecting oxide film on the material surface, but at high contents of chromium, again the risk of the formation of large primary carbides arises, which has to be avoided. Therefore, the content of chromium should be 12-15 %, preferably 13-15 %, most preferably 14-15 %, by weight. Molybdenum is then added in sufficient quantity to give a PRE > 25.
  • a suitable content of Mo is 2,5-4,0 %, preferably 2,6-4,0 %, most preferably 2,6-3,0 %, by weight.
  • Nickel and cobalt are expensive alloying materials, which are stable in a normal metallurgical process, which means that the contents are accumulated over time in steel making based on recycled steel.
  • the content of nickel of max 1 % in order for the material not to be classified as potential carcinogenic and allergenic according to the Euro directive 99/45/EC, and therefore this content has been set as a maximum content regarding nickel for the alloy according to the patent.
  • nickel is not added actively in the material and the content of nickel is determined to max. 0,7 % in order to avoid the austenite stabilization that otherwise would be the consequence.
  • the alloy also contains 0,1-1,0 %, preferably 0,4-0,8 %, most preferably 0,4-0,7 %, by weight, of Mn which is another element that stabilizes the austenite.
  • the maximum content of cobalt has been set to 4 %, on one hand because of the expense and on the other hand to avoid too a fast accumulation of cobalt in the processing of recycled steel depending on the element normally being seen as an impurity in stainless steel, above all within the nuclear power industry.
  • cobalt is not added actively in the material and the content of cobalt is set to max 0,5 %, in spite of the increasing impact of the element on the martensite formation temperature.
  • an addition of cobalt may displace the phase transformation upon cooling after hardening toward more martensite.
  • DE-A-39 01 470 discloses a material suited for, among other things, razor blades and knives.
  • the patent teaches a pressurized metallurgy in order to achieve contents of nitrogen above 0,20 % by weight, and thereby maximally twice as high content of carbon as of nitrogen.
  • two experimental alloys are mentioned, both with hardness below 600 HV.
  • the patent also teaches additions of vanadium in low contents. Therefore, the material will not meet the above-mentioned demand on hardness and avoidance of the alloy element vanadium, and furthermore, the production cost will become very high.
  • EP-A-638 658 vanadium is used in order to achieve a strong secondary hardening upon tempering to high temperatures, which may be an advantage, for instance if the material is to be coated or used at high temperatures. However, this is objectionable if the material is to be etched into final form or be used to produce very sharp edges, according to the above.
  • the patent states 40 ⁇ m as the largest allowable size of carbonitrides unlike the 5 ⁇ m stated as the maximum limit according to the present invention.
  • EP-A-750 687 states the maximum content (carbon + nitrogen) to 0,55 % by weight, which according to the present invention is judged to be a minimal content in order to achieve sufficient hardness.
  • a first object of the present invention is to provide a new steel alloy, which overcomes all the above-mentioned drawbacks of prior art.
  • the object of the present invention is to provide a steel alloy that has a hardness of at least 56 HRC, has excellent corrosion resistance and can be machined by means of photoetching.
  • the maximum size of carbides, nitrides and carbonitrides is ⁇ ⁇ 5 ⁇ m, in order to reduce the risk of edge related problems and to be able to dissolve the carbides, nitrides and carbonitrides during austenitisation.
  • the steel alloy according to the present invention has the following composition (in % by weight): C 0, 42-0, 60 Si 0,15-0,80 Mn 0,4-0,8 Cr 13-15 Mo 2,6-4,0 Ni 0-0,7 Co 0-0,5 N 0,15-0,20, as well as the balance Fe and normally occurring impurities.
  • the steel alloy according to the present invention has the following composition (in % by weight): C 0,42-0,50 Si 0,15-0,55 Mn 0,4-0,7 Cr 14-15 Mo 2,6-3,0 Ni 0-0,7 Co 0-0,5 N 0,15-0,20, as well as the balance Fe and normally occurring impurities.
  • Materials manufactured according to the present disclosure are especially suitable for the use in applications such as, for instance, knives in the food industry having high demands on hardness and edge durability in combination with corrosion resistance due to chloride ion-containing environment as well as corrosive dishwashing detergents. Other areas are cutting edges for dry and wet shaving, surgical edge applications as well as diving knives. Additional fields of application for the new material are, for instance, doctor blades in the printing industry as well as doctor blades (also known as coater blades) and creping blades in the pulp industry.
  • the metallurgical process comprises melting in an electric arc furnace or a high frequency furnace.
  • the content of carbon is adjusted either by the choice of alloying materials or by carbon elimination in AOD or CLU or another refining process.
  • the content of nitrogen is adjusted either by the supply in the form of gas or by the use of nitrogenous alloying materials.
  • the material may be remelted in a secondary metallurgical process such as VIM, VAR, ESR or the like.
  • Casting may be effected into ingot or via continuous casting, and then hot working follows down to strip form. After the hot working, the material is spheroidized and then cold-rolled in a plurality of steps into desired thickness including intermediate recrystallization annealing operations. Upon customer want of a hardened and tempered delivery finish, this hardening takes place in a continuous strip process in the form of an austenitizing in protective atmosphere, a quenching (for the phase transformation into martensite), and finally a tempering to desired hardness. The material is then cut into desired widths or is cut into planar lengths depending on the customer want.
  • the final product may be produced by any conventional process; for example, from hardened strip material by photoetching and forming, or from cold-rolled strip material by punching/cutting, forming, hardening, tempering and finally grinding. It is also conceivable to sell the material in the wire, tube or ingot form.
  • One melt of material of the present disclosure has been produced in ten ton scale with CLU-metallurgy.
  • the material has been ingot casted, hot rolled and thereafter cold rolled with intermediate annealings down to suitable thickness for evaluation.
  • the melt of the present invention has the composition as indicated in Table 1, Alloy 1.
  • the material according to the present disclosure is compared with three grades: Comparative examples 1-3.
  • the nominal composition of the comparative examples 1-3 is also given in Table 1.
  • Table 1 Chemical composition in percent by weight of the test melt and nominal composition in percent by weight of comparative examples 1-3.
  • FIG. 1 A general outline between the comparative examples is illustrated in Figure 1 , showing the hardness versus corrosion resistance as well as the influence of the alloying elements C, N, Cr and Mo. Table 2. Result from testing according to ISO 8442.1 and ISO 8442.5. Blade description Hardness Retained Austenite ISO 8442.5 ISO 8442.1 ICP, Catra resharpening TCC, Catra resharpening Corrosion (HV 1 kg) (HRC, Calculated) (%) (mm) (mm) Alloy 1, A 666 58,6 7,7 104,5 503,7 P1 Alloy 1, B 665 58,5 8,7 102,8 402,4 P2 Alloy 1, C 673 58,9 8,2 104,8 485,9 P1 Comp.
  • the corrosion test according to ISO 8442.1 shows that the material according to the present disclosure passes the test whereas the Comparative example 1 fails in the test.
  • the results from the edge testing according to ISO 8442.5 are on the very same level for the new grade and for Comparative example 1.
  • the corrosion properties of the material of the present disclosure were also measured by anodic polarization/critical pitting potential (CPP) and compared with Comparative example 1 and Comparative example 2.
  • Samples were taken from Alloy 1 and from Comparative example 1 and Comparative example 2 respectively, all compositions given in Table 1.
  • the sample of Alloy 1 was hardened at 1035°C
  • the samples of Comparative example 1 were hardened at 1080°C
  • the samples of Comparative example 2 were hardened at 1030°C, according to recommendation for each alloy.
  • the tempering for all grades was performed at 225°C. All surfaces of the samples were finished with 600 grit wet grinding.
  • test solution was 0,1% NaCl, the test was performed at 20°C, and the potential over the sample was increased with 75 mV/minute with a start at -600 mV. Nitrogen gas was bubbled through the solution to reduce the oxygen level. The criteria used for start of pitting was set to I > 10 ⁇ A/cm 2 . The result from the test is shown in Figure 2 .
  • Hardening tests were performed on material of Alloy 1 and compared with typical data for Comparative example 1, Comparative example 2 and Comparative example 3.
  • the hardening of Alloy 1 was done at 1035°C and quenching to 20°C, but also at 1055°C in combination with deep freezing at -70°C.
  • the hardness is shown in Figure 3 as a function of tempering temperature after tempering for 30 minutes.
  • the typical microstructure for material of Alloy 1 in the annealed condition is a ferritic matrix with uniformly distributed secondary carbides, nitrides and carbonitrides. Furthermore, the microstructure of Alloy 1 is free from primary carbides, nitrides or carbonitrides with a diameter bigger than 5 ⁇ m.
  • a typical structure of Alloy 1 is shown in Figure 5 , wherein the microphotograph is taken in light optical microscope at 1000 x magnification after polishing and etching of a transverse cross section. Etching was done in 4% Picric acid with a minor addition of hydrochloric acid. The average diameter of the carbides, nitrides and/or carbonitrides was estimated to approximately 0,4 ⁇ m.
  • the database used has been TCFE3.
  • Optimal hardening temperatures have been selected and used in the modelling for the different grades.
  • values for PRE, M s and weight percent of the interstitials nitrogen and carbon have been calculated.
  • phase percentage of M 23 C 6 carbide in equilibrium with the austenitic phase which is an important factor for wear and edge durability, has been calculated.
  • PRE the previously discussed equation has been used.
  • Comparative example 1 shows that the steel according to the invention has significantly higher PRE-values but at the same time comparable interstitial content and amount of carbide phase, which should result in a steel with similar hardness and edge performance but significantly increased corrosion resistance.
  • Comparative example 2 is closer to Alloy 1 in PRE but the lower amount of interstitials in the matrix together with a lower amount of carbide phase predicts a lower hardness and inferior edge properties.
  • Alloys 2-6 are other possible embodiments of the composition according to the present disclosure, that result in different properties even though the difference in chemical composition is small. Alloys 2 and 4 have comparable values for PRE, interstitial content and M s , which results in similar corrosion resistance, hardness and hardenability but with about twice the amount of M 23 C 6 carbides in Alloy 4, the edge durability will be higher in this grade. Highest amount of interstitials in the matrix and thus the highest expected hardness is achieved in Alloy 3, which still has a sufficient hardenability due to the addition of Cobalt. Alloy 5 has even higher amount of cobalt compared to Alloy 6, which improves the hardenability even further without drastically changing the other properties.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Articles (AREA)
  • Heat Treatment Of Steel (AREA)
  • Knives (AREA)
  • Accessories And Tools For Shearing Machines (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
EP05728087A 2004-03-26 2005-03-22 Steel alloy for cutting details Not-in-force EP1735478B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE0400806A SE526805C8 (sv) 2004-03-26 2004-03-26 Stållegering
PCT/SE2005/000422 WO2005093112A1 (en) 2004-03-26 2005-03-22 Steel alloy for cutting details

Publications (2)

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EP1735478A1 EP1735478A1 (en) 2006-12-27
EP1735478B1 true EP1735478B1 (en) 2010-06-16

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EP05728087A Not-in-force EP1735478B1 (en) 2004-03-26 2005-03-22 Steel alloy for cutting details

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US (1) US20070274855A1 (sv)
EP (1) EP1735478B1 (sv)
JP (1) JP2007530784A (sv)
CN (1) CN100463996C (sv)
AT (1) ATE471392T1 (sv)
AU (1) AU2005226606B2 (sv)
DE (1) DE602005021872D1 (sv)
SE (1) SE526805C8 (sv)
WO (1) WO2005093112A1 (sv)

Families Citing this family (10)

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US8052703B2 (en) * 2005-06-29 2011-11-08 Boston Scientific Scimed, Inc. Medical devices with cutting elements
JP5426117B2 (ja) * 2008-07-07 2014-02-26 株式会社東芝 ジェットポンプビームのボルト固定装置
ES2367855T3 (es) * 2008-12-17 2011-11-10 Saab Ab Restauración de la fuerza y de la resistencia al desgaste de un compuesto de matriz metálica (mmc).
KR101268800B1 (ko) * 2009-12-21 2013-05-28 주식회사 포스코 고탄소 마르텐사이트계 스테인리스강 및 그 제조방법
RU2733516C2 (ru) 2011-10-06 2020-10-02 Бик-Вайолекс Са Цельное жесткое бритвенное лезвие
US10196718B2 (en) * 2015-06-11 2019-02-05 Hitachi Metals, Ltd. Steel strip for cutlery
CN109136770B (zh) * 2018-10-18 2020-10-27 西安交通大学 一种镁冶炼用高铬合金钢坩埚及其制备方法
US20220250266A1 (en) * 2019-02-28 2022-08-11 Edgewell Personal Care Brands, Llc Razor blade and composition for a razor blade
BR112021024509A2 (pt) * 2019-06-05 2022-01-18 Ab Sandvik Materials Tech Uma liga de aço inoxidável martensítico
CN111270165B (zh) * 2020-02-18 2020-12-22 北京科技大学 一种速滑冰刀材料的制造方法

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US3595643A (en) * 1965-10-18 1971-07-27 Sandvikens Jernverks Ab Razor blade of a chromium containing steel
DE3901470C1 (en) * 1989-01-19 1990-08-09 Vereinigte Schmiedewerke Gmbh, 4630 Bochum, De Cold-working steel and its use
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JPH07197130A (ja) * 1993-12-29 1995-08-01 Nkk Corp 溶接部の耐孔食性と低温靭性に優れた二相ステンレス溶接鋼管の製造方法
MY114984A (en) * 1995-01-13 2003-03-31 Hitachi Metals Ltd High hardness martensitic stainless steel with good pitting corrosion resistance
JP2968844B2 (ja) * 1995-01-13 1999-11-02 日立金属株式会社 耐孔食性の優れた高硬度マルテンサイト系ステンレス鋼
JPH11303874A (ja) * 1997-04-16 1999-11-02 Nippon Seiko Kk 転動部材
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JP4724275B2 (ja) * 2000-07-17 2011-07-13 株式会社リケン 耐スカッフィング性、耐クラッキング性及び耐疲労性に優れたピストンリング及びその製造方法

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Publication number Publication date
DE602005021872D1 (de) 2010-07-29
US20070274855A1 (en) 2007-11-29
WO2005093112A1 (en) 2005-10-06
CN1918315A (zh) 2007-02-21
SE0400806L (sv) 2005-09-27
SE526805C8 (sv) 2006-09-12
ATE471392T1 (de) 2010-07-15
CN100463996C (zh) 2009-02-25
SE526805C2 (sv) 2005-11-08
JP2007530784A (ja) 2007-11-01
SE0400806D0 (sv) 2004-03-26
EP1735478A1 (en) 2006-12-27
AU2005226606B2 (en) 2010-04-08
AU2005226606A1 (en) 2005-10-06

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