Classifications

• • 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.
• the hardness is of great importance. A harder material resists plastic deformation better, which is a common degradation mechanism for cutting edges - that they simply bend and/or are deflected when stressed. Furthermore, a harder material will resist wear better and thereby an edge will remain sharp longer, or in other words, have better edge durability.
• An additional advantage of a harder material is that the normally seen decreasing toughness gives an improved burr breaking in mechanical grinding and polishing, whereby a sharper edge may be obtained.
• An absolute minimum in hardness of a material intended for edges with demands on edge durability and possibility of mechanical sharpening is judged to be 56 HRC (hardness on the Rockwell C-scale, which corresponds to approx. 615 HV 1 kg measured as hardness in Vickers with the load of 1 kg) .
• 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.
• the etching medium for instance a mixture of HC1 and FeCl 3
• the etching will be accelerated in the border between bulk mass and carbonitride . This entails that the carbonitrides risk being etched out of the material. In order for this phenomenon not to affect the finished product negatively, carbonitrides of a diameter larger than 5 ⁇ m must not be present in the material.
• 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.
• martensitic stainless chro- mium steel they are most often of the type pitting corrosion.
• the three most important alloying elements to control this corrosion type are chromium, molybdenum and nitrogen.
• PRE-value Pultting Resistance Equivalent
• PRE % Cr + 3, 3 • % Mo + 16 • % N.
• 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 con- tinuous process (strip widths up to 1000 mm and strip thicknesses down to 15 ⁇ m) including furnace for the aus- tenitizing, quenching for the conversion to martensite and finally a furnace for tempering.
• the carbonitrides in the material are dissolved to a certain extent and the contents of alloying elements increase in the matrix. In order for this dissolution to occur evenly (enables good dimensional tolerances) and within a short time (high productivity) , it is required that the carbonitrides are small in size (0 ⁇ 5 ⁇ m) and furthermore that the size distribution is even, which is controlled by an accurately controlled production process.
• 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
• 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 car- bonitride formers such as chromium and molybdenum are pres- ent.
• 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.
• 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.
• 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 inven- tion.
• 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. This is confirmed by the fact that the aim what relates to hardness in the EP publication is HRC > 50, and that the experimental alloy that achieves the highest hardness reaches 56,3 HRC (this is after tempering for 1 h at only 180 °C) . This limited hardness in combination with a small share of remaining carbonitrides will cause inadequate edge durability for edge applications with high demands. Foremost, the patent specification also focuses articles with extremely high demands on corrosion resistance, why also copper has been added, and therefore the hardness and the hot workability has been neglected.
• 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 steel alloy according to the present invention has the following composition (in % by weight) :
• the steel alloy according to the present invention has the following composition (in % by weight) :
• 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. Choice of way of manufacture of the material depends, among other things, on desired material volume, maximum allowed production cost and demands on slag purity.
• 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 fol- lows down to strip form.
• the material is spheroidized and then cold-rolled in a plurality of steps into desired thickness including intermediate recrys- tallization annealing operations.
• 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.
• Figure 1 illustrates a general outline between three comparative examples with regard to hardness/edge durability and corrosion resistance.
• Figure 2 illustrates the result of a CPP test of Alloy
• Figure 3 illustrates the hardness as a function of the tempering temperature for Alloy 1 and three comparative examples .
• Figure 4 illustrates the hardness and CPP corrosion resistance for Alloy 1 and two comparative examples.
• Figure 5 shows a microphotograph of Alloy 1 according to the present disclosure illustrating the microstructure of the composition.
• Figure 6 shows a microphotograph of a comparative example illustrating the microstructure of the composition.
• Figure 7 illustrates a comparison between Alloy 1 and two comparative examples with regard to the hardness levels and structures.
• Example 1 One melt of material of the present disclosure, Alloy 1, 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.
• Figure 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.
• Example 2 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, and 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.
• CPP anodic polarization/critical pitting potential
• 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.
• Example 3 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
• Example 4 In Figure 4, Alloy 1 is compared with Comparative example 1 and Comparative example 2 with regard of corrosion resistance and hardness. All samples were tempered at 225°C and heat treated as described above. It is desired that the composition possesses a high corrosion resistance as well as a high hardness. This is illustrated by an arrow in Figure 4 showing the desired direction of the properties. It is easily seen that Alloy 1 of the present invention combines an improved hardness as compared with Comparative example 1 with an improved corrosion resistance as compared with Comparative example 2.
• the typical microstructure for material of Alloy 1 in the annealed condition is a ferritic matrix with uniformly distributed secondary carbides, nitrides and carbonitrides.
• 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. For edge applications where very keen edges are to be produced either by mechanical methods or by etching the above structure free from primary carbides with a diameter larger than 5 ⁇ m is necessary to avoid tear outs or etching defects on the edge.
• a microphotograph taken under the same conditions, showing the typical structure for Comparative example 3 is shown in Figure 6.
• Figure 7 the hardness levels and structures are compared for Alloy 1 of the invention, Comparative example 1 and Comparative example 3.
• Example 5 Since the properties of the steel are highly dependent on the hardening conditions, estimations outgoing from the basic chemical composition may be misleading. Equilibrium calculations at a predetermined suitable hardening temperature using the software ThermoCalc is one way to more accurately calculate the final properties and have been performed for Alloys 2-6, Alloy 1, as well as Comparative examples 1-3. The compositions of Alloys 2-6 are given in Table 3 and the results of the calculations are shown in Table 4. The database used has been TCFE3. Optimal hardening temperatures have been selected and used in the modelling for the different grades. Outgoing from the austenite phase composition at hardening temperature, values for PRE, M s and weight percent of the interstitials nitrogen and carbon have been calculated. Also the phase percentage of M 23 C ⁇ carbide in equilibrium with the austenitic phase, which is an important factor for wear and edge durability, has been calculated. For PRE, the previously discussed equation has been used. M s was calculated using Andrew's formula, as shown below:
• Comparison between Alloy 1 and 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. These data correspond to the actual measurements in the previous example.
• the M s -temperature for Alloy 1 is lower than both Comparative example 2 and Comparative example 1 but in the same range as Comparative example 3, which has a known good hardenability, but where the carbide content significantly higher resulting in a coarser microstructure as shown before in Figure 6.
• 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 3 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)
• Accessories And Tools For Shearing Machines (AREA)
• Cutting Tools, Boring Holders, And Turrets (AREA)
• Manufacture Of Alloys Or Alloy Compounds (AREA)
• Knives (AREA)

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• 2004
  • 2004-03-26 SE SE0400806A patent/SE526805C8/sv not_active IP Right Cessation
• 2005
  • 2005-03-22 WO PCT/SE2005/000422 patent/WO2005093112A1/en active Application Filing
  • 2005-03-22 EP EP05728087A patent/EP1735478B1/de not_active Not-in-force
  • 2005-03-22 US US10/584,246 patent/US20070274855A1/en not_active Abandoned
  • 2005-03-22 AU AU2005226606A patent/AU2005226606B2/en not_active Ceased
  • 2005-03-22 CN CNB200580004712XA patent/CN100463996C/zh not_active Expired - Fee Related
  • 2005-03-22 DE DE602005021872T patent/DE602005021872D1/de active Active
  • 2005-03-22 JP JP2007504917A patent/JP2007530784A/ja active Pending
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