EP1570096A1 - Produit metallique composite et son procede de production - Google Patents

Produit metallique composite et son procede de production

Info

Publication number
EP1570096A1
EP1570096A1 EP03812741A EP03812741A EP1570096A1 EP 1570096 A1 EP1570096 A1 EP 1570096A1 EP 03812741 A EP03812741 A EP 03812741A EP 03812741 A EP03812741 A EP 03812741A EP 1570096 A1 EP1570096 A1 EP 1570096A1
Authority
EP
European Patent Office
Prior art keywords
hard phase
atomic
type
product according
max
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.)
Withdrawn
Application number
EP03812741A
Other languages
German (de)
English (en)
Inventor
Stefan Sundin
Lars-Olov Nordberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Erasteel Kloster AB
Original Assignee
Erasteel Kloster AB
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Erasteel Kloster AB filed Critical Erasteel Kloster AB
Publication of EP1570096A1 publication Critical patent/EP1570096A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides
    • 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
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
    • 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
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
    • 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
    • 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

Definitions

  • the present invention concerns a composite metal product suitable to be used as a material for shearing, cutting, punching and moulding tools as well as for wearing parts and construction elements, when high demands are raised on hardness and wear resistance in combination with an adequate strength.
  • the invention also relates to a method for the manufacturing of such product.
  • cemented carbide materials means materials having an extremely high content of carbides which are sintered together in a binder metal, which normally consists of a cobalt base alloy. Many attempts have been made during the last fifty years to bridge this gap through the development of steel alloys having a high content of titanium carbides. An early suggested material belonging to this caterogy is known under the trade name “Ferro- TiC”, which however achieved only limited practical use. Another material having the trade name “Coronite”, which is disclosed in the US Patent No 4,145,213, is no longer on the market place, as far as is known to the applicant.
  • the material according to said US Patent No 4,145,213 contains a very high content of titanium carbide in a matrix consisting of hardenable steel.
  • the titanium carbides in turn contain a larger amount of nitrogen than carbon.
  • the material may be produced through liquid phase sintering of a cold pressed powder body, or through liquid phase sintering of a powder body under pressure - so called pressure sintering -, through isostatic hot pressurising, or through forging of a powder body with or without the presence of liquid phase.
  • This objective can be achieved through the invention by means of a composite metal product which contains 30-90 vol-% of a hard phase in the form of particles of substantially M(C,N)-carbonitride or M(C,N,O)-carbonitrideoxide 5 commonly referred to as hard phase of MX-type, where M to at least 50 atomic-% consists of titanium and
  • N the atomic-% ratio between C and N shall satisfy the condition 0.1 ⁇ ⁇
  • N 0.7 preferably satisfy the condition 0.2 ⁇ ⁇ 0.6, suitably satisfy the condition
  • 30 atomic-%, in said hard phase of MX-type may consist of one or more of the metals which belong to the group consisting of N, ⁇ b, Ta, Hf, and Zr.
  • M might consist of at least 5 and max. 30 atomic-% N and/or of at least 5 and max. 30 atomic-% ⁇ b, however, totally max. 40 atomic-%, preferably max. 30 atomic-%.
  • Ta, Zr and/or Hf shall be included, the total amount of those metals should not amount to more than 3 atomic-% of the total metal content of the hard phase of MX-type.
  • the metal M in said hard phase of MX-type consists of titanium to at least 70 atomic-%, preferably at least 80 atomic-%, and most conveniently to at least 90 atomic-%.
  • the total content of hard phase of MX-type amounts, according to an aspect of the invention, to 30-70 vol-%, preferably to 40-60 vol-%, of the metal product.
  • the invention also aims at providing a method for manufacturing, with good reproducibility, a composite metal product which contains 30-90 vol-% of a hard phase having the form of particles, which consist mainly of M(C,N)-carbonitride or M(C,N,O)-carbonitrideoxide, commonly referred to as hard phase of MX-type, which particles are substantially homogenously distributed in a matrix of hardenable steel.
  • a powder mixture which contains powder of titanium carbide, titanium nitride, and/or titanium carbonitride in such an amount that its content of titanium atoms correspond to at least 50 % of the metal atoms in said hard phase of MX-type in the final metal product, and at least the main part of other constituents of the final metal product, is milled together, that a body is formed of the milled mixture, and that said body is liquid phase sintered at a temperature between 1350 and 1600 °C and subsequently cooled, causing the liquid phase to solidify, said hard phase particles of MX-type obtaining their final composition and size during said liquid phase sintering and subsequent solidification.
  • at least 90 % of the number of particles which can be observed in a viewed section of the material by means an optical microscope, have a size smaller than 1 ⁇ m.
  • N hard phase in the finished product will satisfy that value of the ratio which has been mentioned in the foregoing.
  • the milling of the powder mixture is performed with a power supply of at least 10 MJ (megajouleVkg powder, preferably at least 20 MJ/kg powder.
  • a power supply of 25 MJ/kg powder has turned out to be suitable.
  • the power supply therefore, according to an aspect of the invention, should be limited to max. 50 MJ/kg powder, suitably be limited to max. 40 MJ/kg powder, in order not to make the manufacturing unnecessarily expensive.
  • hard phase particles of MX-type will be evenly distributed in the said matrix.
  • Evenly distributed means that not more than 0.5 % of a section of the product should consist of regions having a length of at least 8 ⁇ m in the direction of the longest extension of the region, a width crosswise said direction of the longest extension, in any section of the region, of not more than 8 ⁇ m, and an area of at least 50 ⁇ m 2 , which regions are void of hard phase particles of MX-type, and that not more than 10 %, and preferably not more than 5 % of the section of the product, consists of regions having a length of at least 6 d in the direction of the longest extension of the region, a width crosswise said direction of the longest extension, in any section of the region, of at least 6 d, and an area of at least 9 ⁇ d 2 where d is the mean value of the size of the hard phase particles of MX-type in the longest extension of the particles in the observed section, which
  • the content of oxygen in this hard phase is 0.01-4 atomic-% of the total content of C+N+O in the hard phase.
  • Fig.1 - Fig.5 show microstructures of samples made of a powder mixture containing
  • the hard phase powder consisted of vanadium carbide (NC), niobium carbide ( ⁇ bC), hafnium carbide (HfC), hafnium- titanium carbide ((Hf,Ti)C), titanium nitride (Ti ⁇ ), and titanium carbide (TiC). More specifically, there was used as hard phase commercially available powders of said hard phases with a powder grain size in the order of 1 ⁇ m. These powders contained several thousands ppm oxygen. In other words, they were highly oxidised.
  • the order of the oxygen content could be estimated to about 4000 ppm (0.4 %) but could be even higher and amount to the order of 1 weight-%.
  • the base metal powder consisted of a commercially available high speed steel obtained from the applicant's own production. This high speed steel is known by its trade name ASP 2030 ® , which has the chemical composition in weight-%: 1.28 C, 0.5 Si, 0.3 Mn, 4.2 Cr, 5.0 Mo, 3.1 N, 6.4 W, 8.5 Co, balance Fe and unavoidable impurities.
  • This powder consisted of a gas atomised powder, which was sieved to a maximal grain size of 125 ⁇ m.
  • the different powder mixtures were milled in a so called attritor mill, which is a type of ball mill having milling balls made of a ball bearing steel.
  • attritor mill which is a type of ball mill having milling balls made of a ball bearing steel.
  • the energy is supplied to the milling balls through the rotation of the mill housing
  • the energy is supplied to the balls by means of a rotating propeller. This affords a very high velocity to the milling bodies and hence a capacity to transfer more energy to the product which is being milled. Therefore, in an attritor mill, the supply of energy/time is about fifteen times larger than in a more conventional ball mill. This is important, because it promotes the homogenisation of the material that is being milled.
  • the particles that are being milled are crushed, deformed and repeatedly put together again. Due to the deformation, which is an important part of this treatment, a great amount of dislocation energy is supplied to the product that is milled, leading to a changed, higher state of energy of the milled material.
  • the energy which was supplied to the milled powder in this mode amounted to about 25 MJ (Megajoule)/kg powder. No milling liquid was used during the milling. The milling was performed at atmospheric pressure. Pick up of oxygen through oxidation could take place during the handling of the powder.
  • the green bodies were consolidated through liquid phase sintering in a vacuum furnace, heated by graphite electric heaters.
  • the sintering temperatures were varied from 1300 to 1540 °C with a holding time of 30 min. at the sintering temperature.
  • the samples Prior to mechanical tests, the samples were hardened from 1180 °C, followed by tempering at 560 °C, 3xlh.
  • the powder mixtures were milled for ten hours in an attritor mill with an energy supply of about 25 MJ/kg powder, were pressed to green bodies, and were sintered in the mode described above.
  • the microstructure of samples sintered at 1300, 1350 and 1400 °C were studied.
  • samples of the same powder mixtures which had been consolidated through hot isostatic pressing (HIP-ing) were studied.
  • HIP-ing hot isostatic pressing
  • Powder mixtures with compositions according to Table III were prepared. Also these powders had the same physical character as in the series of experiments I and II. Table 3 Ingredients (gram) of the powder mixtures
  • the ingredients of the powder mixtures were selected such that only the contents of carbon and nitrogen were varied, while the other elements existed in essentially equal amounts in the mixtures.
  • the chemical composition of the powder mixtures contained in weight-%: 0.39 Si, 0.18 Mn, 2.66 Cr, 3.34 Mo, 4.18 W, 2.05 V, 5.60 Co and 25.3 Ti.
  • the oxygen content amounted to about 0.27 weight-%.
  • Balance was iron, carbon, nitrogen and unavoidable impurities.
  • the contents of carbon and nitrogen in the powder mixtures are given in Table 5.
  • the powder mixtures were milled in an attritor mill in the mode which has been described in the foregoing, e.g. for a period time of 10 hours, with an energy supply of 25 MJ/kg powder.
  • Green bodies were made of the milled powder, and the green bodies were consolidated through HIP-ing and through liquid phase sintering, respectively.
  • the liquid phase sintering was carried out at varying temperatures between 1300 and 1540 °C during a holding time of 30 minutes at the sintering temperature.
  • the differences can be attributed to any of the following factors: the chemical composition of the powder mixtures, chemical reactions between existing elements during the liquid phase sintering, and take up or loss of light elements during milling and sintering.
  • carbon may have been taken up from heat elements of graphite at the sintering operation.
  • oxygen can be taken up from the environment as well as nitrogen during the milling process.
  • various elements are dissolved in the liquid phase to be incorporated in the MX-phase, so that M will consist not entirely of titanium but to some degree also of vanadium and other metals from the base alloy ASP 2030 ® .
  • a minor fraction of titanium is also likely to be dissolved in the melt, despite that the solubility of titanium is low.
  • the tool member - the insert - on the other hand was made of a sintered carbide material, one should also have reason to count on an additional increase of the cutting capacity, which confirms that the composite metal product of the invention may fill the gap between high speed steels and sintered carbide materials.
  • Alloy no 160 was studied with reference to the microstructure after a heat treatment, which comprised hardening from 1150 °C, but which in other respects was performed in the same way as for alloy no 110 according to the above; see Fig. 12, which shows a homogenous microstructure of essentially evenly distributed, rounded carbides in the hardened and tempered matrix.
  • This steel alloy provides, in the finished product, a matrix which can be hardened to a hardness > 500 HV30.
  • the chemical composition of that high speed steel is the most suitable one, in order, in combination with the other constituents of the powder mixture, to provide a matrix having an optimal chemical composition.
  • ASP 2030 ® has a comparatively high content of metals, which may form M 6 C-carbides. It is true that carbides of that type can be dissolved during the liquid phase sintering according to the invention, but it is also true that they can be re-established in the matrix and/or on the M(C,N)- and/or on the M(C,N,O)- phase particles, which may be disadvantageous.
  • a high speed steel having a lower content of W and Mo may be more suitable, as has been demonstrated in the foregoing with reference to the use of the alloy ASP 20XX in the series of experiments V.
  • other steel alloys are conceivable, high speed steels as well as other hardenable steels, e.g. cold work steels.
  • a base alloy there should preferably be used a steel alloy, which in combination with other constituents provides a matrix in the finished material, which matrix can be hardened to a hardness ⁇ 500 HV30 after tempering.
  • the content of hard phase in the powder mixture can be varied.
  • titanium carbide-, titanium nitride-, and/or titanium carbonitride powders one may thus, at least for certain applications, consider moderate additions of other carbides or nitrides of MX-type, such as VC, NbC, TaC, ZrC, HfC, and/or (HfTi)C and corresponding nitrides, however not more than 30 mol-% of the total content of the achieved hard phase of MX- type in the finished product.
  • MX-type such as VC, NbC, TaC, ZrC, HfC, and/or (HfTi)C and corresponding nitrides
  • stimulating the generation of mixed carbonitrides may be that the formation of a dense material is accelerated even when sintering at a relatively low temperature, which could justify the addition of a certain amount of VC and/or NbC in the powder mixture or a higher content of vanadium and/or niobium in the base metal alloy.
  • niobium carbide in the powder mixture also might stimulate the milling.
  • mixed carbonitrides will be harder than pure titanium carbonitrides or pure titanium carbonitrideoxides, which could increase the hardness of the manufactured metal product.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

L'invention concerne un produit métallique composite contenant 30-90 % en volume d'une phase dure se présentant sous la forme de particules sensiblement de M(C,N)-carbonitrure ou de M(C,N,O)-carbonitrure-oxyde, communément appelés phase dure de type MX, où M représente au moins un pourcentage atomique de 50 % de titane, ces particules étant distribuées de manière sensiblement homogène dans une matrice constituée d'acier durcissable, et où le rapport entre les pourcentages atomiques de C et N doit satisfaire l'équation 0.1< < 0.7. Lors de la production de ce produit, on broie ensemble un mélange poudreux contenant de la poudre de carbure de titane, de nitrure de titane et/ou de carbonitrure de titane dans une quantité telle que le nombre d'atomes de titane contenu correspond au moins au pourcentage atomique de 50 % du métal de cette phase dure de type MX du produit final, et au moins la partie principale d'autres constituants du produit métallique final. Un corps vert, constitué du produit broyé, est soumis à un frittage en phase liquide à une température de 1350-1600 °C et puis à un refroidissement qui entraîne la solidification de cette phase liquide. C'est lors du frittage de cette phase liquide et du refroidissement consécutif que les particules phase dure de MX obtiennent leur composition et taille finales.
EP03812741A 2002-12-12 2003-12-09 Produit metallique composite et son procede de production Withdrawn EP1570096A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE0203668 2002-12-12
SE0203668A SE524583C2 (sv) 2002-12-12 2002-12-12 Sammansatt metallprodukt och förfarande för framställning av en sådan
PCT/SE2003/001908 WO2004053178A1 (fr) 2002-12-12 2003-12-09 Produit metallique composite et son procede de production

Publications (1)

Publication Number Publication Date
EP1570096A1 true EP1570096A1 (fr) 2005-09-07

Family

ID=20289829

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03812741A Withdrawn EP1570096A1 (fr) 2002-12-12 2003-12-09 Produit metallique composite et son procede de production

Country Status (6)

Country Link
US (1) US20060048603A1 (fr)
EP (1) EP1570096A1 (fr)
JP (1) JP2006509908A (fr)
AU (1) AU2003302772A1 (fr)
SE (1) SE524583C2 (fr)
WO (1) WO2004053178A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10361772B4 (de) * 2003-12-31 2006-10-12 Henning Kloss Bandscheibenimplantat
AT507215B1 (de) * 2009-01-14 2010-03-15 Boehler Edelstahl Gmbh & Co Kg Verschleissbeständiger werkstoff
EP2369031B1 (fr) * 2010-03-18 2016-05-04 Oerlikon Trading AG, Trübbach Revêtement à base de nial2o4 dans une structure de spinelle
JP5807850B2 (ja) * 2013-06-10 2015-11-10 住友電気工業株式会社 サーメット、サーメットの製造方法、および切削工具
US10047014B2 (en) * 2014-10-13 2018-08-14 Zhiguo XING Plasma-sprayed tin coating having excellent hardness and toughness, the preparation method therefor, and a mold coated with said tin coating
CN105296802B (zh) * 2015-11-03 2017-03-22 华南理工大学 一种高强韧双尺度结构钛合金及其制备方法与应用
CN105420612B (zh) * 2015-12-14 2017-10-20 布库 一种打结器钳嘴合金材料及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE392482B (sv) * 1975-05-16 1977-03-28 Sandvik Ab Pa pulvermetallurgisk veg framstelld legering bestaende av 30-70 volymprocent
JPS59133352A (ja) * 1983-01-14 1984-07-31 Fuji Die Kk 超高合金鋼製の熱間圧延ロ−ル
JPH07173568A (ja) * 1990-12-26 1995-07-11 Hitachi Tool Eng Ltd 超硬質合金
DE4340652C2 (de) * 1993-11-30 2003-10-16 Widia Gmbh Verbundwerkstoff und Verfahren zu seiner Herstellung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004053178A1 *

Also Published As

Publication number Publication date
SE0203668D0 (sv) 2002-12-12
SE0203668L (sv) 2004-06-13
JP2006509908A (ja) 2006-03-23
US20060048603A1 (en) 2006-03-09
WO2004053178A1 (fr) 2004-06-24
SE524583C2 (sv) 2004-08-31
AU2003302772A1 (en) 2004-06-30

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