EP2570507A1 - Procédé de production d'acier à haute vitesse - Google Patents

Procédé de production d'acier à haute vitesse Download PDF

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Publication number
EP2570507A1
EP2570507A1 EP11181771A EP11181771A EP2570507A1 EP 2570507 A1 EP2570507 A1 EP 2570507A1 EP 11181771 A EP11181771 A EP 11181771A EP 11181771 A EP11181771 A EP 11181771A EP 2570507 A1 EP2570507 A1 EP 2570507A1
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European Patent Office
Prior art keywords
high speed
speed steel
weight
content
producing
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EP11181771A
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German (de)
English (en)
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Tomas Berglund
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Sandvik Intellectual Property AB
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Sandvik Intellectual Property AB
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Priority to EP11181771A priority Critical patent/EP2570507A1/fr
Priority to EP12759474.5A priority patent/EP2758558A1/fr
Priority to US14/345,413 priority patent/US20140356218A1/en
Priority to JP2014530277A priority patent/JP2014530294A/ja
Priority to CN201280045555.7A priority patent/CN103814145A/zh
Priority to PCT/EP2012/068428 priority patent/WO2013041558A1/fr
Publication of EP2570507A1 publication Critical patent/EP2570507A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • 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
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • 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
    • C22C38/36—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.7% by weight of carbon

Definitions

  • This invention refers to a method for producing a high speed steel with the composition according to the preamble of claim 1.
  • Such application areas may include, hot forging tools for metal forming, combustion engine parts etc.
  • FeCrAl-alloys FeCrAl-alloys, NiCrAl-alloys, Ni-base alloys, Co-base alloys and special stainless steels.
  • FeCrAl- NiCrAl- and Ni- alloys are too soft to be used in the aforementioned areas of applications.
  • Some Co-base alloys are sufficiently hard but too expensive to be a practical alternative for most applications.
  • High speed steel offers good hardness at room temperature and is able to maintain that hardness up to 600°C. However, for some applications it is desirable to maintain the room temperature hardness at temperatures well above 600°C.
  • alloying elements such as tungsten, molybdenum and vanadium increases the high speed steel's ability to withstand high-temperature, i.e their hot hardness and high temperature wear, thanks to formation of carbides based on said alloying elements.
  • ion-implantation Ion beam modification of metals, G. Dearnley, Nuclear Instruments and Methods in Physics Research B50 1990 p358-367 .
  • ion-implantation Ion beam modification of metals, G. Dearnley, Nuclear Instruments and Methods in Physics Research B50 1990 p358-367 .
  • a problem with ionimplantation is the Gaussian distribution of ions, which causes depth varying material characteristics. Ionimplantation also implies a limited useful thickness of the modified layer; therefore it is not suited for use in the aforementioned applications.
  • US Patent No. 5989491 to Isamoto et al. discloses a method that uses oxide dispersion strengthening for a powder metallurgy alloy.
  • the inventors behind this patent noted that fine dispersion of particles of an oxide in an oxide dispersion strengthened heat resisting powder metallurgy alloy enhanced creep rupture strength in addition to fundamental heat resisting properties inherent to heat resisting alloys.
  • the alloy disclosed in US5989491 is not suitable for mechanical applications involving wear such as those aforementioned, since the wear resistance of the end product will not be affected by the addition of fine particles of an oxide.
  • JP57085952A discloses an alloy with a composition corresponding to the composition according to the preamble of claim 1 of the present invention. It must be assumed that the document in question also discloses casting as the method of producing the alloy. It must be assumed that the steel disclosed therein has a microstructure that results in poor strength of the material and therefore makes it less usable as a wear part.
  • the object of this invention is to present a method by means of which the above mentioned problems associated with manufacturing of high speed steel comprising of rare earth element Y for applications that involve wear at elevated temperatures, are reduced or solved.
  • the present invention also aims at providing a manufacturing method which increases the ability of high speed steel to withstand wear at elevated temperatures.
  • the present invention is based on the insight of the problems of segregation and coarse carbide structures associated with casting and the addition of yttrium into conventional high speed steel.
  • the method comprises the steps of: providing a powder comprising the elements of said high speed steel, forming a body of said powder, and subjecting said body to elevated heat (temperature) and elevated pressure such that a consolidation of the powder thereof is achieved.
  • This step may be referred to as the consolidation step or a hot isostatic pressure (HIP) step.
  • the steel is in solid state, i.e. non-molten state.
  • the temperature during said step of elevated temperature is within the range of 950-1200 °C, wherein lower temperatures may be required for alloys with relatively high content of C and low content of alloying elements such as Mo, W, Co, Y, etc and wherein higher temperatures within said range is required for alloys with relatively low content of C and high content of said further alloying elements. If the temperature is too low, the final result will be a porous material, and if the temperature is too high, the material might start to melt, which should be avoided.
  • the pressure during the consolidation step is dependent on the temperature that is chosen for each respective steel composition.
  • a relatively low temperature may be compensated for by means of a higher pressure.
  • the pressure should be in the range of 800-1500 bar. In general, higher content of alloying elements will require a higher pressure for a specific chosen temperature.
  • the body of consolidated powder that now has a very low porosity level or no porosity at all, is then subjected to soft annealing.
  • the soft annealing is performed in order to facilitate subsequent machining of the alloy.
  • the maximum temperature of the soft annealing step is the temperature of the foregoing consolidation step, while the minimum temperature is the temperature at which the steel undergoes softening and carbides in the steel spheroidize and the martensite transforms to ferrite. In any case, the temperature must not be so high that it results in severe coarsening of the carbide grain size.
  • the selected soft annealing temperature will depend on the composition of the alloy. Generally, higher contents of alloying elements will require a higher annealing temperature. Accordingly, for the compositions within the scope of the present invention, the soft annealing temperature will preferably be from 600 to 900 °C.
  • the duration of the soft annealing should be sufficiently long to reach ferrite content in the material that is sufficiently high. Preferably, after soft annealing the ferrite-austenite ratio should be at least 95/5.
  • the steel is cooled relatively slowly, in order to avoid formation of martensite, or bainite in the alloy. Preferably, the cooling rate is within the range of 5-20°C/hour, depending on the composition of the alloy.
  • Cooling with this rate is performed down to a temperature below which the cooling rate will no longer affect the formation of bainite, martensite. Below that temperature, the cooling may be natural, and the cooling rate may depend only on the outer conditions reigning. For the alloys within the scope of the invention, this temperature may be in the range of 600-700°C.
  • the body is thereafter preferably subjected to machining if necessary and thereafter heat treated with a hardening (austenizing) step at a temperature in the range of 950-1200°C, depending on the specific composition of the steel that is hardened.
  • a hardening (austenizing) step at a temperature in the range of 950-1200°C, depending on the specific composition of the steel that is hardened.
  • This austenite is removed by means of subsequent annealing steps.
  • During the first step remaining austenite is transformed into martensite.
  • this martensite being very brittle will require a further annealing step in order to become sufficiently ductile.
  • the number and duration of the annealing steps may vary. According to a preferred embodiment of the invention, annealing steps are performed until the level of remaining austenite is maximum 5%, preferably maximum 2%.
  • the technical effect of the inventive method is that the rare earth element yttrium is evenly distributed in the powder. If the high speed steel according to the inventive concept would have been produced by a conventional casting method, the highly reactive element yttrium would segregate and not be evenly distributed. An even distribution of yttrium in the high speed steel base-matrix causes an oxide scale that is formed to adhere effectively to the high speed steel. The added yttrium also changes the growth kinetics of the oxide scale so that the scale quickly grows to a saturation thickness. The growth rate of the oxide scale is drastically reduced above this saturation thickness. The beneficial technical effect on the wear resistance, at elevated temperatures, due to the fine dispersion of yttrium in the base-matrix of the high speed steel is unexpectedly good.
  • the steel will have a mean carbide particle size which is much lower than that of a corresponding material made using casting method. According to the invention, the steel should have a mean carbide particle size of ⁇ 3 ⁇ m, something it will have if the method of the invention is being used for the production thereof.
  • the steel will also have an isotropic microstructure, which is also advantageous for its wear properties.
  • the invention teaches that the consolidation step and the subsequent heat treating steps shall be performed such that the steel obtains a mean carbide particle size which is ⁇ 3 ⁇ m and an isotropic microstructure.
  • the properties of the formed oxide scale are extremely important in applications that besides high temperature and wear also include oxidation/corrosion. In oxidative/corrosive applications it is of great importance that damages in the oxide scale are quickly repaired by a fast growth of the oxide scale itself, and this is achievable by using the material produced by the inventive method.
  • the provision of the powder mixture comprises the step of argon-atomisation of molten metal comprising said elements into said powder.
  • the yttrium content of the high speed steel is within the range 0.20 to 1.0 weight%. It is preferred that the yttrium content of the high speed steel is more than 0.40 weight%, and less than 0.70 weight% more preferably less than 0.60 weight%. In a particularly preferred embodiment, the Yttrium content is with the range of 0.45-0.60 weight%.
  • the yttrium content defined in the interval above gives the aforementioned positive effects on the oxide scale. Especially the yttrium content in the range of 0.45-0.60 weight% gives a very good increase in the ability of the high speed steel to withstand high temperature wear.
  • the lower limit 0.20% of the interval defines a starting point from where a significant positive effect of yttrium on the high temperature wear can be identified.
  • the higher limit of 1% indicates the end of the interval from where a significant positive effect of yttrium on the high temperature wear can be identified.
  • the carbon (C) content of said high speed steel is in the range of 1.1-1.4 weight%.
  • the amount of carbon should be sufficient to form the carbides necessary for the wear resistance of the high speed steel.
  • Preferably the amount of carbon should be enough to produce a high speed steel with sufficient hardenability.
  • the lower limit of 1.1% defines a minimum carbon content in order to form a high speed steel with the desired carbides and hardenability.
  • the higher limit of 1.4% defines maximum carbon content in this embodiment, above which austenite may be formed.
  • the chromium (Cr) content is in the range of 3.0-6.0 weight%. This interval causes good hardenability as well as the necessary forming of carbides. However, too much chromium causes formation of residual austenite and increased risk for over-tempering; therefore the upper limit of Cr must not be exceeded. According to yet another preferred embodiment, the Cr content is within the range of 4.0-5.0 weight%.
  • the molybdenum (Mo) content is in the range of 4.5-5.5 weight%. This interval causes secondary hardening by precipitation of carbides that will increase the hot hardness and wear resistance of the high speed steel.
  • the tungsten (W) content is in the range of 6.0-7.0 weight%. This interval causes secondary hardening by precipitation of carbides that will increase the hot hardness and wear resistance of the high speed steel.
  • Mo and W have similar effects on this kind of steel and that they are therefore to a large extent replaceable with each other.
  • Mo+0.5W 2-10 weight%.
  • Mo+0.5W 5-8.5 weight%.
  • the vanadium (V) content is in the range of 3.0-5.0 weight%. This interval causes secondary hardening by precipitation of carbides that will increase the hot hardness and wear resistance of the high speed steel. However, too much vanadium causes the high speed steel to become brittle and therefore, the upper limit must not be exceeded. According to yet another preferred embodiment the V content is in the range of 3.0-3.5 weight%.
  • the cobalt (Co) content of said high speed steel is in the range of 8.0-9.0 weight%.
  • the alloying of high speed steel with cobalt improves the tempering resistance and hot hardness, both of which are of great importance for the high speed steel to be used in a high temperature wear application.
  • the amount of cobalt also has an effect on the hardness of the high speed steel by affecting the amount of retained austenite, causing said retained austenite to easily be converted to martensite during tempering.
  • the selected interval for cobalt is a suitable interval for a high speed steel of this composition wherein the upper level is more an economic compromise than a scientific constraint.
  • the cobalt content is 0% or at an impurity level.
  • Powder metallurgical high speed steel produced by the inventive method possesses properties such as very good resistance to high temperature wear even in oxidative/corrosive environments.
  • the industrial production of semi-finished products, components and cutting tools based on powder metallurgical high speed steel started 35 years ago.
  • the first powder metallurgical production of high speed steel was based on hot isostatic pressing (HIP) and consolidation of atomized powders.
  • the HIP step was normally followed by hot forging of the hipped billets. This method of production is still the dominating powder metallurgical method to produce high speed steel.
  • the original objective for research and development on powder metallurgical processing of high speed steel was to improve its functional properties and performance in demanding applications.
  • the main advantages from the powder metallurgical manufacturing process are no segregation and uniform and isotropic microstructure.
  • the well known problems with coarse and severe carbide segregation in conventional cast steel and forged steel are thus avoided in powder metallurgical high speed steel.
  • the powder metallurgical manufacturing method of a high speed steel with sufficient amount of carbon and carbide forming elements results in a disperse distribution of carbides that to a large extent solves the problem of low strength and toughness associated with conventionally produced high speed steel.
  • the present invention refers to a method for producing a high speed steel.
  • the elements having a lower limit of 0 % are optional.
  • the provision of the powder mixture comprises the step of argon gas-atomisation of molten metal comprising said elements into said powder.
  • the argon gas-atomisation of the molten high speed steel causes high speed steel particles of a maximum size of 160 ⁇ m to be formed.
  • a body is formed from said powder.
  • This forming may for example comprise pouring said powder into a capsule.
  • the capsule is then evacuated, e.g. by being subjected to a negative pressure of below 0.004 mbar for 24 hours in order to evacuate said capsule.
  • the capsule is then sealed in order to maintain said negative pressure in the capsule.
  • the consolidation of the powder is achieved by subjecting the capsule to an elevated temperature, e.g. about 1150°C, and an elevated pressure, e.g. about 1000 bar, for a long period of time, e.g. two hours. This last consolidation step is called hot isostatic pressing, HIP.
  • a soft annealing step follows the HIP step, preferably the soft annealing step is performed at 900°C followed by a temperature decrease to 700°C at a cooling rate of 10°C/hour, from thereon the body is allowed to naturally cool down to room temperature.
  • the body After soft annealing the body may be subjected to machining and preferably a hardening (austenizing) step at 1100°C and three subsequent annealing steps at 560°C for 60 minutes each, with natural cooling to room temperature there between.
  • a hardening (austenizing) step at 1100°C and three subsequent annealing steps at 560°C for 60 minutes each, with natural cooling to room temperature there between.
  • Table 1 shows the elements of the high speed steel used in the experiment. Smelts were produced with the elements in table 1, and from these smelts powders were produced by means of gas atomisation using argon.
  • the powders of alloy B and C in table 1 have a particle size of ⁇ 160 ⁇ m, while the powder of alloy A has a particle size of ⁇ 500 ⁇ m.
  • the preparation of samples continued with a filling of the capsules with powder, said capsules were made from spiral welded tubes with a diameter of 73 mm. The capsules were then exposed to an pressure below 0.004 mbar for 24 hours; the capsules were then sealed in order to maintain said pressure.
  • a hot isostatic pressing operation was performed at 1150°C and 1000 bar for 2 hours.
  • the samples were then subjected to a soft annealing step at 900°C followed by a temperature decrease to 700°C at a cooling rate of 10°C/hour, from thereon the samples were allowed to naturally cool down to room temperature.
  • the samples were then machined and heat treated with a hardening (austenizing) step at 1100°C and three subsequent annealing steps at 560°C for 60 minutes each, with natural cooling to room temperature there between.
  • a hardening (austenizing) step at 1100°C and three subsequent annealing steps at 560°C for 60 minutes each, with natural cooling to room temperature there between.
  • the final preparation step comprises stepwise grinding and polishing of the sample in automatic grinding/polishing equipment. During the final polishing step a 1 ⁇ m diamond suspension was used.
  • Figure 1 shows a simplified test set-up used for the tribological testing; this set-up is known in the art and has been referred to as "pin on disc".
  • the principle for the "pin on disc” tribological testing is as follows; a sample 1 is rotated around an axis 5 with a speed ⁇ for a number of revolutions. Simultaneous with the rotation of the sample 1 a force F is applied to a pin 2 that in its turn applies the same force F to a ball 3.
  • the ball 3 is made of Al 2 O 3 and has a diameter of 6 mm. The rotation of the sample 1 and the force F on the ball 3 causes a groove 6 to be formed in the sample 1.
  • the lower part of the "pin on disc” set-up is accommodated in a furnace 4.
  • the furnace 4 can heat the sample 1, the ball 3 and the lower part of the pin 2 to the desired operating temperature.
  • Figure 2 shows a cross section of the groove 6 perpendicular to the longitudinal direction of the groove 6.
  • the depth d measured from the polished surface of the sample to the bottom of the groove 6 is used as a measure of the wear resistance of the sample.
  • Another figure of the wear resistance is the cross-sectional area 7, which is defined as the cross-sectional area of the groove 6 below the polished surface of the sample 1 perpendicular to the longitudinal direction of the groove 6.
  • the profile and depth d of the groove 6 was estimated using a Veeco Wyko NT9100 white light interferometer.
  • a more representative measure of the wear resistance is the volume loss per meter (mm 3 /m).
  • the calculation of the volume loss per meter is performed by integrating the cross sectional area 7 over the longitudinal direction of the track and divide by the circumference of the groove.
  • the volume loss per meter is presented; volume loss for alloy A is 4.6x10 -5 mm 3 /m, volume loss for alloy B is 1.8 ⁇ 10 -5 mm 3 /m and finally the volume loss for alloy C is 4 ⁇ 10 -5 mm 3 /m.
  • the relation between the yttrium content of the high speed steel and the volume loss per meter thereof is illustrated in figure 4 . From figure 4 one can conclude that the yttrium content of 0.5 % clearly results in the lowest volume loss per meter. A higher yttrium content than 1% also has a beneficial effect on the volume loss per meter. This relation implies that the yttrium content of 0.5% gives a superior increase in the implied wear resistance of the high speed steel.
  • the yttrium content of the high speed steel is within the range 0.2 to 1 weight%. It is preferred that the yttrium content of the high speed steel is more than 0.4 weight%, and less than 0.7 weight% more preferably less than 0.6 weight%, most preferably 0.5 weight%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
EP11181771A 2011-09-19 2011-09-19 Procédé de production d'acier à haute vitesse Withdrawn EP2570507A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP11181771A EP2570507A1 (fr) 2011-09-19 2011-09-19 Procédé de production d'acier à haute vitesse
EP12759474.5A EP2758558A1 (fr) 2011-09-19 2012-09-19 Procédé de production d'acier à coupe rapide
US14/345,413 US20140356218A1 (en) 2011-09-19 2012-09-19 Method for producing high speed steel
JP2014530277A JP2014530294A (ja) 2011-09-19 2012-09-19 高速度鋼の製造方法
CN201280045555.7A CN103814145A (zh) 2011-09-19 2012-09-19 用于制造高速钢的方法
PCT/EP2012/068428 WO2013041558A1 (fr) 2011-09-19 2012-09-19 Procédé de production d'acier à coupe rapide

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EP11181771A EP2570507A1 (fr) 2011-09-19 2011-09-19 Procédé de production d'acier à haute vitesse

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EP2570507A1 true EP2570507A1 (fr) 2013-03-20

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EP12759474.5A Withdrawn EP2758558A1 (fr) 2011-09-19 2012-09-19 Procédé de production d'acier à coupe rapide

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US (1) US20140356218A1 (fr)
EP (2) EP2570507A1 (fr)
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CN (1) CN103814145A (fr)
WO (1) WO2013041558A1 (fr)

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US10612432B2 (en) * 2015-07-21 2020-04-07 Mahle International Gmbh Tribological system, comprising a valve seat ring and a valve

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CN105568152B (zh) * 2015-12-28 2017-11-28 珠海格力节能环保制冷技术研究中心有限公司 合金粉末和合金原料组合物以及合金件及其成型方法与叶片和滚子压缩机
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CN107999759A (zh) * 2017-12-21 2018-05-08 西安欧中材料科技有限公司 基于PREP工艺的CoCrMo粉末的热等静压成形方法
DE112020007281T5 (de) * 2020-12-28 2023-04-13 Mitsubishi Heavy Industries Engine & Turbocharger, Ltd. Düsenkomponente, variabler düsenmechanismus eines turboladers mit variabler geometrie, turbolader mit variabler geometrie und verfahren zur herstellung einer düsenkomponente
CN113714497B (zh) * 2021-08-04 2023-06-06 湖南工业大学 梯度粉末冶金高速钢预处理粉末及其处理方法和梯度粉末冶金高速钢制备方法
CN114574774B (zh) * 2022-01-19 2023-04-07 长沙市萨普新材料有限公司 一种湿式旋转模切刀辊用不锈粉末冶金高速钢及其制备方法
CN116352085A (zh) * 2023-05-04 2023-06-30 昆山双儒模具科技有限公司 一种热等静压净成形工艺

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JPS57143471A (en) 1981-02-28 1982-09-04 Daido Steel Co Ltd High-speed steel
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WO2013041558A1 (fr) 2013-03-28

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