US20030156965A1 - Nitrogen alloyed steel, spray compacted steels, method for the production thereof and composite material produced from said steel - Google Patents

Nitrogen alloyed steel, spray compacted steels, method for the production thereof and composite material produced from said steel Download PDF

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Publication number
US20030156965A1
US20030156965A1 US10/240,886 US24088603A US2003156965A1 US 20030156965 A1 US20030156965 A1 US 20030156965A1 US 24088603 A US24088603 A US 24088603A US 2003156965 A1 US2003156965 A1 US 2003156965A1
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steel
mass
content
nitrogen
spray
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Claudia Ernst
Volker Schuler
Bernd Gehricke
Ingolf Schruff
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EDELSTAHL WITTEN-KREFELD GmbH
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EDELSTAHL WITTEN-KREFELD GmbH
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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
    • C22C38/36—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.7% by weight of carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
    • B22D23/003—Moulding by spraying metal on a surface
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1042—Alloys containing non-metals starting from a melt by atomising
    • 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
    • C22C38/001—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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/123—Spraying molten metal
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the invention relates to a nitrogen-alloyed, ledeburitic steel with a high wear resistance.
  • the invention relates to the manufacture of this type of steel and a composite, which is manufactured using steel according to the invention.
  • Ledeburitic chromium steels are often used for tools and components requiring a high wear resistance. Such steels are indicated, for example, in the steel iron list under material numbers 1.2080 (X210Cr12), 1.2201 (X165CrV12), 1.2376 (X96CrMoV12), 1.2378 (X220CrVMo12-2), 1.2379 (X155CrVMo12-1), 1.2380 (X220CrVMo13-4), 1.2436 (X210CrW12), 1.2601 (X165CrMoV12), 1.2880 (X165CrCoMo12) and 1.2884 (X210CrCoW12).
  • the respective steels each have carbon contents exceeding 0.9 mass-%, chromium contents exceeding 10 mass-% and various additives of the elements molybdenum, vanadium and tungsten. They are primarily used for manufacturing tools and components employed for separating or cold-forming metals or processing plastics.
  • the known steels of the aforementioned kind are melted in an electric arc furnace under an ambient pressure. After the melt has been tapped, it is treated further with pan-metallurgical procedures, e.g., with a pan furnace or a degassing system, to reduce gases dissolved in the steel, e.g., the hydrogen, oxygen and nitrogen shares contained in the respective steel.
  • gases dissolved in the steel e.g., the hydrogen, oxygen and nitrogen shares contained in the respective steel.
  • gases dissolved in the steel e.g., the hydrogen, oxygen and nitrogen shares contained in the respective steel.
  • 0.1 to 0.4 mass-% of the element silicon is used for deoxidation to bind the oxygen dissolved in the liquid melt to oxides.
  • Nitrogen solubility during manufacture in electric slag furnaces under an ambient pressure is by nature very low.
  • H. Berns and J. Lueg in “Nitrogen-Alloyed Tool Steels”, Neue Wilsonte 36 (1991) 1, pp. 13-18 explained that only 0.04% nitrogen dissolves in pure iron smelts at a temperature of 1600° C. Since these contents are further reduced during the mentioned pan-metallurgical treatments, steels manufactured in this way contain only nitrogen contents of between 0.005 and 0.025 mass-%, according to experience.
  • the steels in question are additionally refined in an electric slag or arc-vacuum melting procedure.
  • the ingots or continuously cast bars are varyingly sized for delivery in a thermoforming process, e.g., via forging or rolling.
  • the object of the invention is to provide a steel material having a further improved wear resistance and dimensional stability. Also to be indicated are a procedure for manufacturing this kind of steel, and a composite generated with the use of this steel.
  • a Cr Cr content in mass-%
  • a Mo Mo content in mass-%
  • a V V content in mass-%
  • a Nb Nb content in mass-%
  • a W W content in mass-%
  • V SiN A Si +2A N ,
  • a Si Si content in mass-%
  • a N N content in mass-%.
  • an alloyed steel according to the invention fabricated via spray compacting is characterized by a high carbon and elevated nitrogen content given a simultaneously high content of special carbide-forming and nitride-forming elements, which results in a high wear resistance.
  • the work pieces manufactured out of the steel according to the invention have a higher service life even under an abrasive load.
  • the steel according to the invention is readily thermoformable despite the high alloy and hard phase contents due to the homogeneity of its structure. These properties make the steel according to the invention particularly suitable for manufacturing tools or components subjected to high levels of wear, e.g., those generally encountered during materials separation or in the plastics-processing industry owing to the filler content of modern plastics.
  • the spray-compacted, nitrogen-alloyed steels according to the invention have an elevated wear resistance and/or improved tenacity relative to the respective application.
  • the improved properties of steels according to the invention increase the service life of tools or components made out of these steels.
  • Cutting tools made out of steel according to the invention have an improved edge-holding property and improved cutting edge stability.
  • components made out of steels according to the invention have an improved resistance to cracking.
  • Steel according to the invention can further be hardened to a hardness of up to 68 HRC with the use of a suitable heat treatment procedure.
  • the advantages of steel according to the invention are achieved by combining its alloy constituents with a special manufacturing process, the known spray-compacting method.
  • Spherical drops of a steel melt are atomized in a protective gas stream using a gas atomizer during the spray compacting of steel.
  • the gas quickly cools the metal drops to a temperature lying between the liquidus and solidus, often even under the solidus.
  • the fast-moving drops with a solid or pasty consistency cooled in this way become compacted on a substrate into a dense material composite as a result of their intrinsic kinetic energy.
  • the rapid solidification from the liquid phase here makes it possible to directly influence how the structure of the sprayed ingot is formed.
  • Spray compacting has proven to be an effective process in particular to incorporate the desired nitrogen content into the mentioned ledeburitic steels.
  • spray compacting is characterized both by its effectiveness and economic efficiency. While testing the procedure according to the invention, contents of up to 0.85 mass-% nitrogen could be established in the solidified ingot by spraying with a nitrogen gas. In addition, this procedure makes it possible to preliminarily alloy the melt with a basic quantity of dissolved nitrogen and further nitrogenize the metal drops in the gas stream prior to spraying with charges like chromium nitrogen or nitrated ferrochromium.
  • spray compacting enables the manufacture of segregation and pore-free products having a homogeneous structure and high density.
  • product properties similar to those during the powder metallurgical manufacture of such products can be achieved at a higher dimensional flexibility and given fewer procedural steps.
  • steels according to the invention with particularly outstanding properties have a C content of 1.0-1.9 mass-%, an N content of 0.05-0.5 mass-%, an Si content of 0.15-1.5 mass-%, a Cr content of 5.0-10.0 mass-%, an Mo content of 0.5-5.5 mass-%, a V content ⁇ 3.5 mass-%, an Nb content ⁇ 3.5 mass-% and a W content ⁇ 3.0%.
  • Steels of this composition have an especially high wear resistance.
  • a carbon share exceeding 1 mass-% and nitrogen content exceeding 0.05 mass-% is advantageous to achieve a hardness exceeding 60 HRC.
  • the presence of the carbon and nitrogen also has a favorable influence on the quantity of included hard phases, and hence the wear behavior.
  • alloying with nitrogen has a homogenizing effect on the microstructure and limits the hard phase size during spray compacting. This has positive effects on the tenacity properties of steels according to the invention.
  • contents of the element nitrogen that exceed the value of 0.75 mass-% lead to a deterioration in the wear behavior due to higher residual austenite contents and greatly diminished hard phase sizes.
  • the silicon usually contained in steels in small quantities for reasons of deoxidation is provided with a content by weight of 0.1 to preferably 1.5 mass-% in steel according to the invention, since it remains dissolved in the basic matrix and increases secondary hardness. It was also found that increasing silicon content yields a reduction in the residual austenite content caused by increasing nitrogen contents. The residual austenite content reduces wear resistance as a “soft” structural component. In this way, the nitrogen and silicon contained in the steel according to the invention in the specified limits optimally enhance and influence each other in their effect on hardness and wear resistance. The joint effect of the nitrogen and silicon contents on the residual austenite content is shown on FIG.
  • Cobalt is not contained in steel with a composition according to the invention, since this element can have negative effects on the tenacity, and would help drive up material costs.
  • the chromium content is limited to values ⁇ 11.5 mass-%, and preferably lies in the specified, lower content range, so as to also positively influence the tenacity of the steel generated according to the invention.
  • steel according to the invention may also be beneficial for steel according to the invention to have additional precipitation-hardening elements, such as up to 0.75 mass-% nitrogen, up to 0.05 mass-% boron, up to 0.5 mass-% titanium, up to 0.5 mass-% zirconium and/or up to 0.25 mass-% aluminum.
  • additional precipitation-hardening elements such as up to 0.75 mass-% nitrogen, up to 0.05 mass-% boron, up to 0.5 mass-% titanium, up to 0.5 mass-% zirconium and/or up to 0.25 mass-% aluminum.
  • steel according to the invention has an optimized wear resistance if the wear factor S v corresponding to the sum of its weighted contents of carbide-forming elements Cr, Mo, V, Nb and W measures between 0.55 and 3.42.
  • an optimized silicon-nitrogen ratio V SiN is to be set in order to influence the effect of the austenite stabilizing element nitrogen by the ferrite stabilizing effect of the element silicon, and further optimize the wear resistance in steels according to the invention. It has been shown that, when observing the range of 0.21 to 3.31 provided according to the invention for the nitrogen-silicon ratio, the residual austenite constituents harmful to wear resistance can be diminished to values ⁇ 25% already after a single tempering.
  • nitrogen-alloyed steel according to the invention contains additional hard materials, such as titanium carbide (TiC), silicon carbide (SiC), niobium carbide (NbC), chromium carbide (CrC), titanium nitride (TiN), tungsten carbide (WC), in its matrix, which had been injected as solid particles in the spray jet during spray compacting.
  • additional hard materials such as titanium carbide (TiC), silicon carbide (SiC), niobium carbide (NbC), chromium carbide (CrC), titanium nitride (TiN), tungsten carbide (WC), in its matrix, which had been injected as solid particles in the spray jet during spray compacting.
  • the aforementioned object is achieved by spray compacting the steel using nitrogen as the spray gas, thermoforming the steel after spray compacting at initial temperatures of up to 1150° C., cooling the thermoformed steel, reheating the cooled steel to an austenizing temperature of 1075° C. to 1225° C., quenching the reheated steel and tempering the quenched steel at temperatures of 150° C.-625° C. Tempering preferably takes place at temperatures of between 150° C. and 300° C. or between 500° C. and 625° C. As opposed to the pressure-nitrogenized steels, the optimal setting of the silicon-nitrogen ratio eliminates the need for deep-freezing for residual austenite conversion. Observing the procedural parameters according to the invention makes it possible to achieve a hardness of up to 68 HRC, even if supplementary forming steps are required during further processing. Thermoforming can here take place via forging or rolling.
  • steel according to the invention can be used especially well to generate a composite material having at least one first layer produced by a first steel and at least a second layer formed by a spray compacted steel according to the invention, wherein the steel of the first layer has a different composition than the spray-compacted steel.
  • the varying properties of the individual layers can be optimally combined.
  • the steel according to the invention can form a wear resistant cover layer on a tenacious first layer.
  • Table 1 shows the chemical compositions of seven steels A-G in mass-%.
  • the wear factor S v the silicon-nitrogen ratio V SiN and the abrasion in grams determined in a wear test are recorded for each of the steels.
  • Steels A-D are steels according to the invention, while steels E-G are cited for comparison.
  • FIGS. 2 and 3 each show the micrograph of nitrogen-alloyed steel manufactured via spray compacting according to the invention in an annealed state, FIG. 2 showing the respective microstructure at a magnification of 100:1, and FIG. 3 at a magnification of 500:1.
  • FIGS. 4 and 5 show a corresponding depiction of the microstructure of the same steel without added nitrogen when the steel is manufactured in a conventional manner via smelt metallurgy.
  • FIGS. 2 and 3 The high structural homogeneity readily visible from FIGS. 2 and 3 enables the problem-free forming of the spray-compacted ingot via forging or rolling. Ingot or diffusion annealing can precede forming.
  • the improved formability of steels generated according to the invention makes it possible to execute thermoforming at lower temperatures relative to the conventional procedure.
  • the respectively required hardness of the components or tools made out of the steels according to the invention can be set after shaping by hardening at an austenizing temperature of between 1075° C. and 1225° C. with subsequent tempering between 150° C. and 625° C., wherein hardnesses of up to 68 HRC can be reached.
  • Steels according to the invention have a balanced ratio between the carbide or carbonitride-forming elements, which is characterized by a wear factor S v determined in the manner described above and lying between 0.55 and 3.42. This balanced ratio between the carbide/carbonitride formers results in a superior wear resistance of steels according to the invention, which was corroborated in wear tests (FIG. 6).
  • the forged ingot was then soft annealed. Thread rolling dies with dimensions of 85 mm ⁇ 50 mm ⁇ 24 mm and 95 mm ⁇ 50 mm ⁇ 24 mm were then manufactured out of the soft annealed material. These tools were subsequently brought to a hardness of 62 HRC via heat treatment.
  • the thread rolling dies were used to manufacture screws out of a stainless steel with material number 1.4401 according to the steel-iron list.
  • the work results and wear condition of the tools manufactured out of the steel according to the invention were compared with the work results and wear condition of thread rolling dies manufactured out of a steel made via smelt metallurgy having an identical chemical composition, but no added nitrogen. It was shown that thread rolling dies manufactured out of the steel according to the invention had twice the service life as the thread rolling dies made out of conventional steel of identical composition.
  • the tools fabricated out of the steel according to the invention could be used to make 140,000 screws, while the tools manufactured out of the conventionally produced steel were worn after making 70,000 screws. Special emphasis in this regard must be placed on the excellent dimensional stability of the tools made out of the steel according to the invention at the thread crests.
  • the nitrogen-alloyed steel C on Table 1 manufactured via spray compacting was drawn out to dimensions of 160 mm ⁇ 160 mm and soft annealed.
  • the forged steel was used to make blanking dies for chain links comprised of a micro-alloyed steel, which were punched out of 4 mm thick sheets.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Heat Treatment Of Articles (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Heat Treatment Of Steel (AREA)
US10/240,886 2000-04-18 2001-04-18 Nitrogen alloyed steel, spray compacted steels, method for the production thereof and composite material produced from said steel Abandoned US20030156965A1 (en)

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DE10019042A DE10019042A1 (de) 2000-04-18 2000-04-18 Stickstofflegierter, sprühkompaktierter Stahl, Verfahren zu seiner Herstellung und Verbundwerkstoff hergestellt aus dem Stahl
DE10019042.1 2000-04-18

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US (1) US20030156965A1 (ja)
EP (1) EP1274872B1 (ja)
JP (1) JP2004501276A (ja)
AT (1) ATE278816T1 (ja)
DE (2) DE10019042A1 (ja)
DK (1) DK1274872T3 (ja)
ES (1) ES2230308T3 (ja)
WO (1) WO2001079575A1 (ja)

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US20100291407A1 (en) * 2008-01-21 2010-11-18 Hitachi Metals, Ltd. Alloy to be surface-coated and sliding members
US20120107170A1 (en) * 2010-11-03 2012-05-03 Kuen-Shyang Hwang Alloy steel powder and their sintered body
TWI415956B (zh) * 2010-10-01 2013-11-21 Taiwan Powder Technologies Co Ltd 具有一大燒結窗的含鈦合金鋼金屬粉末及其燒結體
CN105112788A (zh) * 2015-08-10 2015-12-02 霍邱县忠振耐磨材料有限公司 一种球磨机用中碳中铬合金钢球及其制备方法
CN105112787A (zh) * 2015-08-10 2015-12-02 霍邱县忠振耐磨材料有限公司 一种球磨机用稀土铬钼钒合金钢球及其制备方法
US20160271667A1 (en) * 2014-06-19 2016-09-22 Nippon Steel & Sumkin Hardfacing Co., Ltd. Roll for winding equipment in hot rolling factory
EP3305934A4 (en) * 2016-03-18 2018-05-02 Hitachi Metals, Ltd. Cold working tool material and cold working tool manufacturing method
CN109468533A (zh) * 2018-11-22 2019-03-15 杨佳意 一种生产钻头的合金钢材料及其制备工艺
US10422018B2 (en) 2013-05-17 2019-09-24 G. Rau Gmbh & Co. Kg Method and device for remelting and/or remelt-alloying metallic materials, in particular Nitinol

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DE102006051936B4 (de) * 2006-11-01 2014-03-20 Zollern Bhw Gleitlager Gmbh & Co. Kg Verfahren zur Herstellung zweier miteinander verbundener Schichten und nach dem Verfahren herstellbares Funktionsbauteil
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WO2001079575A1 (de) 2001-10-25
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EP1274872A1 (de) 2003-01-15
EP1274872B1 (de) 2004-10-06

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