USRE39884E1 - Coated milling insert and method of making it - Google Patents

Coated milling insert and method of making it Download PDF

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Publication number
USRE39884E1
USRE39884E1 US11/483,381 US48338196A USRE39884E US RE39884 E1 USRE39884 E1 US RE39884E1 US 48338196 A US48338196 A US 48338196A US RE39884 E USRE39884 E US RE39884E
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Prior art keywords
layer
insert
tic
cemented carbide
thickness
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Expired - Fee Related
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US11/483,381
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English (en)
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{dot over (A)}ke Östlund
Jeanette Persson
Björn Ljungberg
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Sandvik Intellectual Property AB
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Sandvik Intellectual Property AB
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    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
    • 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
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • 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
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • 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
    • 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
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y10T428/24975—No layer or component greater than 5 mils thick
    • 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 a coated cutting tool (cemented carbide insert) particularly useful for wet and dry milling of low and medium alloyed steels, with raw surfaces such as cast skin, forged skin, hot or cold rolled skin or pre-machined surfaces.
  • the cutting edge When milling low and medium alloyed steels with cemented carbide tools, the cutting edge is worn according to different wear mechanisms, such as chemical wear, abrasive wear, adhesive wear and by edge chipping caused by cracks formed along the cutting edge, the comb cracks.
  • the comb crack formation is particularly severe when wet milling is employed (using coolant). Coolant and work piece material may penetrate and widen the comb cracks and the edge will start to chip. A chipped edge will generate a bad surface finish of the machined component.
  • a coated cemented carbide insert when cutting in steels with raw surface zones, must consist of a tough carbide and have very good coating adhesion.
  • the adhesive wear is generally the dominating wear type.
  • thin (1-3 ⁇ m) CVD- or PVD-coatings have to be used.
  • Measures can be taken to improve the cutting performance with respect to a specific wear type. However, very often such action will have a negative effect on other wear properties.
  • Swedish patent application 9501286-0 which corresponds to U.S. Ser. No. 08/616,012, herein incorporated by reference discloses a coated cutting insert particularly useful for dry milling of grey cast iron.
  • the insert is characterized by a straight WC-Co cemented carbide grade and a coating including a layer of TiC x N y O z with columnar grains and a top layer of fine grained textured ⁇ -Al 2 O 3 .
  • Swedish patent application 9502640-7 which corresponds to U.S. Ser. No. 08/675,034, herein incorporated by reference, discloses a coated turning insert particularly useful for intermittent turning in low alloyed steel.
  • the insert is characterized by a WC-Co cemented carbide body having a highly W-alloyed Co-binder phase and a coating including a layer of TiC x N y O z with columnar grains and a top layer of a fine grained, textured ⁇ -Al 2 O 3 .
  • Swedish patent application 9503056-5 which corresponds to U.S. Ser. No. 08/703,965, herein incorporated by reference, discloses a coated turning cutting tool particularly useful for cutting in hot and cold forged low alloyed steel.
  • the insert is characterized by a WC-Co cemented carbide body having a highly W-alloyed Co-binder phase and a coating including a layer of TiC x N y O z with columnar grains and a top layer of a fine grained, ⁇ -Al 2 O 3 .
  • a cutting tool insert for milling low and medium alloyed steels with or without raw surfaces during wet or dry conditions comprising a cemented carbide body and a coating wherein said cemented carbide body comprises WC, 8.6-9.5 wt-% Co and 0.2-1.8 wt-% cubic carbides of Ta, Ti and Nb, with Ti present on a level corresponding to a technical impurity, and a highly W-alloyed binder phase with a CW-ratio of 0.78-0.93 and said coating comprises
  • a milling insert comprising a cemented carbide body and a coating comprising a WC-Co-based cemented carbide body with a highly W-alloyed binder phase with a CW-ratio of 0.78-0.93 with
  • the FIGURE is a micrograph in 10,000 ⁇ magnification of a coated insert according to the present invention in which
  • the milling cutting insert according to the invention is: a cemented carbide body with a highly W-alloyed binder phase and with a well-balanced chemical composition and grain size of the WC, a columnar TiC x N y O z -layer, a ⁇ -Al 2 O 3 -layer, a TiN-layer and optionally followed by smoothening, the cutting edges by brushing the edges with, e.g., a SiC based brush.
  • a milling tool insert is provided with a cemented carbide body with a composition of 8.6-9.5 wt % Co, preferably 8.7-9.5 wt % Co, most preferably 8.8-9.4 wt % Co, 0.2-1.8 wt % cubic carbides, preferably 0.4-1.8 wt % cubic carbides, most preferably 0.5-1.7 wt % cubic carbides of the metals Ta, Nb and Ti and balance WC.
  • the cemented carbide may also contain other carbides from elements from group IVb, Vb or VIb of the periodic table.
  • the content of Ti is preferably on a level corresponding to a technical impurity.
  • the average grain size of the WC is in the range of about 1.5-2 ⁇ m, preferably about 1.7 ⁇ m.
  • the cobalt binder phase is highly alloyed with W.
  • the CW-value is a function of the W content in the Co binder phase. A low CW-value corresponds to a high W-content in the binder phase.
  • the cemented carbide body has a CW-ratio of 0.78-0.93, preferably 0.80-0.91, and most preferably 0.82-0.90.
  • the cemented carbide may contain small amounts, ⁇ 1 volume %, of ⁇ -phase (M 6 C), without any detrimental effect. From the CW-value, it follows that no free graphite is allowed in the cemented carbide body according to the present invention.
  • the cement carbide body may contain a thin (about 5-25 ⁇ m) surface zone depleted in cubic carbides and often enriched in binder phase according to prior art such as disclosed in U.S. Pat. No. 4,610,931.
  • the cemented carbide may contain carbonitride or even nitride.
  • the coating comprises
  • a cemented carbide milling tool in accordance with the invention inserts of style SEKN 1204 AZ with the composition 9.1 wt-% Co, 1.25 wt-% TaC, 0.30 wt-% NbC and balance WC, with a binder phase highly alloyed with W, corresponding to a CW-ratio of 0.86 were coated with a 0.5 ⁇ m equiaxed TiCN-layer (with a high nitrogen content corresponding to an estimated C/N-ratio of 0.05) followed by a 4 ⁇ m thick TiCN-layer with columnar grains by using MTCVD-technique (temperature 885-850° C. and CH 3 CN as the carbon/nitrogen source).
  • a 1.0 ⁇ m thick layer of Al 2 O 3 was deposited using a temperature 970° C. and a concentration of H 2 S dopant of 0.4% as disclosed in EP-A-523 021 which corresponds to U.S. Pat. No. 5,674,564.
  • a thin (0.3 ⁇ m) layer of TiN was deposited on top, according to known CVD-technique. XRD-measurement showed that the Al 2 O 3 -layer consisted of 100% ⁇ -phase.
  • the cemented carbide body had a WC grain size in average of 1.65 ⁇ m.
  • the coated inserts were brushed by a nylon straw brush containing SiC grains.
  • a strongly competitive cemented carbide grade in style SEKN 1204 from an external leading carbide producer was selected for comparison in a wet milling test.
  • the carbide had a composition of 9.0 wt-% Co, 0.2 wt-% TiC, 0.5 wt-% TaC, 0.1 wt % NbC balance WC and a CW-ratio of 0.95.
  • the WC-grain size was 2.5 ⁇ m.
  • the insert had a coating consisting of a 6 ⁇ m TiCN layer and a 0.3 ⁇ m TiN layer.
  • Two parallel bars, each having a thickness of 35 mm, were centrally positioned relative to the cutter body (diameter 100 mm), and the bars were placed with an air gap of 10 mm between them.
  • the cutting data were:
  • Variant A showed no comb cracks and variant B showed 14 comb cracks. After milling 1800 mm, variant B broke down due to a lot of chipping and fracture between the comb cracks. Variant A, according to the invention, lasted 4200 mm, corresponding to an effective tool life of 11 min compared with about 4 min for variant B.
  • a cemented carbide milling tool in accordance with the invention inserts of style SEKN 1204 AZ with the composition 9.1 wt-% Co, 1.23 wt-% TaC, 0.30 wt-% NbC and balance WC, with a binder phase highly alloyed with W corresponding to a CW-ratio of 0.85 were coated with a 0.5 ⁇ m equiaxed TiCN-layer (with a high nitrogen content corresponding to an estimated C/N-ratio of 0.05) followed by a 3.7 ⁇ m thick TiCN-layer with columnar grains by using MTCVD-technique (temperature 885-850° C. and CH 3 CN as the carbon/nitrogen source).
  • a 0.9 ⁇ m thick layer of Al 2 O 3 was deposited using a temperature 970° C. and a concentration of H 2 S dopant of 0.4% as disclosed in EP-A-523 021 which corresponds to U.S. Pat. No. 5,674,564.
  • a thin (0.3 ⁇ m) layer of TiN was deposited on top according to known CVD-technique. XRD-measurement showed that the Al 2 O 3 -layer consisted of 100% ⁇ -phase.
  • the cemented carbide body had a WC grain size in average of 1.6 ⁇ m.
  • a strongly competitive cemented carbide grade in style SEKN 1204 from an external leading cemented carbide producer was selected for comparison in a wet milling test.
  • the carbide had a composition of 11.0 wt-% Co, 0.2 wt-% TaC, 0.3 wt % NbC balance WC and a CW-ratio of 0.90.
  • the insert had a coating consisting of a 0.5 ⁇ m equiaxed TiCN layer, 2.0 ⁇ m TiCN columnar layer, 2.0 ⁇ m ⁇ -Al 2 O 3 -layer and a 0.3 ⁇ m TiN-layer.
  • the bars were, as very common extremely rusty due to outdoor stocking.
  • Two parallel bars each of a thickness having 32 mm were centrally positioned relative to the cutter body (diameter 100 mm), and the bars were placed with an air gap of 10 mm between them.
  • the cutting data were:
  • the insert C broke after 1100 mm
  • the insert B broke after 2150 mm
  • the insert A broke after 2400 mm.
  • a cemented carbide milling tool in accordance with the invention inserts of style SEKN 1204 AZ with the composition 9.1 wt-% Co, 1.23 wt-% TaC, 0.30 wt-% NbC and balance WC, with a binder phase highly alloyed with W corresponding to a CW-ratio of 0.86 were coated with a 0.5 ⁇ m equiaxed TiCN-layer (with a high nitrogen content corresponding to an estimated C/N-ratio of 0.05) followed by a 3.7 ⁇ m thick TiCN-layer with columnar grains by using MTCVD-technique (temperature 885-850° C. and CH 3 CN as the carbon/nitrogen source).
  • a 1.1 ⁇ m thick layer of Al 2 O 3 was deposited using a temperature of 970° C. and a concentration of H 2 S dopant of 0.4% as disclosed in EP-A-523 021 which corresponds to U.S. Pat. No. 5,674,564.
  • a thin (0.3 ⁇ m) layer of TiN was deposited on top according to known CVD-technique. XRD-measurement showed that the Al 2 O 3 -layer consisted of 100% ⁇ -phase.
  • the cemented carbide body had a WC grain size in average of 1.7 ⁇ m.
  • the coated inserts were brushed by a nylon straw brush containing SiC grains.
  • a strongly competitive cemented carbide grade in style SEKN 1204 from an external leading carbide producer was used.
  • the carbide had a composition of 8.0 wt-% Co, 1.9 wt-% TaC, 0.2 wt % NbC, 0.2 wt % TiC balance WC and a CW-ratio of 0.85.
  • the insert had a coating consisting of a 1.1 ⁇ m TiN layer and 3.3 ⁇ m TiC layer.
  • a strongly competitive cemented carbide grade in style SEKN 1204 from an external leading carbide producer was used.
  • the carbide had a composition of 10.0 wt-% Co, 2.0 wt-% TaC, 0.2 wt % TiC, balance WC and a CW-ratio of 0.90.
  • the insert had a coating consisting of a 0.5 ⁇ m equiaxed TiCN layer, 3.3 ⁇ m TiCN columnar layer, 0.7 ⁇ m ⁇ -Al 2 O 3 -layer and a 0.5 ⁇ m TiN layer.
  • a bar with a thickness of 180 mm was centrally positioned relative to the cutter body (diameter 250 mm).
  • the cutting data were:
  • Insert B broke after 5000 mm after comb crack formation and chipping.
  • Insert C broke after 5400 mm by similar wear pattern and insert A was stopped after 6000 mm without other visible wear than a few small comb cracks.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Vapour Deposition (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coating By Spraying Or Casting (AREA)
US11/483,381 1995-11-30 1996-11-29 Coated milling insert and method of making it Expired - Fee Related USRE39884E1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9504304A SE9504304D0 (sv) 1995-11-30 1995-11-30 Coated milling insert
PCT/SE1996/001577 WO1997020081A1 (en) 1995-11-30 1996-11-29 Coated milling insert and method of making it

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US09/077,360 Reissue US6177178B1 (en) 1995-11-30 1996-11-29 Coated milling insert and method of making it

Publications (1)

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USRE39884E1 true USRE39884E1 (en) 2007-10-16

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US11/483,381 Expired - Fee Related USRE39884E1 (en) 1995-11-30 1996-11-29 Coated milling insert and method of making it
US09/077,360 Ceased US6177178B1 (en) 1995-11-30 1996-11-29 Coated milling insert and method of making it

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US (2) USRE39884E1 (enExample)
EP (1) EP0871796B1 (enExample)
JP (2) JP2000515587A (enExample)
KR (1) KR100430361B1 (enExample)
CN (1) CN1203638A (enExample)
AT (1) ATE231565T1 (enExample)
BR (1) BR9611780A (enExample)
DE (1) DE69625934T2 (enExample)
IL (1) IL124474A (enExample)
SE (1) SE9504304D0 (enExample)
WO (1) WO1997020081A1 (enExample)

Cited By (2)

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US8080323B2 (en) 2007-06-28 2011-12-20 Kennametal Inc. Cutting insert with a wear-resistant coating scheme exhibiting wear indication and method of making the same
US20190010606A1 (en) * 2015-08-29 2019-01-10 Kyocera Corporation Coated tool

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ATE380890T1 (de) * 2000-05-31 2007-12-15 Mitsubishi Materials Corp Beschichtetes schneidwerkzeug aus zementiertem karbid und verfahren zu dessen herstellung
US6638571B2 (en) 2000-05-31 2003-10-28 Mitsubishi Materials Corporation Coated cemented carbide cutting tool member and process for producing the same
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US6805944B2 (en) * 2001-03-26 2004-10-19 Mitsubishi Materials Corporation Coated cemented carbide cutting tool
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US7220098B2 (en) * 2003-05-27 2007-05-22 General Electric Company Wear resistant variable stator vane assemblies
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SE526599C2 (sv) * 2003-06-16 2005-10-18 Seco Tools Ab CVD-belagt hårdmetallskär
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JP2006026814A (ja) * 2004-07-16 2006-02-02 Tungaloy Corp 被覆切削チップ
KR100576321B1 (ko) * 2004-12-14 2006-05-03 한국야금 주식회사 고인성 절삭공구/내마모성 공구
SE528673C2 (sv) * 2005-01-03 2007-01-16 Sandvik Intellectual Property Belagt hårdmetallskär för torrfräsning i höglegerat grått gjutjärn samt sätt och användning
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EP0871796A1 (en) 1998-10-21
DE69625934D1 (de) 2003-02-27
US6177178B1 (en) 2001-01-23
JP2008183708A (ja) 2008-08-14
ATE231565T1 (de) 2003-02-15
SE9504304D0 (sv) 1995-11-30
WO1997020081A1 (en) 1997-06-05
KR19990071775A (ko) 1999-09-27
IL124474A (en) 2001-08-26
IL124474A0 (en) 1998-12-06
BR9611780A (pt) 1999-02-23
KR100430361B1 (ko) 2004-07-19
DE69625934T2 (de) 2003-11-13
JP2000515587A (ja) 2000-11-21
EP0871796B1 (en) 2003-01-22
CN1203638A (zh) 1998-12-30

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