EP2253398B1 - Wear-resistant material - Google Patents
Wear-resistant material Download PDFInfo
- Publication number
- EP2253398B1 EP2253398B1 EP09450242.4A EP09450242A EP2253398B1 EP 2253398 B1 EP2253398 B1 EP 2253398B1 EP 09450242 A EP09450242 A EP 09450242A EP 2253398 B1 EP2253398 B1 EP 2253398B1
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- EP
- European Patent Office
- Prior art keywords
- carbon
- nitrides
- nitrogen
- niobium
- wear
- 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.)
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- 239000000463 material Substances 0.000 title claims description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 79
- 239000010955 niobium Substances 0.000 claims description 50
- 229910052799 carbon Inorganic materials 0.000 claims description 48
- 229910052757 nitrogen Inorganic materials 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 229910045601 alloy Inorganic materials 0.000 claims description 36
- 239000000956 alloy Substances 0.000 claims description 36
- 229910052758 niobium Inorganic materials 0.000 claims description 33
- 239000011651 chromium Substances 0.000 claims description 30
- 239000011159 matrix material Substances 0.000 claims description 25
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 20
- 238000005260 corrosion Methods 0.000 claims description 20
- 230000007797 corrosion Effects 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- 229910052715 tantalum Inorganic materials 0.000 claims description 18
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 150000004767 nitrides Chemical class 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 16
- 150000001247 metal acetylides Chemical class 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- 238000001513 hot isostatic pressing Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000889 atomisation Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000734 martensite Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- -1 carbon nitrides Chemical class 0.000 claims 4
- 238000011109 contamination Methods 0.000 claims 4
- 238000000926 separation method Methods 0.000 claims 1
- 238000003856 thermoforming Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 description 12
- 235000019589 hardness Nutrition 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000005496 tempering Methods 0.000 description 7
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005255 carburizing Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910020598 Co Fe Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910001315 Tool steel Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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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
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- 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
- C22C33/0207—Using a mixture of prealloyed powders or a master alloy
- C22C33/0228—Using a mixture of prealloyed powders or a master alloy comprising other non-metallic compounds or more than 5% of graphite
-
- 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%
- C22C33/0292—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 more than 5% preformed carbides, nitrides or borides
-
- 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
-
- 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
- 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
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/28—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in one step
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- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/004—Dispersions; Precipitations
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
Definitions
- the invention relates to a method for the production and to a wear-resistant material containing carbon (C), nitrogen (N), oxygen (O), niobium and / or tantalum (Nb / Ta) and metallic elements and impurities as the remainder with a Microstructure consisting of a metal matrix and embedded in these hard phases.
- metallic materials consist of a tough or tough matrix and distributed in this hard phases, which are usually formed as interstitial compounds.
- a wear-reducing effect of hard phase deposits is well known, with a higher hard phase content in the matrix as much as possible reducing abrasive removal from the workpiece surface when the support force for the hard particles and the matrix hardness are high.
- wear-resistant iron base materials e.g. Cold work steels, from a hard, preferably thermally tempered metal matrix with distributed in this, precipitated from the residual melt of the alloy during solidification, carbides.
- Carbide formation in a ledeburitic solidification of an alloyed melt in a cast billet may also be inhomogeneous due to a low solidification rate in the center thereof and segregation to coarse hard phases
- it is known, for example from EP 1721 999 A1 apply powder metallurgical manufacturing process.
- an alloyed liquid melt after flowing out of a nozzle is separated by high-pressure gas jets into small droplets which naturally cool at high speed and thereby precipitate fine hard phase particles upon solidification.
- hot isostatic pressing (HIP) or by deformation of the powder in a container a production of a largely dense material with a high proportion of uniformly distributed hard phases with a small particle size takes place.
- HIP hot isostatic pressing
- alloys which have a high content of carbide formers, in particular monocarbide formers, with a corresponding carbon content and a chromium concentration in the matrix of more than 12.0% by weight.
- a corrosion and wear resistant tool steel discloses the EP 1721999 , wherein contents of 6.0 to 11.0 vol .-% vanadium are provided in the alloy to form a high hard phase content. In this case, a tendency to form ferrite in the structure by cobalt concentrations of 1.5 to 5.0 % by weight is overcome.
- Alloys in which no expensive chromium is to be lost by carbide formation discloses the DE 42 31 695 A1 and proposes to alloy a PM tool steel with 1 to 3.5 wt% nitrogen.
- Nitrogen for hard phase formation becomes an advantageous measure for the production of wear resistant materials in the WO 2007/024 192 A1 proposed.
- the invention has the object to provide a method for creating a material which has a high resistance to abrasion under abrasion stress.
- this material in an alloy variant should also be resistant to chemical corrosion.
- the object of the aforementioned invention is essentially achieved by a method for producing a wear-resistant material, wherein in a first step, a metallic, liquid alloy containing Nioblotantal (NbTa) with a concentration of 3.0 to 18.0 wt .-%, and a content of carbon and / or nitrogen, in which no primary precipitates of carbides and / or nitrides are formed above the atomization temperature or liquidus, is atomized to powder material, after which the powder is subjected to a process for increasing the carbon content and / or the nitrogen content and / or the oxygen content and subsequently subjected to a hot compacting, in particular a hot isostatic pressing, or wherein the pressed body or HIP body is subjected to a hot deformation or a heat treatment.
- the powder is mixed with elemental carbon and / or treated in a carbon and nitrogen-releasing atmosphere optionally at elevated temperature and subsequently compacted to produce wear-resistant materials .
- the advantages of the method according to the invention for the production of wear-resistant materials consist essentially in the fact that due to the niobium / tantalum concentration of 3.0 to 18.0 wt .-% and increasing the carbon content to 0.3 to 3.0 wt .-% and the nitrogen content to 0.05 bis 4.0 wt .-% high-hardness niobium and / or tantalum monocarbides, Mononitride or Monokarbonitride be achieved in a homogeneous distribution with a small diameter and such a high abrasion resistance is achieved.
- the oxygen content of 0.002 to 0.25 in the material acts on the one hand as a formation nucleus for the hard phase with respect to hard particles with specific, small size in a homogeneous distribution in the matrix and on the other hand as a separate hard material former.
- the hard material particles have a diameter of at most 50 microns, because at larger phases, the risk of breaking them out of the matrix is increased dramatically. Smaller diameters than 0.2 ⁇ m of the hard phases provide only a slight, abrasion-reducing effect.
- the matrix of the wear-resistant alloy has a martensitic microstructure, then the material itself has an increased abrasion-reducing hardness, minimizing as far as possible the risk of breaking hard phases out of the structure during wear.
- compositions for a material with high resistance to abrasion with Abrasionsbe carriedung and with high corrosion resistance containing, in wt .-% Carbon (C) 0.5 to 2.5 Nitrogen (N) 0.15 to 0.6 Silicon (Si) 0.2 to 1.5 Manganese (Mn) 0.3 to 2.0 Chrome (Cr) 10.0 to 20.0 Niobium / tantalum (Nb / Ta) 3.0 to 15.0 Molybdenum (Mo) 0.5 to 3.0 Vanadium (V) 0.1 to 1.0 Titanium (Ti) 0.001 to 1.0 Iron (Fe) rest and production-related impurities, with a structure consisting of a metal matrix and embedded in these hard phases, with the proviso that the hard phases are formed as carbides and / or nitrides and / or carbonitrides and / or Oxikarbonitrife and have a diameter of at most 50 microns and at least 0.2 microns, with The proviso that the relationship
- the concentrations of the alloying metals are coordinated in this material with respect to the carbon activity and the carbide formation kinetics of the respective elements, the contents of the monocarbide formers being decisive for the intended carbon concentration.
- Nitrogen is limited with a content of 0.6 wt .-% to the top, because in the given case, the hard phases should be designed mainly as carbides. Below 0.15 wt.% Nitrogen, the solidification effect of the matrix is too low, so that the content limits in wt.% Are 0.15 to 0.6 nitrogen.
- Silicon acts as a deoxidation metal and influences the microstructural transformation of the alloy during the heat treatment.
- a minimum content of 0.2% by weight of Si is important in terms of effective oxide formation, whereas higher contents than 1.5% by weight adversely affect toughness.
- a manganese content of 0.3% by weight or more is intended for setting sulfur in the metal, with more than 2.0% by weight of Mn promoting disadvantageous austenite stability.
- Chromium and molybdenum provide corrosion resistance of the alloy at minimum concentrations of 10.0 and 0.5 wt%, but may also be effective as carbide formers. Higher contents than 20.0% by weight of Cr and 3.0% by weight of Mo disadvantageously lead to a stabilization of ferrite in a heat treatment.
- Vanadium and titanium should not exceed contents of 1.0 wt .-%, because carbides of these elements to a large extent dissolve Cr or incorporate into the crystal lattice, which can cause depletion of Cr in the edge region of the matrix.
- the elements niobium and tantalum are elements that form in the alloy from a content of 3.0 wt .-% hard, the wear resistance of the material promoting monocarbides. It is important that these elements Nb / Ta show only a slight tendency to incorporate further elements, in particular chromium, in the carbide or carbonitride formation in the crystal lattice, so that in the vicinity of these hard phases no depletion of the matrix of alloy components, especially of chromium and Molybdenum, and thus no adverse effect on the corrosion resistance of the material is formed.
- a low wear and a high corrosion resistance of the material is achieved, which contains material in wt .-% Carbon (C) more than 0.3 to 1.0 Nitrogen (N) 1.0 to 4.0 Silicon (Si) 0.2 to 1.5 Manganese (Mn) 0.3 to 1.5 Chrome (Cr) 10.0 to 20.0 Niobium / tantalum (Nb / Ta) 3.0 to 15.0 Molybdenum (Mo) 0.5 to 3.0 Vanadin (V) 0.1 to 1.0 Titanium (Ti) 0.001 to 1.0 Iron (Fe) rest and production-related impurities, with a structure consisting of a metal matrix and embedded in it Hard phases, with the proviso that the hard phases as carbides and / or nitrides and / or carbonitrides and / or Oxikarbonitride are formed and have a maximum diameter of 50 microns and at least 0.2 microns, with the proviso that
- the high nitrogen content of 1.0 to 4.0 wt .-% at carbon concentrations of 0.3 to 1.0 wt .-% leads to substantially nitrides formed hard phases, whereby the chromium and molybdenum induced passive layer formation and corrosion resistance are promoted.
- a material produced by a method mentioned above can be provided cheaply and economically, which in wt .-% Carbon (C) 0.5 to 3.0 Nitrogen (N) 0.15 to 0.6 Silicon (Si) 0.2 to 1.5 Manganese (Mn) 0.3 to 2.0 Chrome (Cr) 10.0 to 20.0 Niobium / tantalum (Nb / Ta) 3.0 to 15.0 Molybdenum (Mo) 0.5 to 3.0 Vanadin (V) 0.1 to 1.0 Titanium (Ti) 0.001 to 1.0 Iron (Fe) rest with manufacturing-related impurities, with a structure consisting of a metal matrix and embedded in these hard phases, with the proviso that the hard phases are formed as carbides and / or nitrides and / or carbonitrides and / or Oxikarbonitride and a diameter of at most 50 micro
- the alloy may have the following composition and ratios of the elements in% by weight with lowered chromium contents Carbon (C) 1.0 to 3.5 Nitrogen (N) 0.05 to 0.4 Silicon (Si) 0.2 to 1.5 Manganese (Mn) 0.3 to 1.0 Chrome (Cr) 2.5 to 6.0 Niobium / tantalum (Nb / Ta) 3.0 to 18.0 Molybdenum (Mo) 2.0 to 10.0 Tungsten (W) 0.1 to 12.0 Vanadin (V) 0.1 to 3.0 Cobalt (Co) 0.1 to 12.0 Iron (Fe) rest with production-related impurities, with a microstructure consisting of a metal matrix and embedded in these hard phases, with the proviso that the hard phases are formed as carbides and / or nitrides and / or carbonitrides and / or Oxkarbonitride
- the highly wear-resistant tool material which is based on a type of high-speed steel alloy, can be easily tempered to high hardness values and has outstanding toughness despite its high hardness. Particularly pronounced is the wear resistance of the cutting tools formed from this alloy, which Tools thus have a particularly long service life in rough and interrupted cut.
- the inventive method of the type mentioned is determined such that in a first step, a metallic liquid alloy containing niobium / tantalum (Nb / Ta) with a concentration of 3.0 to 18.0 wt .-%, and a content of carbon and / or Nitrogen, in which no primary precipitates of carbides and / or nitrides are formed above the atomization temperature or liquidus temperature, is atomized to powder material, after which the powder subjected to a process for increasing the carbon content and / or the nitrogen content and / or the oxygen content and then a hot compacting , in particular a hot isostatic pressing, wherein the pressed body or HIP body is alternatively subjected to a hot working and / or a heat treatment.
- the method according to the invention has the advantage that materials with a high carbide-nitride or carbonitride hard material content can be produced, the hard-material particles having small diameters and homogeneous distribution in the matrix.
- the matrix elements can by a thermal tempering or by hardening and tempering of the material impart this high strength and prevent stripping or breaking the larger, optimized hard particles as far as possible. As a result, a particularly pronounced wear resistance of the material is achieved.
- a carburizing and / or an increase in the nitrogen content in adjusting the oxygen content of the pre-alloyed metal powder according to the invention by admixed, elemental carbon and / or by a carbon and / or nitrogen and / or oxygen-releasing atmosphere, in particular at elevated temperature before or at a Hot compaction done.
- other hard material particles having a size of from 2 to 50 .mu.m can be admixed to the powder material to an extent of up to 25% by volume, which are consequently effective in reducing the wear on the given material.
- Tab. 1 on page 11 shows the composition of two commercially available, wear-resistant alloys with the designations X190 CrVMo 20 4 1, X90 CrVMo 18 1 1, corrosion-resistant, inventive alloys with the designations A, B, C, and of cutting materials according to the invention with the designations D, E, F.
- the commercial alloys were produced by the PM method with a deformation of the HIP block ( H schreib- I sostatisch-ge p resst) greater than 6-fold.
- Powders for the samples designated A, B, C were made from alloys having the following main components in wt%: description Si Mn Cr Not a word V W Nb Co Fe A 12:43 12:42 11.92 2.21 12:08 12:07 9:02 12:08 rest B 12:51 12:44 16:41 2.19 12:09 12:07 9:56 12:05 rest C 12:43 12:42 11.92 2.21 12:05 12:06 9:02 12:08 rest produced by atomizing by means of nitrogen gas.
- Atomization with nitrogen was further carried out using melts designated D, E, F with the main constituents in% by weight: description Si Mn Cr Not a word V W Nb Co Fe D 0.3 0.4 4.15 2.94 1:52 2.13 3:34 12:12 rest e 12:28 12:35 3.95 2.84 1:47 2.23 3:45 8.21 rest F 12:37 12:33 3:58 4.1 1.84 5:07 10.73 7:07 rest
- the alloyed metal powder was then placed under nitrogen atmosphere in steel containers and knock compacted, followed by welding of the containers and hot isostatic pressing at a temperature of 1165 ° C.
- Tab. 1 shows the chemical composition of known materials (X190 CrVMo 20 4 1 and X90 CrMoV 18 1 1) and those of steel samples according to the invention
- the corrosion behavior of the alloys was determined from current density potential curves on the samples according to ASTM G65 in 1N H 2 SO 4 , 20 ° C, with a quenching of the same from 1100 ° C and 1070 ° C and a tempering at 200 ° C. ,
- Fig. 1 shows, in the relevant potential range of about -300mV to + 300mV, the comparative alloy X190 CrVMo 20 4 1 essentially the highest passive current density in comparison with the inventively assembled samples A, B, C, which reveals their improved corrosion behavior.
- Fig. 2 shows the hardness of the differently composite alloys after curing, depending on the tempering temperature after two times Tempering.
- the respective hardening temperature can be taken from the designation field for the alloys.
- the materials A and C of the alloy according to the invention on a comparatively low tempering hardness, because their respective carbon content of improved corrosion resistance due to (see Fig.1 ) was chosen low.
- alloys D, E and F are significantly higher in the range of tempering temperatures between 500 and 600 ° C, which discloses a clear superiority of the same for use of, for example, cutting and forming elements.
- Fig. 3 shows the wear behavior of the samples made from the alloys, determined according to the VDI progress reports " Nitrogen-alloyed tool steels ", Series 5, No. 188 (1990), p. 129 described pin-disk test with Flint 80 grit. The hardnesses of the samples are above the respective bars in Fig. 3 specified. Both the corrosion resistant alloy B and the alloys E and F according to the invention show superior resistance to wear, indicating a correspondingly favorable choice of carbon and niobium contents.
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Description
Die Erfindung bezieht sich auf ein Verfahren zur Herstellung und auf einen verschleißbeständigen Werkstoff, enthaltend Kohlenstoff (C), Stickstoff (N), Sauerstoff (O), Niob und/oder Tantal (Nb/Ta) sowie metallische Elemente und Verunreinigungen als Rest mit einem Gefüge, bestehend aus einer Metallmatrix und in diese eingelagert Hartphasen.The invention relates to a method for the production and to a wear-resistant material containing carbon (C), nitrogen (N), oxygen (O), niobium and / or tantalum (Nb / Ta) and metallic elements and impurities as the remainder with a Microstructure consisting of a metal matrix and embedded in these hard phases.
Gemäß dem technischen Ansatz bestehen verschleißresistente, metallische Werkstoffe aus einer zähfesten oder zähharten Matrix und in dieser verteilt Hartphasen, welche zumeist als interstitielle Verbindungen ausgeformt sind.According to the technical approach wear-resistant, metallic materials consist of a tough or tough matrix and distributed in this hard phases, which are usually formed as interstitial compounds.
Eine verschleißmindernde Wirkung von Hartphaseneinlagerungen ist allgemein bekannt, wobei ein höherer Hartphasenanteil in der Matrix einen abrasiven Abtrag von der Werkstückoberfläche höchstmöglich vermindert, wenn die Stützkraft für die Hartstoffpartikel und die Matrixhärte hoch sind.A wear-reducing effect of hard phase deposits is well known, with a higher hard phase content in the matrix as much as possible reducing abrasive removal from the workpiece surface when the support force for the hard particles and the matrix hardness are high.
Nach dem Stand der Technik bestehen verschleißresistente Eisenbasiswerkstoffe, z.B. Kaltarbeitsstähle, aus einer harten, vorzugsweise thermisch vergüteten Metallmatrix mit in dieser verteilten, aus der Restschmelze der Legierung bei der Erstarrung ausgeschiedenen, Karbiden.According to the prior art, wear-resistant iron base materials, e.g. Cold work steels, from a hard, preferably thermally tempered metal matrix with distributed in this, precipitated from the residual melt of the alloy during solidification, carbides.
Eine Karbidbildung bei einer ledeburitischen Erstarrung einer legierten Schmelze in einem Gussblock kann auch aufgrund einer niedrigen Erstarrungsgeschwindigkeit im Zentrum desselben und durch Seigerung zu groben Hartphasen mit inhomogener Um eine höhere Konzentration von Hartphasen im Werkstoff, insbesondere bei gleichmäßiger Verteilung in diesem, zu erreichen, ist es bekannt, z.B. aus
Eine Steigerung der Verschleißresistenz mittels Erhöhung des Volumenanteils von Hartphasen in der Matrix eines Werkstoffes und in der Folge einer Erhöhung der Konzentration der die Hartphasen bildenden Elemente hat jedoch verfahrenstechnische und reaktionskinetische Grenzen. Primäre Ausscheidungen im Flüssigmetall können während des Verdüsungsablaufes zu einer Verringerung der Ausströmung derselben aus der Düse oder zu einem totalen Zuwachsen der Durchtrittsöffnung führen und derart die Herstellbarkeit nachteilig beeinflussen. Größere Legierungsüberhitzungen im Vorratsgefäß einer Anlage zur Metallpulverherstellung können auch metallurgische und/oder reaktionskinetische Nachteile haben.An increase in the wear resistance by increasing the volume fraction of hard phases in the matrix of a material and in consequence of an increase in the concentration of the hard phase-forming elements, however, has procedural and reaction kinetic limits. Primary precipitations in the liquid metal can lead to a reduction in the outflow of the same from the nozzle or to a total growth of the passage opening during the atomization process and thus adversely affect the manufacturability. Larger alloy overheating in the storage vessel of a plant for the production of metal powder may also have metallurgical and / or reaction kinetic disadvantages.
Aufgrund des Bedarfs an höchst verschleißresistenten Werkstoffen, welche gegebenenfalls eine überlegene Korrosionsbeständigkeit aufweisen sollen, wurden vielfach Legierungen vorgeschlagen, welche einen hohen Gehalt an Karbidbildnern, insbesondere Monokarbidbildnern, mit entsprechendem Kohlenstoffgehalt und einer Chromkonzentration in der Matrix von über 12.0 Gew.-% haben.Due to the need for highly wear resistant materials, which are believed to have superior corrosion resistance, have been In many cases, alloys have been proposed which have a high content of carbide formers, in particular monocarbide formers, with a corresponding carbon content and a chromium concentration in the matrix of more than 12.0% by weight.
In der
Um auch bei langsamer Abkühlung eines Bauteiles eine verschleißfeste Matrix mit harter, martensitischer Struktur und einem hohen Karbidanteil zu erreichen, ist gemäß
Einen korrosions-und verschleißbeständigen Werkzeugstahl offenbart die
Legierungen, bei welchen kein teures Chrom durch Karbidbildung verloren gehen soll, offenbart die
Stickstoff zur Hartphasenbildung wird als vorteilhafte Maßnahme für die Herstellung von verschleißbeständigen Werkstoffen in der
Ausgehend vom technischen Bedarf und dem technologischen Stand der Technik setzt sich die Erfindung zum Ziel, ein Verfahren zur Schaffung eines Werkstoffes anzugeben, welcher einen hohen Widerstand gegen Abtrag bei Abrasionsbeanspruchung aufweist. Mit Vorteil soll dieser Werkstoff in einer Legierungsvariante auch gegen chemische Korrosion beständig zusammengesetzt sein.Based on the technical requirements and the technological state of the art, the invention has the object to provide a method for creating a material which has a high resistance to abrasion under abrasion stress. Advantageously, this material in an alloy variant should also be resistant to chemical corrosion.
Das Ziel der eingangs genannten Erfindung wird im Wesentlichen durch ein Verfahren zur Herstellung eines verschleißbeständigen Werkstoffes erreicht, wobei in einem ersten Schritt eine metallische, flüssige Legierung enthaltend NioblTantal (NbTa) mit einer Konzentration von 3.0 bis 18.0 Gew.-%, sowie einem Gehalt an Kohlenstoff und/oder Stickstoff, bei welcher keine Primärausscheidungen an Karbiden und/oder Nitriden oberhalb der Verdüsungstemperatur oder Liquidustemperatur gebildet werden, zu Pulvermaterial verdüst wird, wonach das Pulver einem Verfahren zur Erhöhung des Kohlenstoffgehaltes und/oder des Stickstoffgehaltes und/oder des Sauerstoffgehaltes unterworfen und im Folgenden einem Heißkompaktieren, insbesondere einem heißisostatischen Pressen unterworfen wird, oder wobei der Pressling bzw. HIP-Körper einer Warmverformung oder einer Wärmebehandlung unterworfen wird. Verfahrenstechnisch wird zur Herstellung von verschleißfesten Werkstoffen das Pulver mit elementarem Kohlenstoff gemischt und/oder in einer Kohlenstoff und Stickstoff abgebenden Atmosphäre gegebenenfalls bei erhöhter Temperatur behandelt und nachfolgend kompaktiert. The object of the aforementioned invention is essentially achieved by a method for producing a wear-resistant material, wherein in a first step, a metallic, liquid alloy containing Nioblotantal (NbTa) with a concentration of 3.0 to 18.0 wt .-%, and a content of carbon and / or nitrogen, in which no primary precipitates of carbides and / or nitrides are formed above the atomization temperature or liquidus, is atomized to powder material, after which the powder is subjected to a process for increasing the carbon content and / or the nitrogen content and / or the oxygen content and subsequently subjected to a hot compacting, in particular a hot isostatic pressing, or wherein the pressed body or HIP body is subjected to a hot deformation or a heat treatment. Technically, the powder is mixed with elemental carbon and / or treated in a carbon and nitrogen-releasing atmosphere optionally at elevated temperature and subsequently compacted to produce wear-resistant materials .
Die Vorteile des erfindungsgemäßen Verfahrens zur Herstellung von verschleißfesten Werkstoffen bestehen im Wesentlichen darin, dass infolge der Niob/Tantal-Konzentration von 3.0 bis 18.0 Gew.-% und der Steigerung des Kohlenstoffgehaltes auf 0.3 bis 3.0 Gew.-% sowie des Stickstoffgehaltes auf 0.05 bis 4.0 Gew.-% hochharte Niob und/oder Tantal-Monokarbide, Mononitride oder Monokarbonitride in homogener Verteilung mit geringem Durchmesser erreicht werden und derart ein hoher Abrasionswiderstand erreicht wird.The advantages of the method according to the invention for the production of wear-resistant materials consist essentially in the fact that due to the niobium / tantalum concentration of 3.0 to 18.0 wt .-% and increasing the carbon content to 0.3 to 3.0 wt .-% and the nitrogen content to 0.05 bis 4.0 wt .-% high-hardness niobium and / or tantalum monocarbides, Mononitride or Monokarbonitride be achieved in a homogeneous distribution with a small diameter and such a high abrasion resistance is achieved.
Durch geringere Anteile an Kohlenstoff als 0.3 Gew.-% und Stickstoff als 0.05 Gew.-% kann das Bildungspotential von Verbindungen mit Gehalten von 3.0 bis 18.0 Gew.-% Nb/Ta nicht ausreichend ausgenützt werden, hingegen wirken höhere Gehalte als 3.0 bis 4.0 Gew.-% an Kohlenstoff und Stickstoff gefügeverschlechternd.With lower contents of carbon than 0.3% by weight and nitrogen than 0.05% by weight, the formation potential of compounds with contents of 3.0 to 18.0% by weight Nb / Ta can not be sufficiently exploited, whereas higher contents than 3.0 to 4.0 are effective Wt .-% of carbon and nitrogen microstructural.
Der Sauerstoffgehalt von 0.002 bis 0.25 im Werkstoff wirkt einerseits als Bildungskeim für die Hartphase im Hinblick auf Hartstoffteilchen mit bestimmter, geringer Größe in homogener Verteilung in der Matrix und andererseits als eigener Hartstoffbildner.The oxygen content of 0.002 to 0.25 in the material acts on the one hand as a formation nucleus for the hard phase with respect to hard particles with specific, small size in a homogeneous distribution in the matrix and on the other hand as a separate hard material former.
Höhere Sauerstoffgehalte als 0.25 Gew.-% verspröden die Hartphasen, wohingegen geringere Gehalte als 0.002 Gew.-% keine ausgeprägte Keimwirkung haben.Higher oxygen contents than 0.25 wt .-% embrittle the hard phases, whereas lower contents than 0.002 wt .-% have no pronounced germination.
Es ist erfindungsgemäß wichtig, dass die Hartstoffteilchen einen Durchmesser von höchstens 50 µm aufweisen, weil bei größeren Phasen die Gefahr des Ausbrechens derselben aus der Matrix sprunghaft erhöht ist. Geringere Durchmesser als 0.2 µm der Hartphasen erbringen nur eine geringe, abrasionsvermindernde Wirkung.It is important in the invention that the hard material particles have a diameter of at most 50 microns, because at larger phases, the risk of breaking them out of the matrix is increased dramatically. Smaller diameters than 0.2 μm of the hard phases provide only a slight, abrasion-reducing effect.
Wenn, wie gemäß der Erfindung, die Matrix der verschleißbeständigen Legierung eine martensitische Gefügestruktur aufweist, so hat der Werkstoff selbst eine erhöhte abrasionsmindernde Härte, wobei höchstmöglich eine Gefahr des Ausbrechens von Hartphasen aus dem Gefüge bei Verschleißbeanspruchung minimiert ist.If, as in the invention, the matrix of the wear-resistant alloy has a martensitic microstructure, then the material itself has an increased abrasion-reducing hardness, minimizing as far as possible the risk of breaking hard phases out of the structure during wear.
Erfindungsgemäß hat sich für einen Werkstoff mit hohem Widerstand gegen Abtrag bei Abrasionsbeanspruchung und mit hoher Korrosionsbeständigkeit eine Zusammensetzung ergeben, enthaltend in Gew.-%
mit einem Gefüge bestehend aus einer Metallmatrix und in diese eingelagert Hartphasen, mit der Maßgabe, dass die Hartphasen als Karbide und/oder Nitride und/oder Karbonitride und/oder Oxikarbonitrife gebildet sind und einen Durchmesser von höchstens 50 µm und mindestens 0.2 µm aufweisen, mit der Maßgabe, dass der Zusammenhang von Kohlenstoffgehalt und der Konzentration von Niob/Tantal sowie Vanadin und Titan einen Wert, gebildet aus
erfüllt, und die Zahl U größer als 6, jedoch kleiner als 10 ist. According to the invention there has been a composition for a material with high resistance to abrasion with Abrasionsbeanspruchung and with high corrosion resistance containing, in wt .-%
with a structure consisting of a metal matrix and embedded in these hard phases, with the proviso that the hard phases are formed as carbides and / or nitrides and / or carbonitrides and / or Oxikarbonitrife and have a diameter of at most 50 microns and at least 0.2 microns, with The proviso that the relationship of carbon content and the concentration of niobium / tantalum and vanadium and titanium has a value formed from
fulfilled, and the number U is greater than 6, but less than 10.
Die Konzentrationen der Legierungsmetalle sind in diesem Werkstoff bezüglich der Kohlenstoffaktivität und der Karbidbildungskinetik der jeweiligen Elemente aufeinander abgestimmt, wobei die Gehalte der Monokarbidbildner maßgebend für die vorgesehene Kohlenstoffkonzentration sind. Stickstoff ist mit einem Gehalt von 0.6 Gew.-% nach obenhin begrenzt, weil im gegebenen Fall die Hartphasen hauptsächlich als Karbide ausgebildet sein sollen. Unter 0.15 Gew.-% Stickstoff ist die Verfestigungswirkung der Matrix zu gering, sodass die Gehaltsgrenzen in Gew.-% 0.15 bis 0.6 Stickstoff sind.The concentrations of the alloying metals are coordinated in this material with respect to the carbon activity and the carbide formation kinetics of the respective elements, the contents of the monocarbide formers being decisive for the intended carbon concentration. Nitrogen is limited with a content of 0.6 wt .-% to the top, because in the given case, the hard phases should be designed mainly as carbides. Below 0.15 wt.% Nitrogen, the solidification effect of the matrix is too low, so that the content limits in wt.% Are 0.15 to 0.6 nitrogen.
Silicium wirkt als Desoxidationsmetall und beeinflusst die Gefügeumwandlung der Legierung bei der Wärmebehandlung. Ein Mindestgehalt von 0.2 Gew.-% Si ist im Hinblick auf eine wirksame Oxidbildung wichtig, wo hingegen höhere Gehalte als 1.5 Gew.-% die Zähigkeit nachteilig beeinflussen.Silicon acts as a deoxidation metal and influences the microstructural transformation of the alloy during the heat treatment. A minimum content of 0.2% by weight of Si is important in terms of effective oxide formation, whereas higher contents than 1.5% by weight adversely affect toughness.
Ein Mangangehalt von 0.3 Gew.-% und mehr ist für eine Abbindung von Schwefel im Metall vorgesehen, wobei über 2.0 Gew.-% Mn eine nachteilig wirkende Austenitstabilität fördert.A manganese content of 0.3% by weight or more is intended for setting sulfur in the metal, with more than 2.0% by weight of Mn promoting disadvantageous austenite stability.
Chrom und Molybdän begründen eine Korrosionsbeständigkeit der Legierung bei Mindestkonzentrationen von 10.0 und 0.5 Gew.-%, können jedoch auch als Karbidbildner wirksam sein. Höhere Gehalte als 20.0 Gew.-% Cr und 3.0 Gew.-% Mo führen in nachteiliger Weise bei einer Wärmebehandlung zu einer Stabilisierung von Ferrit.Chromium and molybdenum provide corrosion resistance of the alloy at minimum concentrations of 10.0 and 0.5 wt%, but may also be effective as carbide formers. Higher contents than 20.0% by weight of Cr and 3.0% by weight of Mo disadvantageously lead to a stabilization of ferrite in a heat treatment.
Vanadin und Titan sollen Gehalte von jeweils 1.0 Gew.-% nicht übersteigen, weil Karbide dieser Elemente im hohen Maße Cr lösen bzw. in das Kristallgitter einbauen, wodurch im Randbereich der Matrix eine Verarmung an Cr entstehen kann.Vanadium and titanium should not exceed contents of 1.0 wt .-%, because carbides of these elements to a large extent dissolve Cr or incorporate into the crystal lattice, which can cause depletion of Cr in the edge region of the matrix.
Durch diese örtliche Chromverarmung erfolgt eine Störung der Ausbildung einer stabilen Passivschicht an der Oberfläche, wodurch die Korrosionsbeständigkeit der Legierung verschlechtert ist. In Gew.-% 0.1 Vanadin und 0.001 Titan wirken für eine Bildung von Monokarbidkeimen günstig.This local chromium depletion interferes with the formation of a stable passive layer on the surface, thereby deteriorating the corrosion resistance of the alloy. In% by weight 0.1 vanadium and 0.001 titanium are favorable for the formation of monocarbide nuclei.
Die Elemente Niob und Tantal sind Elemente, die in der Legierung ab einem Gehalt von 3.0 Gew.-% harte, die Verschleißfestigkeit des Werkstoffes fördernde Monokarbide ausformen. Dabei ist es wichtig, dass diese Elemente Nb/Ta nur eine geringe Neigung zeigen, weitere Elemente, insbesondere Chrom, bei der Karbid- oder Karbonitridbildung in das Kristallgitter einzubauen, sodass im Umfeld dieser Hartphasen keine Verarmung der Matrix an Legierungskomponenten, insbesondere an Chrom und Molybdän, und somit kein nachteiliger Einfluss auf die Korrosionsbeständigkeit des Werkstoffes entsteht.The elements niobium and tantalum are elements that form in the alloy from a content of 3.0 wt .-% hard, the wear resistance of the material promoting monocarbides. It is important that these elements Nb / Ta show only a slight tendency to incorporate further elements, in particular chromium, in the carbide or carbonitride formation in the crystal lattice, so that in the vicinity of these hard phases no depletion of the matrix of alloy components, especially of chromium and Molybdenum, and thus no adverse effect on the corrosion resistance of the material is formed.
Gemäß einer Ausgestaltung der Erfindung werden bei einem nach dem vorgenannten Verfahren hergestellten Werkstoff ein geringer Verschleiß und eine hohe Korrosionsbeständigkeit des Werkstoffes erreicht, welcher Werkstoff in Gew.-% enhält
mit einem Gefüge bestehend aus einer Metallmatrix und in diese eingelagert Hartphasen, mit der Maßgabe, dass die Hartphasen als Karbide und/oder Nitride und/oder Karbonitride und/oder Oxikarbonitride gebildet sind und einen Durchmesser von höchstens 50 µm und mindestens 0.2 µm aufweisen, mit der Maßgabe, dass der Zusammenhang von Stickstoffgehalt und der Konzentration von Niob sowie Vanadin einen Wert, gebildet aus
erfüllt ist, und die Zahl U1 größer als 4 und kleiner als 8 ist.According to one embodiment of the invention, in a material produced by the aforementioned method, a low wear and a high corrosion resistance of the material is achieved, which contains material in wt .-%
with a structure consisting of a metal matrix and embedded in it Hard phases, with the proviso that the hard phases as carbides and / or nitrides and / or carbonitrides and / or Oxikarbonitride are formed and have a maximum diameter of 50 microns and at least 0.2 microns, with the proviso that the relationship between nitrogen content and the concentration of niobium as well as vanadin a value formed from
is satisfied, and the number U1 is greater than 4 and less than 8.
Der hohe Stickstoffgehalt von 1.0 bis 4.0 Gew.-% bei Kohlenstoffkonzentrationen von 0.3 bis 1.0 Gew.-% führt zu im Wesentlichen aus Nitriden gebildeten Hartphasen, wobei die durch Chrom und Molybdän bewirkte Passivschichtbildung und die Korrosionsbeständigkeit gefördert werden.The high nitrogen content of 1.0 to 4.0 wt .-% at carbon concentrations of 0.3 to 1.0 wt .-% leads to substantially nitrides formed hard phases, whereby the chromium and molybdenum induced passive layer formation and corrosion resistance are promoted.
Unter Berücksichtigung des Chromgehaltes im Hinblick auf eine Korrosionsbeständigkeit und bei Ausrichtung des Verschleißwiderstandes auf im Wesentlichen Karbide kann gemäß einer weiteren Ausgestaltung der Erfindung ein Werkstoff, hergestellt nach einem vorgenannten Verfahren, günstig und wirtschaftlich bereitstellbar sein, der in Gew.-%
erfüllt, und die Zahl U2 größer als 6 und kleiner als 10
und die Zahl U3 größer als 9 und kleiner als 17 sind.Taking into account the chromium content in terms of corrosion resistance and in the orientation of the wear resistance to substantially carbides, according to a further embodiment of the invention, a material produced by a method mentioned above, can be provided cheaply and economically, which in wt .-%
fulfilled, and the number U2 greater than 6 and less than 10
and the number U3 is greater than 9 and less than 17.
Werden von einem erfindungsgemäßen Werkstoff neben hoher Verschleißfestigkeit auch eine hohe Warmhärte und dergleichen Zähigkeit gefordert, wie dies für spanabhebende Werkzeuge von besonderer, größter Bedeutung ist, so kann die Legierung bei abgesenkten Chromgehalten folgende Zusammensetzung und Relationen der Elemente in Gew-% aufweisen
erfüllt ist, wobei die Zahlenwerte U4 = 6 bis 10 / U5 = 80 bis 100 sind.If, in addition to high wear resistance, a high hot hardness and the same toughness are demanded by a material according to the invention, as is of particular importance for cutting tools, the alloy may have the following composition and ratios of the elements in% by weight with lowered chromium contents
is satisfied, wherein the numerical values U4 = 6 to 10 / U5 = 80 to 100 are.
Der auf einer Art Schnellstahllegierung basierende, hochverschleißfeste Werkzeugwerkstoff kann auf einfache Weise auf hohe Härtewerte vergütet werden und weist trotz hoher Härte überragende Zähigkeit auf. Besonders ausgeprägt ist die Verschleißfestigkeit der aus dieser Legierung gebildeten Schneidwerkzeuge, welche Werkzeuge dadurch eine besonders hohe Standzeit im groben und unterbrochenen Schnitt haben.The highly wear-resistant tool material, which is based on a type of high-speed steel alloy, can be easily tempered to high hardness values and has outstanding toughness despite its high hardness. Particularly pronounced is the wear resistance of the cutting tools formed from this alloy, which Tools thus have a particularly long service life in rough and interrupted cut.
Das erfindungsgemäße Verfahren der genannten Art ist derart bestimmt, dass in einem ersten Schritt eine metallische, flüssige Legierung, enthaltend Niob/Tantal (Nb/Ta) mit einer Konzentration von 3.0 bis 18.0 Gew.-%, sowie einem Gehalt an Kohlenstoff und/oder Stickstoff, bei welcher keine Primärausscheidungen an Karbiden und/oder Nitriden oberhalb der Verdüsungstemperatur oder Liquidustemperatur gebildet werden, zu Pulvermaterial verdüst wird, wonach das Pulver einem Verfahren zur Erhöhung des Kohlenstoffgehaltes und/oder des Stickstoffgehaltes und/oder des Sauerstoffgehaltes unterworfen und im Folgenden einem Heißkompaktieren, insbesondere einem Heißisostatischen Pressen unterworfen wird, wobei der Pressling bzw. HIP-Körper alternativ einer Warmverformung und/oder einer Wärmebehandlung unterworfen wird.The inventive method of the type mentioned is determined such that in a first step, a metallic liquid alloy containing niobium / tantalum (Nb / Ta) with a concentration of 3.0 to 18.0 wt .-%, and a content of carbon and / or Nitrogen, in which no primary precipitates of carbides and / or nitrides are formed above the atomization temperature or liquidus temperature, is atomized to powder material, after which the powder subjected to a process for increasing the carbon content and / or the nitrogen content and / or the oxygen content and then a hot compacting , in particular a hot isostatic pressing, wherein the pressed body or HIP body is alternatively subjected to a hot working and / or a heat treatment.
Weil bei hohen Nb/Ta-Gehalten primäre Karbid- und Nitridausscheidungen gebildet werden können, ist es erfindungsgemäß wesentlich, in einer sonst vollständig zusammengesetzten, flüssigen Vorlegierung die Gehalte an Kohlenstoff und Stickstoff unter der Grenze für eine Ausscheidungsbildung zu halten und dieses Flüssigmetall, insbesondere mittels Stickstoffs, zu Pulvermaterial zu verdüsen. Ein derart erhaltenes, festes Metallpulver wird in der Folge bei erhöhter Temperatur durch geeignete Mittel gezielt aufgekohlt und/oder dessen Stickstoffgehalt und/oder Sauerstoffgehalt bis auf vorgesehene Gehalte erhöht. Ein derart in der Zusammensetzung nach der Erfindung eingestelltes Pulver wird in Behältnissen gemäß dem Stand der Technik eingeschlossen, kann durch Heißisostatisches Pressen (HIPen) oder Verformen bei hoher Temperatur kompaktiert und auf gewünschte Abmessungen gebracht werden.Because primary carbide and nitride precipitates can be formed at high Nb / Ta contents, it is important in accordance with the present invention to maintain carbon and nitrogen levels below the limit for precipitate formation in an otherwise fully composite liquid master alloy, and this liquid metal, particularly by Nitrogen, to atomize powder material. A solid metal powder obtained in this way is subsequently carburetted in a targeted manner at elevated temperature by suitable means and / or its nitrogen content and / or oxygen content is increased to intended levels. Such a powder adjusted in the composition of the invention is enclosed in containers of the prior art, can be compacted by hot isostatic pressing (HIPing) or high temperature molding desired dimensions are brought.
Das erfindungsgemäße Verfahren hat den Vorteil, dass Werkstoffe mit hohem Karbid-Nitrid- oder Karbonitrid-Hartstoffanteil hergestellt werden können, wobei die Hartstoffpartikel geringe Durchmesser und homogene Verteilung in der Matrix haben. Die Matrixelemente können durch eine thermische Vergütung bzw. durch ein Härten und Anlassen des Werkstoffes diesem eine hohe Festigkeit vermitteln und ein Ausschalen oder Ausbrechen der größeren, optimierten Hartstoffteilchen weitestgehend verhindern. Dadurch wird eine besonders ausgeprägte Verschleißbeständigkeit des Werkstoffes erreicht.The method according to the invention has the advantage that materials with a high carbide-nitride or carbonitride hard material content can be produced, the hard-material particles having small diameters and homogeneous distribution in the matrix. The matrix elements can by a thermal tempering or by hardening and tempering of the material impart this high strength and prevent stripping or breaking the larger, optimized hard particles as far as possible. As a result, a particularly pronounced wear resistance of the material is achieved.
Eine Aufkohlung und/oder eine Erhöhung des Stickstoffgehaltes bei Einstellung des Sauerstoffgehaltes des vorlegierten Metallpulvers kann gemäß der Erfindung durch beigemischten, elementaren Kohlenstoff und/oder durch eine Kohlenstoff und/oder Stickstoff und/oder Sauerstoff abgebende Atmosphäre, insbesondere bei erhöhter Temperatur vor oder bei einer Heißkompaktierung erfolgen.A carburizing and / or an increase in the nitrogen content in adjusting the oxygen content of the pre-alloyed metal powder according to the invention by admixed, elemental carbon and / or by a carbon and / or nitrogen and / or oxygen-releasing atmosphere, in particular at elevated temperature before or at a Hot compaction done.
In einer Ausgestaltung der Erfindung können dem Pulverwerkstoff auch weitere Hartstoffpartikel mit einer Größe von 2 bis 50 µm in einem Ausmaß bis 25 Vol.-% beigemischt werden, welche in der Folge für den gegebenen Werkstoff verschleißsenkend wirksam sind.In one embodiment of the invention, other hard material particles having a size of from 2 to 50 .mu.m can be admixed to the powder material to an extent of up to 25% by volume, which are consequently effective in reducing the wear on the given material.
Anhand von lediglich Ausführungswege darstellenden Beispielen sollen im Vergleich mit bekannten Werkstoffen die Eigenschaften der erfindungsgemäßen Legierung näher dargestellt werden.By way of examples which represent merely exemplary ways, the properties of the alloy according to the invention are to be described in more detail in comparison with known materials.
Tab. 1 auf Seite 11 zeigt die Zusammensetzung von zwei handelsüblichen, verschleißfesten Legierungen mit den Bezeichnungen X190 CrVMo 20 4 1, X90 CrVMo 18 1 1, von korrosionsfesten, erfindungsgemäßen Legierungen mit den Bezeichnungen A, B, C, und von Schneidwerkstoffen nach der Erfindung mit den Bezeichnungen D, E, F.Tab. 1 on page 11 shows the composition of two commercially available, wear-resistant alloys with the
Die handelsüblichen Legierungen waren nach dem PM-Verfahren mit einer Verformung des HIP-Blockes (Heiß-Isostatisch-gepresst) von größer 6-fach hergestellt worden.The commercial alloys were produced by the PM method with a deformation of the HIP block ( H eiß- I sostatisch-ge p resst) greater than 6-fold.
Pulver für die Proben mit der Bezeichnung A, B, C wurden aus Legierungen mit folgenden Hauptbestandteilen in Gew.-%:
Ein Verdüsen mit Stickstoff erfolgte weiters unter Verwendung von Schmelzen mit der Bezeichnung D, E, F mit den Hauptbestandteilen in Gew.-%:
Als Aufkohlungsmittel wurden versuchsweise für die Werkstoffe mit den Bezeichnungen A bis C verwendet:
- CH4 + O
- Graphit (beigemischt) und Stickstoff + O
- CH4 + Stickstoff + O, wobei den Metallpulvern ca. 10% NbC mit einer Korngröße von 28µm beigemischt war.
- CH 4 + O
- Graphite (admixed) and nitrogen + O
- CH 4 + nitrogen + O, wherein the metal powders about 10% NbC was mixed with a particle size of 28 .mu.m.
Die Metallpulver der weiteren Legierungen D bis F wurden in den Versuchen mit folgenden Aufkohlungs- und Aufstickungsmitteln behandelt:
- CO + CH4 + IO
- CO + N + O
- Graphit + CO + N + O
- CO + CH 4 + IO
- CO + N + O
- Graphite + CO + N + O
Ein Auflegieren der Legierungspulver mit Kohlenstoff, Stickstoff und Sauerstoff erfolgte bei erhöhter Temperatur.Alloying of the alloy powders with carbon, nitrogen and oxygen was carried out at elevated temperature.
Das auflegierte Metallpulver wurde in der Folge unter Stickstoffatmosphäre in Stahlbehälter eingebracht und klopfverdichtet, wonach ein Verschweißen der Behälter und ein Heiß-Isostatisches-Pressen bei einer Temperatur von 1165°C erfolgte.The alloyed metal powder was then placed under nitrogen atmosphere in steel containers and knock compacted, followed by welding of the containers and hot isostatic pressing at a temperature of 1165 ° C.
Nach einem Warmverformen des HIP-Blockes wurden dem Erzeugnis Proben entnommen, analysiert (Tab. 1) und untersucht, wobei wichtige Ergebnisse in
Tab. 1 zeigt die chemische Zusammensetzung von bekannten Werkstoffen (X190 CrVMo 20 4 1 sowie X90 CrMoV 18 1 1) und jene von Stahlproben gemäß der Erfindung Tab. 1 shows the chemical composition of known materials (
Das Korrosionsverhalten der Legierungen wurde anhand von Stromdichte-PotentialKurven an den Proben nach ASTM G65 in 1 n H2SO4, 20°C ermittelt, wobei eine Abschreckung derselben von 1100°C bzw. 1070°C und ein Anlassen bei 200°C erfolgten.The corrosion behavior of the alloys was determined from current density potential curves on the samples according to ASTM G65 in 1N H 2 SO 4 , 20 ° C, with a quenching of the same from 1100 ° C and 1070 ° C and a tempering at 200 ° C. ,
Wie aus
Die jeweilige Härtetemperatur ist dem Bezeichnungsfeld für die Legierungen entnehmbar.The respective hardening temperature can be taken from the designation field for the alloys.
Im Vergleich mit X190 CrVMo 20 4 1 weisen die Werkstoffe A und C der erfindungsgemäßen Legierung eine vergleichbar niedrige Anlasshärte auf, weil deren jeweiliger Kohlenstoffgehalt einer verbesserten Korrosionsbeständigkeit wegen (siehe
Die Werkstoffhärte der Legierungen D, E und F liegen im Bereich von Anlasstemperaturen zwischen 500 und 600°C entscheidend höher, was eine deutliche Überlegenheit derselben für einen Einsatz von beispielsweise Schneid- und Formelementen offenlegt.The material hardness of alloys D, E and F are significantly higher in the range of tempering temperatures between 500 and 600 ° C, which discloses a clear superiority of the same for use of, for example, cutting and forming elements.
Claims (7)
- A method for the production of a wear-resistant material, wherein in a first step, a metallic, liquid alloy, containing niobium/tantalum (Nb/Ta) at a concentration of 3.0 to 18.0% by weight, as well as a content of carbon and/or nitrogen, in which no primary separations of carbides and/or nitrides are formed above the atomization temperature, or the liquidus temperature, is atomized into powder material, whereupon the powder is subjected to a method for increasing the carbon content, and/or the nitrogen content, and/or the oxygen content, and subsequently to hot compacting, in particular a hot isostatic pressing, or wherein the compacted waste, or the HIP body, is subjected to thermoforming, or heat treatment.
- The method according to claim 1 for the production of wear-resistant materials, wherein the powder is mixed with elemental carbon, and/or treated, optionally at an increased temperature, in an atmosphere releasing carbon and nitrogen, and subsequently compacted.
- A wear-resistant material of high corrosion resistance, produced using a method according to one of the claims 1 or 2, containing, in % by weight:
Carbon (C) 0.5 to 2.5 Nitrogen (N) 0.15 to 0.6 Oxygen (O) more than 0.002 to 0.25 Silicon (Si) 0.2 to 1.5 Manganese (Mn) 0.3 to 2.0 Chromium (Cr) 10.0 to 20.0 Niobium/Tantalum (Nb/Ta) 3.0 to 15.0 Molybdenum (Mo) 0.5 to 3.0 Vanadium (V) 0.1 to 1.0 Titanium (Ti) 0.001 to 1.0 Iron (Fe) rest
having a structure consisting of a metal matrix and hard phases embedded therein, provided that the hard phases are formed as carbides, and/or nitrides, and/or carbon nitrides, and/or oxicarbon nitrides, and have a diameter of not more than 50 µm, and at least 0.2 µm, provided that the correlation of carbon content and the concentration of niobium/tantalum, as well as vanadium and titanium meets a value, formed from
and the number U is greater than 6, but smaller than 10. - The wear-resistant material of high corrosion resistance, produced using a method according to one of the claims 1 or 2, containing, in % by weight:
Carbon (C) more than 0.3 to 1.0 Nitrogen (N) 1.0 to 4.0 Oxygen (O) more than 0.002 to 0.25 Silicon (Si) 0.2 to 1.5 Manganese (Mn) 0.3 to 1.5 Chromium (Cr) 10.0 to 20.0 Niobium/tantalum (Nb/Ta) 3.0 to 15.0 Molybdenum (Mo) 0.5 to 3.0 Vanadium (V) 0.1 to 1.0 Titanium (Ti) 0.001 to 1.0 Iron (Fe) rest
having a structure consisting of a metal matrix and hard phases embedded therein, provided that the hard phases are formed as carbides, and/or nitrides, and/or carbon nitrides, and/or oxicarbon nitrides, and have a diameter of not more than 50 µm, and at least 0.2 µm, provided that the correlation of nitrogen content and the concentration of niobium, as well as vanadium, meets a value, formed from
and the number U1 is greater than 4, but smaller than 8. - The wear-resistant material of high corrosion resistance, produced using a method according to one of the claims 1 or 2, containing, in % by weight:
Carbon (C) 0.5 to 3.0 Nitrogen (N) 0.15 to 0.6 Oxygen (O) more than 0.002 to 0.25 Silicon (Si) 0.2 to 1.5 Manganese (Mn) 0.3 to 2.0 Chromium (Cr) 10.0 to 20.0 Niobium/Tantalum (Nb/Ta) 3.0 to 15.0 Molybdenum (Mo) 0.5 to 3.0 Vanadium (V) 0.1 to 1.0 Titanium (Ti) 0.001 to 1.0 Iron (Fe) rest
Wherein the numeric values of U2 are greater than 6, but smaller than 10, and of U3 greater than 9, but smaller than 17. - The wear-resistant material of high thermal hardness and toughness, in particular for metal cutting tools, produced using a method according to one of the claims 1 or 2, containing, in % by weight:
Carbon (C) 1.0 to 3.5 Nitrogen (N) 0.05 to 0.4 Oxygen (O) more than 0.002 to 0.4 Silicon (Si) 0.2 to 1.5 Manganese (Mn) 0.3 to 1.0 Chromium (Cr) 2.5 to 6.0 Niobium/tantalum (Nb/Ta) 3.0 to 18.0 Molybdenum (Mo) 2.0 to 10.0 Tungsten (W) 0.1 to 12.0 Vanadium (V) 0.1 to 3.0 Cobalt (Co) 0.1 to 12.0 Iron (Fe) rest
wherein the numeric values of U4 = 6 to 10 / U5 = 80 to 100. - The wear-resistant material according to one of the claims 3 to 6, in which the matrix has a martensitic structure.
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DE4202339B4 (en) | 1991-01-29 | 2004-12-02 | Dörrenberg Edelstahl GmbH | Corrosion-resistant, highly wear-resistant, hardenable steel |
AT399673B (en) * | 1992-09-11 | 1995-06-26 | Boehler Edelstahl | COMPOSITE ROLLER AND METHOD FOR THEIR PRODUCTION |
DE4231695C2 (en) | 1992-09-22 | 1994-11-24 | Ver Schmiedewerke Gmbh | Use of steel for tools |
GB9404786D0 (en) * | 1994-03-11 | 1994-04-27 | Davy Roll Company The Limited | Rolling mill rolls |
JP3294029B2 (en) * | 1994-11-16 | 2002-06-17 | 財団法人電気磁気材料研究所 | Wear-resistant high-permeability alloy, method for producing the same, and magnetic recording / reproducing head |
US7262240B1 (en) * | 1998-12-22 | 2007-08-28 | Kennametal Inc. | Process for making wear-resistant coatings |
US6649682B1 (en) * | 1998-12-22 | 2003-11-18 | Conforma Clad, Inc | Process for making wear-resistant coatings |
AT410447B (en) * | 2001-10-03 | 2003-04-25 | Boehler Edelstahl | HOT STEEL SUBJECT |
SE524583C2 (en) * | 2002-12-12 | 2004-08-31 | Erasteel Kloster Ab | Composite metal product and process for making such |
DE102005020081A1 (en) | 2005-04-29 | 2006-11-09 | Köppern Entwicklungs-GmbH | Powder metallurgically produced, wear-resistant material |
US20060249230A1 (en) * | 2005-05-09 | 2006-11-09 | Crucible Materials Corp. | Corrosion and wear resistant alloy |
SE528991C2 (en) | 2005-08-24 | 2007-04-03 | Uddeholm Tooling Ab | Steel alloy and tools or components made of the steel alloy |
US7615123B2 (en) * | 2006-09-29 | 2009-11-10 | Crucible Materials Corporation | Cold-work tool steel article |
AT506790B1 (en) * | 2008-11-20 | 2009-12-15 | Boehler Edelstahl Gmbh & Co Kg | HOT STEEL ALLOY |
AT507597B1 (en) * | 2008-12-05 | 2010-09-15 | Boehler Edelstahl Gmbh & Co Kg | STEEL ALLOY FOR MACHINE COMPONENTS |
-
2009
- 2009-01-14 AT AT0005209A patent/AT507215B1/en active
- 2009-12-28 EP EP11004405A patent/EP2374560A1/en not_active Withdrawn
- 2009-12-28 EP EP09450242.4A patent/EP2253398B1/en active Active
-
2010
- 2010-01-13 US US12/686,609 patent/US8623108B2/en not_active Expired - Fee Related
- 2010-01-14 BR BRPI1000065-8A patent/BRPI1000065A2/en active Search and Examination
Also Published As
Publication number | Publication date |
---|---|
US20100192476A1 (en) | 2010-08-05 |
EP2253398A1 (en) | 2010-11-24 |
BRPI1000065A2 (en) | 2011-03-29 |
AT507215B1 (en) | 2010-03-15 |
US8623108B2 (en) | 2014-01-07 |
AT507215A4 (en) | 2010-03-15 |
EP2374560A1 (en) | 2011-10-12 |
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