WO2007001226A1 - Sintered cemented carbides using vanadium as gradient former - Google Patents

Sintered cemented carbides using vanadium as gradient former Download PDF

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Publication number
WO2007001226A1
WO2007001226A1 PCT/SE2006/000785 SE2006000785W WO2007001226A1 WO 2007001226 A1 WO2007001226 A1 WO 2007001226A1 SE 2006000785 W SE2006000785 W SE 2006000785W WO 2007001226 A1 WO2007001226 A1 WO 2007001226A1
Authority
WO
WIPO (PCT)
Prior art keywords
cutting tool
vanadium
coated cutting
binder phase
phase
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.)
Ceased
Application number
PCT/SE2006/000785
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English (en)
French (fr)
Inventor
Alexandra Kusoffsky
Susanne Norgren
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.)
Sandvik Intellectual Property AB
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Sandvik Intellectual Property 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 Sandvik Intellectual Property AB filed Critical Sandvik Intellectual Property AB
Priority to JP2007542989A priority Critical patent/JP4842962B2/ja
Priority to US11/658,055 priority patent/US7794830B2/en
Priority to KR1020077005609A priority patent/KR101353651B1/ko
Priority to CN2006800007964A priority patent/CN101018879B/zh
Priority to EP06757997.9A priority patent/EP1904660B1/en
Publication of WO2007001226A1 publication Critical patent/WO2007001226A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • 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
    • C22C29/06—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 carbides, but not containing other metal compounds
    • C22C29/08—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 carbides, but not containing other metal compounds based on tungsten carbide
    • 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
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component
    • Y10T428/12056—Entirely inorganic
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/24983—Hardness
    • 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
    • Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less

Definitions

  • the present invention relates to cemented carbides with a binder enriched surface zone, a so-called gradient zone.
  • the gradient zone is essentially free from cubic carbides or carbonitrides .
  • vanadium as a gradient former will create unique properties regarding the resistance to thermal cracking.
  • Coated cemented carbide inserts with binder phase enriched surface zone are today used to a great extent for machining of steel and stainless materials. Thanks to the binder phase enriched surface zone, an extension of the application area for cutting tool material has been obtained.
  • EP-A-603143 discloses cemented carbide with binder phase enriched surface zone said cemented carbide containing WC and cubic phases in a binder phase in which the binder phase enriched surface zone has an outer part essentially free of cubic phase and an inner part containing cubic phase and stratified binder phase layers .
  • the amount of binder phase is between 2 and 10 wt-%.
  • the cubic phase can contain varying amount of titanium, tan- talum, niobium, vanadium, tungsten and/or molybdenum.
  • the binder phase enriched surface zone as well as an up to 300 ⁇ m thick zone below it contains no graphite. However, in the interior there is a C-porosity of C04-C08. From a fracture mechanical point of view, an en- richment of binder metal in a surface zone means that the ability of the cemented carbide to absorb deformation and stop growing cracks from propagating. In this way a material is obtained with improved ability to resist fracture by allowing greater deformations or by preventing cracks from growing, compared to a material with mainly the same composition but homogenous structure. The cutting material, thus, exhibits a tougher behavior.
  • cutting inserts with binder phase enriched surface zones have a reduced ability to withstand wear when cutting operations include thermal cycling of the cutting edge, such as interrupted cut with coolant.
  • This wear type includes cracking of the coating and subsequent cracking of the surface zone of the cemented carbide body which leads to that parts of the coating and to some extent also parts of the surface zone are "pulled out” giving an uneven and rapid wear on the rake face and in the edge line of the cutting insert.
  • a cemented car- bide insert with a binder phase enriched surface zone with a combination of high toughness and high deformation resistance and increased resistance to thermal cracking is obtained if V from group 5A is used as gradient former and if the content of Ti is low or 0.
  • Fig 1 and 2 show in 500X magnification the structure of a binder phase enriched surface zone of a coated insert according to the invention.
  • Fig 3 and 4 show in 4Ox magnification the appearance of the cutting edge of coated inserts according to the invention, A and B, and according to prior art, C and D after a turning test.
  • the white areas show where the coating has spalled because of thermal cracking.
  • the present invention concerns cemented carbides used in turning operations consisting of a first phase based on tungsten carbide, WC, having an average grain size larger than 1.5 ⁇ m, preferably smaller that 3 ⁇ m, a metallic binder phase based on Co and/or Ni and finally at least one additional cubic phase comprising at least one solid solution carbonitride containing vanadium.
  • the cemented carbide has a ⁇ 50, preferably 10-35 ⁇ m thick binder phase enriched surface zone essentially free of cubic phase.
  • the binder phase content of the binder phase enriched surface zone has a maximum of 1.2-3 times the nominal binder phase content.
  • the WC has an average grain size larger than 1.5 ⁇ m close to the surface in the gradient zone as well as in the center of the cemented carbide.
  • the composition of the cemented carbide is 3-20 wt-% Co, preferably 4-15 wt-% Co and most preferably 5-13 wt-% Co, 1-15 wt-% V and preferably 2-8 wt-% V.
  • Other cubic carbide forming elements soluble in the cubic phase, except for Ti, from group 4a and or 5a can be addeded, preferably ⁇ 4 wt-% Nb, most preferably 0.2- 3 wt-% Nb, and preferably ⁇ 10 wt-% Ta, most preferably 1-8 wt-% Ta and as rest WC, 70-92 wt-%, preferably 75-90 wt-% with no free graphite present in the microstruc- ture.
  • Ti can only be present in minor amounts, ⁇ 1 wt-%, preferably ⁇ 0.5 wt-% most preferably on the level of technical impurity or 0 wt-% .
  • the total sum of V and other elements soluble in the cubic phase except W is 1- 15 wt-%, preferably 2-10 wt-%.
  • the weight-ratio between the amount of Ti compared to the amount of V should be less then 0.5, preferably less then 0.2.
  • the cobalt binder phase is alloyed with a certain amount of W giving the cemented carbide cutting insert its desired properties.
  • W in the binder phase influences the magnetic properties of cobalt and can hence be related to a value, CW-ratio, defined as
  • CW-ratio magnetic-% Co / wt-% Co where magnetic-% Co is the weight percentage of magnetic Co and wt-% Co is the weight percentage of Co in the cemented carbide.
  • the cemented carbide has a CW-ratio of 0.78-0.95, preferably 0.80-0.92, and most preferably 0.82-0.88.
  • the cemented carbide may contain small amounts, ⁇ 2 volume %, of ⁇ -phase (MgC), without any detrimental effect.
  • Cemented carbide inserts according to the invention are preferably coated with a thin wear resistant coating with CVD-, MTCVD or PVD-technique or a combination of CVD and MTCVD.
  • a thin wear resistant coating with CVD-, MTCVD or PVD-technique or a combination of CVD and MTCVD.
  • an innermost coating of carbides, nitrides and/or carbonitride preferably of titanium
  • Subsequent layers consist of carbides, nitrides and/or carbonitrides preferably of titanium, zirconium and/or hafnium, and/or oxides of aluminium and or zirconium.
  • the present invention also relates to a method of making a coated cutting tool insert consisting of a cemented carbide substrate and a coating, said substrate comprising WC, binder phase and cubic phase, comprising at least one carbide or carbonitride containing vanadium, with a binder phase enriched surface zone essentially free of cubic phase, by powder metallurgical methods including; milling of a powder mixture forming the hard constituents and the binder phase, drying, pressing and sintering. Sintering is performed in nitrogen atmosphere, partly in nitrogen, in vacuum, or in inert atmosphere to obtain the desired binder phase enrichment.
  • V is added as VC or as (V, M) C or as (V,M)(C,N)or as (V, M, M) (C, N) where M is any metallic element soluble in the cubic phase.
  • the method comprises the following steps :
  • a powder mixture with a composition comprising 3-20 wt% cobalt, 70-92 wt-% WC, 1-15 wt-% vanadium as carbide, nitride or carbonitride, and as carbide ⁇ 1 wt-% titanium, other cubic carbide forming elements from the groups 4a and/or 5a than vanadium and titanium in such an amount that the total amount of ele- ments from groups 4a and/or 5a added being 1-15 wt-%, - compacting said powder mixture to bodies of desired shape and dimension,
  • the invention also relates to the use of inserts according to the invention for turning of steel under normal conditions and especially with interrupted cut- ting.
  • the inserts according to the present invention will be used for machining work pieces such as steel within the ISO-P area and stainless steel in the ISO-M area, preferably steel within the P35 area.
  • the cutting speed should be ⁇ 300 m/min, most preferably 190-240 m/min, at a cutting depth of 2-4 mm and a feed of 0.2- 0.6 mm/rev.
  • the structure of the cutting inserts consisted of a 25 ⁇ m thick binder phase enriched surface zone under the clearance and rake faces and a significantly reduced gradient thickness close to the edge portion of the sur- face, see Figure 1.
  • the inserts were edge rounded to 50 ⁇ m and cleaned using conventional methods and coated with a thin layer ⁇ 1 ⁇ m of TiN followed by 9 ⁇ m thick layer of Ti(C 7 N) and a 7 ⁇ m thick layer of (X-Al 2 O 3 according to patent US 5,654,035. On top of the CC-Al 2 O 3 layer a 1 ⁇ m thick TiN layer was deposited. Finally the inserts were wet blasted on the rake face with alumina grit to remove the top TiN-layer.
  • Inserts in style CNMG 120408-PM were pressed and sintered.
  • the inserts had a 25 ⁇ m thick binder enriched surface zone essentially free of cubic phase like the inserts in A.
  • the inserts were edge rounded, cleaned, coated and wet blasted as in A.
  • the CW-ratio was found to be 0.84.
  • Inserts from B and C were tested and compared with respect to thermal cracking in a longitudinal turning with coolant of a square bar 100x100 mm to a diameter of 60 mm.
  • Fig 3 shows in 4Ox magnification the appearance of the cutting edges of the inserts after 2 minutes turn- ing.
  • the white areas show where the coating has spalled because of thermal cracking. It is evident that inserts B have much better resistance against thermal cracking than inserts C.
  • Fig 4 shows in 4Ox magnification the appearance of the cutting edges of the inserts after 2 minutes turning.
  • the white areas show where the coating has spalled because of thermal cracking. It is evident that inserts A have much better resistance against thermal cracking than inserts D.
  • Insert B is slightly better towards flank resistance than insert C.
  • Example 5 Inserts from A and D were tested and compared with respect to flank resistance in longitudinal turning of ball bearing steel SKF25B with coolant present.
  • Example 3 and 4 show the advantage that V has on the thermal properties compared to prior art inserts .
  • Examples 4 and 5 show that the flank wear resistance is as good, or even better, than the commercially available alloys .

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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)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
PCT/SE2006/000785 2005-06-27 2006-06-27 Sintered cemented carbides using vanadium as gradient former Ceased WO2007001226A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2007542989A JP4842962B2 (ja) 2005-06-27 2006-06-27 勾配形成元素としてバナジウムを用いた焼結超硬合金
US11/658,055 US7794830B2 (en) 2005-06-27 2006-06-27 Sintered cemented carbides using vanadium as gradient former
KR1020077005609A KR101353651B1 (ko) 2005-06-27 2006-06-27 구배 형성제로서 바나듐을 이용하는 소결된 초경합금
CN2006800007964A CN101018879B (zh) 2005-06-27 2006-06-27 包括硬质合金基体和涂层的涂覆切削工具刀片及其制造方法
EP06757997.9A EP1904660B1 (en) 2005-06-27 2006-06-27 Sintered cemented carbides using vanadium as gradient former

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE0501489-9 2005-06-27
SE0501489A SE529590C2 (sv) 2005-06-27 2005-06-27 Finkorniga sintrade hårdmetaller innehållande en gradientzon

Publications (1)

Publication Number Publication Date
WO2007001226A1 true WO2007001226A1 (en) 2007-01-04

Family

ID=36933488

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE2006/000785 Ceased WO2007001226A1 (en) 2005-06-27 2006-06-27 Sintered cemented carbides using vanadium as gradient former

Country Status (7)

Country Link
US (2) US7588833B2 (enExample)
EP (2) EP1739198A1 (enExample)
JP (2) JP4842962B2 (enExample)
KR (2) KR20070000358A (enExample)
CN (2) CN101018879B (enExample)
SE (1) SE529590C2 (enExample)
WO (1) WO2007001226A1 (enExample)

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KR102609665B1 (ko) * 2015-04-30 2023-12-04 산드빅 인터렉츄얼 프로퍼티 에이비 절삭 공구
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DE102016207028A1 (de) * 2016-04-26 2017-10-26 H.C. Starck Gmbh Hartmetall mit zähigkeitssteigerndem Gefüge
CN105803288B (zh) * 2016-05-23 2017-11-14 株洲钻石切削刀具股份有限公司 一种非均匀梯度硬质合金及其制备方法
CN109863257B (zh) * 2016-09-30 2021-06-22 山特维克知识产权股份有限公司 机械加工Ti、Ti合金和Ni基合金的方法
CN110284038B (zh) * 2019-04-26 2020-07-28 中南大学 一种具有强(111)织构的pvd涂层及其制备方法
KR20220115089A (ko) * 2019-12-20 2022-08-17 에이비 산드빅 코로만트 절삭 공구
CN111940742B (zh) * 2020-08-08 2022-07-05 邹爱忠 一种梯度硬质合金的制备方法
CN113182524B (zh) * 2021-04-25 2023-06-02 赣州澳克泰工具技术有限公司 一种钛基金属陶瓷及其制造方法和切削刀具
CN115464153A (zh) * 2022-09-14 2022-12-13 郑州轻工业大学 一种基于3d打印的梯度硬质合金及其制备方法

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KR20070000358A (ko) 2007-01-02
SE0501489L (sv) 2006-12-28
US20090011267A1 (en) 2009-01-08
KR20080019571A (ko) 2008-03-04
JP4842962B2 (ja) 2011-12-21
JP2008522027A (ja) 2008-06-26
US7588833B2 (en) 2009-09-15
CN101018879B (zh) 2011-04-06
JP2007007850A (ja) 2007-01-18
EP1904660B1 (en) 2014-08-13
CN1891842A (zh) 2007-01-10
CN100575524C (zh) 2009-12-30
US7794830B2 (en) 2010-09-14
EP1904660A4 (en) 2010-10-06
EP1739198A1 (en) 2007-01-03
KR101353651B1 (ko) 2014-01-20
CN101018879A (zh) 2007-08-15
US20070009764A1 (en) 2007-01-11
EP1904660A1 (en) 2008-04-02

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