WO1999024634A1 - PVD Al2O3 COATED CUTTING TOOL - Google Patents
PVD Al2O3 COATED CUTTING TOOLInfo
- Publication number
- WO1999024634A1 WO1999024634A1 PCT/SE1998/002009 SE9802009W WO9924634A1 WO 1999024634 A1 WO1999024634 A1 WO 1999024634A1 SE 9802009 W SE9802009 W SE 9802009W WO 9924634 A1 WO9924634 A1 WO 9924634A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- cutting tool
- hkl
- deposited
- ai2o3
- 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
Links
Classifications
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/354—Introduction of auxiliary energy into the plasma
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/541—Heating or cooling of the substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
- B23B2228/10—Coatings
-
- 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
- Y10T407/00—Cutters, for shaping
- Y10T407/27—Cutters, for shaping comprising tool of specific chemical composition
-
- 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
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- 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 describes a cutting tool for metal machining, having a body of cemented carbide, cer- met, ceramics or high speed steel and on the surface of said body, a hard and wear resistant refractory coating is deposited.
- the coating is adherently bonded to the body and covering all functional parts of the tool.
- the coating is composed of one or more layers of refractory compounds of which at least one layer consists of fine- crystalline alumina, AI2O3 , deposited by Physical Vapour Deposition (PVD) and the non-Al2U3 -layer (s) , if any at all, consists of metal nitrides and/or carbides with the metal elements chosen from Ti, Nb, Hf, V, Ta, Mo, Zr, Cr, W and Al .
- PVD Physical Vapour Deposition
- s non-Al2U3 -layer
- Cemented carbide cutting tools coated with alumina layers have been commercially available for over two decades.
- the CVD technique usually employed involves the deposition of material from a reactive gas atmosphere on a substrate surface held at elevated temperatures.
- AI2O3 crystallizes into several different phases such as ⁇ (alpha), ⁇ (kappa) and ⁇ (chi) called the " ⁇ -series” with hep (hexagonal close packing) stacking of the oxygen atoms, and into ⁇ (gamma), ⁇ (theta), ⁇ (eta) and ⁇ (delta) called the " ⁇ -series" with fee (face centered cubic) stacking of the oxygen atoms .
- AI2O3 -phases in CVD coatings deposited on cemented carbides at conventional CVD temperatures are the stable alpha and the metastable kappa phases , however, occasionally the metastable theta phase has also been observed.
- the CVD I2O3-coatings of the ⁇ - , K- and/or ⁇ -phase are fully crystalline with a grain size in the range 0.5-5 ⁇ m and having well-facetted grain structures.
- the inherently high deposition temperature of about 1000 °C renders the total stress in CVD AI2O3 -coatings on cemented carbide substrates to be tensile, hence the total stress is dominated by thermal stresses caused by the difference in thermal expansion coefficients between the substrate and the coating and less by intrinsic stresses which have their origin from the deposition process itself and are of compressive nature.
- the tensile stresses may exceed the rupture limit of AI2O3 and cause the coating to crack extensively and thus degrade the performance of the cutting edge in e.g. wet machining where the corrosive chemicals in the coolant fluid may exploit the cracks in the coating as diffusion paths .
- PVD-coated tools perform very well when machining various steels and cast irons under dry or wet cutting conditions.
- PVD coated tool application area Such cutting operations are often referred to as the "PVD coated tool application area" .
- Plasma assisted CVD technique, PACVD makes it possible to deposit coatings at lower substrate tempera- tures as compared to thermal CVD temperatures and thus avoid the dominance of the thermal stresses.
- the PACVD process for depositing AI2O3 includes the reaction between an Al-halogenide, e.g. AICI3, and an oxygen donor, e.g. CC>2, and because of the Al incompleteness of this chemical reaction, chlorine is to a large extent trapped in the AI2O3 -coating and its content could be as large as 3.5 %.
- an Al-halogenide e.g. AICI3
- an oxygen donor e.g. CC>2
- chlorine is to a large extent trapped in the AI2O3 -coating and its content could be as large as 3.5 %.
- these PACVD AI2O3 -coatings are generally composed of, besides the crystalline alfa- and/or gamma-Al2C>3 -phase, a substantial amount of amorphous alumina which in combination with the high content of halogen impurities, degrades both the chemical and mechanical properties of said coating, hence making the coating material non-optimised as a tool material,
- the field of the present invention relates particularly to the art of PVD AI2O3 coated carbide cutting tools or tools of similar hard materials such as cermets, ceramics and high-speed steel.
- PVD Planar Metal Deposition
- IBAD Ion Beam Assisted Deposition
- ARE Activated Reactive Evaporation
- Each method has its own merits and the intrinsic properties of the produced coatings such as microstructure/grain size, hardness, state of stress, intrinsic cohesion and adhesion to the underlying substrate may vary depending on the particular PVD method chosen.
- PVD deposition by HF diode- or magnetron sputtering resulted in crystalline C1-AI2O3 only when the substrate temperature was kept as high as 1000 °C (Thornton and Chin, Ceramic Bulletin, 56(1977)504).
- ARE method for depositing AI2O3 only resulted in fully dense and hard AI2O3 -coatings at substrate temperatures around 1000 °C (Bunshah and Schramm, Thin Solid Films, 40(1977)211) .
- the bipolar pulsed DMS technique (Dual Magnetron Sputtering) which is disclosed in DD 252 205 and DE 195 18 779, a wide range of opportunities opened up for the deposition of insulating layers such as AI2O3 and, furthermore, the method has made it possible to deposit crystalline AI2O3 -layers at substrate temperatures in the range 500 to 800 °C.
- the two magnetrons alternately act as an anode and a cathode and, hence, preserve a metallic anode over long process times. At high enough frequencies, possible electron charging on the insulating layers will be suppressed and the otherwise troublesome phenomenon of "arcing" will be limited.
- the DMS sputtering technique is capable of depositing and producing high- quality, well-adherent , crystalline 01-AI2O3 thin films at substrate temperatures less than 800 °C.
- the " ⁇ - Al 2 C>3 -layers " may partially also contain the gamma ( ⁇ ) phase from the " ⁇ -series" of the Al 2 ⁇ 3-poly- morphs .
- the size of the ⁇ -grains in the coating is much smaller than the size of the ⁇ -grains.
- the ⁇ -Al2C>3 grain size typically varies between 0.05 and 0.1 ⁇ m.
- the novel, pulsed DMS sputtering deposition method has the decisive, important advantage that no impurities such as halogen atoms, e.g. chlorine, are incorporated in the AI2O3 -coating.
- Fig. 1 is an EDS-analysis of an Al2 ⁇ 3 ⁇ layer deposited by PACVD (with AICI3 as a precursor) containing Cl-impurities.
- Fig. 2 is an EDS-analysis of a ⁇ -Al2 ⁇ 3 ⁇ layer according to the invention.
- Fig. 3 shows an X-ray diffraction pattern from an AI2O3-layer containing ⁇ -phase.
- Fig. 4 shows an X-ray diffraction pattern from an AI2O3-layer also containing ⁇ -phase.
- Fig. 5 shows an electron diffraction pattern from an Al2 ⁇ 3 ⁇ layer deposited at a substrate temperature of 650 °C.
- a cutting tool for metal machining such as turning (threading and parting) , milling and drilling comprising a body of a hard alloy of cemented carbide, cermet, ceramics or high speed steel onto which a hard and wear resistant refractory coating is deposited by the DMS PVD method at substrate temperatures of 450 to 700 °C, preferably 550 to 650 °C, depending on the particular material of the tool body, and that said wear resistant coating is composed of one or more layers of refractory compounds of which at least one layer, preferably the outermost layer, consists of AI2O3 and that the innermost layer(s), if any at all, between the tool body and the AI2O3 -layer, is composed of metal nitrides and/or carbides with the metal elements selected from Ti, Nb, Hf, V, Ta, Mo, Zr, Cr
- the AI2O3 -layers consist of high-quality, dense, fine-grained crystalline ⁇ -Al2C>3 with a grain size less than 0.1 ⁇ m. Furthermore, the ⁇ -Al2 ⁇ 3 ⁇ layers are virtually free of cracks and halogen impuri- ties.
- Fig, 1 which is an EDS-analysis of an AI2O3 -layer deposited by PACVD (with AICI3 as a precursor) containing Cl -impurities
- Fig. 2 which is an EDS-analysis of a ⁇ -Al2C>3 -layer according to the invention. In the latter AI2O3 -layer no detectable impurities are present.
- the ⁇ -Al2 ⁇ 3 ⁇ layers according to the invention further give the cutting edges of the tool an extremely smooth surface finish which, compared to prior art ⁇ - AI2O3 coated tools, results in an improved surface finish also of the workpiece being machined.
- the very smooth surface finish can be attributed to the very fine crystallinity of the coating.
- the " ⁇ - l2C ⁇ 3 "-layers may also partially contain other phases from the " ⁇ -series" like ⁇ , ⁇ and ⁇ . Identification of the ⁇ - and/or ⁇ -phases in the AI2O3 -layers according to the invention can pre- ferably be made by X-ray diffraction.
- a second identification method for the AI2O3 -phases is based on electron diffraction in a Transmission Electron Microscope (TEM) .
- TEM Transmission Electron Microscope
- a diffraction pattern from an Al2U3-layer deposited at a substrate temperature of 650 °C is shown in Fig. 5.
- the pattern shows rings from a polycrystalline phase with grains considerably smaller than the diameter of the electron beam and, furthermore, the intensity of the rings and the distances between the rings again unequivocally identifies the ⁇ -phase of
- a Texture Coefficient, TC can be defined as. Tc thki, . yg& . 1 V i (hki ) in _ l 0 (hkl )
- I(hkl) measured intensity of the (hkl) reflection
- I 0 (hkl) standard intensity from the ASTM standard powder pattern diffraction data
- n number of reflections used in the calculation (hkl) reflections used are: (111), (311), (222), (400) and (440) and whenever the TC(hkl) > 1, there is a texture in the [hkl] -direction. The larger the value of TC(hkl), the more pronounced is the texture. According to the present invention, the TC for the set of (440) crystal planes is greater than 1.5.
- the PVD ⁇ -Al2C>3 without containing any portion of the coarser and thermodynamically stable ⁇ -Al2C>3 -phase shows in certain metal machining operations, a wear resistance which is equal to the wear resistance found in coarser CVD OC-AI2O3 -coatings depo- sited at temperatures around 1000 °C.
- edges of the ⁇ -Al2C>3 coated cutting tools according to the invention are treated by a gentle wet-blasting process or by edge brushing with brushes based on e.g. SiC as disclosed in the Swedish patent application 9402534-4.
- the total coating thickness according to the present invention varies between 0.5 and 20 ⁇ m, preferably between 1 and 15 ⁇ m with the thickness of the non-Al2C>3- layer(s) varying between 0.1 and 10 ⁇ m, preferably between 0.5 and 5 ⁇ m.
- the fine-grained ⁇ -Al2 ⁇ 3-coating can also be deposited directly onto the cutting tool sub- strate of cemented carbide, cermet, ceramics or high speed steel and the thickness of said ⁇ -Al2C>3 varies then between 0.5 and 15 ⁇ m preferably between 1 and 10 ⁇ m.
- further coatings of metal nitrides and/or carbides with the metal elements selected from Ti, Nb, Hf , V, Ta, Mo, Zr, Cr, W and Al be deposited on top of the AI2O3 -layer.
- the ⁇ -Al2 ⁇ 3 -layer according to the invention is deposited by a bipolar dual magnetron sputtering technique at substrate temperatures of 450-700 °C, preferably 550- 650 °C, using aluminium targets, a gas mixture of Ar and O2 and a process pressure in the range 1-5 ⁇ bar.
- the substrate may be floating or pulsed biased, the exact conditions depending to a certain extent on the design of the equipment being used. It is within the purview of the skilled artisan to determine whether the requisite grain size and phase compositions have been obtained and to modify the deposition conditions in accordance with the present specification, if desired, to affect the nanostructure of the AI2O3-layer within the frame of the invention.
- the layer (s) described in the present invention comprising metal nitrides and/or carbides and/or car- bonitrides and with the metal elements selected from Ti , Nb, Hf , V, Ta, Mo, Zr, Cr, W and Al can be deposited by PVD-technique, CVD- and/or MTCVD-technique (Medium Temperature Chemical Vapor Deposition) .
- PVD-technique Chemical Vapor Deposition
- Examples 3, 4 and 6 demonstrate the surprisingly good wear resistance properties of the fine-grained ⁇ - AI2O3 -layers compared to traditionally CVD-deposited single phase ⁇ -Al 2 C>3 and single phase 0C-AI2O3 -layers .
- Example. 1 A) Commercially available cemented carbide threading inserts of style R166.OG-16MM01-150 having a composition of 10 w% Co and balance WC, coated with an approximately 2 ⁇ m TiN-layer by an ion plating technique. B) TiN coated tools from A) were coated with a 1 ⁇ m fine-grained ⁇ -Al2U3 -layer in a separate experiment with the pulsed magnetron sputtering technique. The deposition temperature was 650 °C and the process pressure was 1 ⁇ bar. C) Cemented carbide threading inserts of style
- R166.OG-16MM011-150 having a composition of 10 w% Co and balance WC, coated with an approximately 3 ⁇ m TiN-layer by an ion plating technique.
- Coated tool inserts from B) and C) were then tested in a threading operation at a customers site in the production of engine oil plugs of cast iron (SS0125; 180- 240 HB) .
- the thread of the plug being produced was of size M36 x 1.5.
- the alumina coating from E) appeared transparent and very smooth. SEM-studies of a fracture cross section of the alumina coating showed a very fine-grained struc- ture. An XRD- investigation identified the alumina phase as pure ⁇ -Al2C>3.
- Coated tool inserts from D) and E) were then tested in a drilling operation in a workpiece material of a low alloyed, non-hardened steel (SS 2541) .
- the cutting operation was periodically interrupted in order to measure the crater wear of the cutting edges.
- the crater wear was measured in an optical microscope.
- the machining time until the Al2 ⁇ 3 ⁇ layer was worn through, was registered (i.e. when the inner TiCN-coat- ing just becoming visible) .
- the thickness ( ⁇ m) of the AI2O3 -layer was divided by the above defined machining time (min) .
- the re- suits below express the wear rate figure of merit.
- C) invention 0.5 ⁇ m/min
- the deposi- tion temperature was 600 °C and the process pressure was 1 ⁇ bar.
- the cutting operation was periodically interrupted in order to measure the crater wear of the cutting edges.
- the crater wear was measured in an optical microscope.
- the machining time until the AI2O3 -layer was worn through, was registered (i.e. when the inner TiN or
- Example 5 Coated cutting inserts from I) , J) and K) in Example 4 were tested under the same cutting conditions and cut- ting data as in Example 4. The machining time until a predetermined crater wear had developed on the rake face of the inserts was registered. The results below express said machining time until the predetermined crater wear.
- the deposition temperature was 600 °C and the process pressure was 1 ⁇ bar.
- Coated inserts from L) and M) were then tested in a continuous turning operation in a low alloyed, non-hard- ened steel (SS2541) .
- the crater wear of the cutting edges was measured.
- the cutting operation was periodically interrupted in order to measure the crater wear of the cutting edges.
- the crater wear was measured in an optical microscope.
- the machining time until the AI2O3 -layer was worn through, was registered (i.e. when the inner TiCN or
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Physical Vapour Deposition (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Drilling Tools (AREA)
- Chemically Coating (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
Claims
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL98340602A PL340602A1 (en) | 1997-11-06 | 1998-11-06 | Cutting tool plated with a1203 by pvd (physical vacuum depositing) process |
| DE69821516T DE69821516T2 (en) | 1997-11-06 | 1998-11-06 | PVD Al2O3 COATED CUTTING TOOL |
| IL13522398A IL135223A (en) | 1997-11-06 | 1998-11-06 | Aluminum oxide coated cutting tool and processes for the preparation thereof |
| EP98954899A EP1029105B1 (en) | 1997-11-06 | 1998-11-06 | PVD Al2O3 COATED CUTTING TOOL |
| JP2000519623A JP2001522725A (en) | 1997-11-06 | 1998-11-06 | PVDAl2O3 coated cutting tool |
| BR9813186-9A BR9813186A (en) | 1997-11-06 | 1998-11-06 | Cutting tool coated by physical vapor deposition (pvd) deai2o3 |
| AT98954899T ATE259003T1 (en) | 1997-11-06 | 1998-11-06 | PVD AL2O3 COATED CUTTING TOOL |
| KR1020007003870A KR100614961B1 (en) | 1997-11-06 | 1998-11-06 | Cutting tools coated with PPD Al₂O₃ |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE9704066-1 | 1997-11-06 | ||
| SE9704066A SE520802C2 (en) | 1997-11-06 | 1997-11-06 | Cutting tool coated with alumina and process for its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1999024634A1 true WO1999024634A1 (en) | 1999-05-20 |
Family
ID=20408890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/SE1998/002009 Ceased WO1999024634A1 (en) | 1997-11-06 | 1998-11-06 | PVD Al2O3 COATED CUTTING TOOL |
Country Status (12)
| Country | Link |
|---|---|
| US (3) | US6210726B1 (en) |
| EP (2) | EP1029105B1 (en) |
| JP (1) | JP2001522725A (en) |
| KR (1) | KR100614961B1 (en) |
| CN (1) | CN1278307A (en) |
| AT (2) | ATE286155T1 (en) |
| BR (1) | BR9813186A (en) |
| DE (2) | DE69821516T2 (en) |
| PL (1) | PL340602A1 (en) |
| RU (1) | RU2206432C2 (en) |
| SE (1) | SE520802C2 (en) |
| WO (1) | WO1999024634A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6383624B1 (en) | 1999-05-06 | 2002-05-07 | Sandvik Ab | PVD Al2O3 coated cutting tool |
| US6572991B1 (en) | 2000-02-04 | 2003-06-03 | Seco Tools Ab | Deposition of γ-Al2O3 by means of CVD |
| EP1916007A1 (en) * | 2006-10-18 | 2008-04-30 | DePuy Products, Inc. | Aluminium oxide coated implants and components |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5516588A (en) * | 1991-03-27 | 1996-05-14 | Widia Gmbh | Composite body, its use and a process for its production |
| EP0744473A1 (en) * | 1995-05-22 | 1996-11-27 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Vacuum coated composite body and method of its production |
| US5674564A (en) * | 1991-06-25 | 1997-10-07 | Sandvik Ab | Alumina-coated sintered body |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE252205C (en) | ||||
| CH540991A (en) | 1971-07-07 | 1973-08-31 | Battelle Memorial Institute | Method for increasing the wear resistance of the surface of a "hard metal" part |
| SE464818B (en) * | 1989-06-16 | 1991-06-17 | Sandvik Ab | COVERED SHOULD BE CUTTING |
| DE4209975A1 (en) | 1992-03-27 | 1993-09-30 | Krupp Widia Gmbh | Composite body and its use |
| EP0592986B1 (en) | 1992-10-12 | 1998-07-08 | Sumitomo Electric Industries, Limited | Ultra-thin film laminate |
| SE501527C2 (en) | 1992-12-18 | 1995-03-06 | Sandvik Ab | Methods and articles when coating a cutting tool with an alumina layer |
| SE509201C2 (en) | 1994-07-20 | 1998-12-14 | Sandvik Ab | Aluminum oxide coated tool |
| US5700551A (en) | 1994-09-16 | 1997-12-23 | Sumitomo Electric Industries, Ltd. | Layered film made of ultrafine particles and a hard composite material for tools possessing the film |
| DE19518779C1 (en) | 1995-05-22 | 1996-07-18 | Fraunhofer Ges Forschung | Stable aluminium oxide coating on sintered body |
| US5879823A (en) * | 1995-12-12 | 1999-03-09 | Kennametal Inc. | Coated cutting tool |
| SE520802C2 (en) | 1997-11-06 | 2003-08-26 | Sandvik Ab | Cutting tool coated with alumina and process for its manufacture |
-
1997
- 1997-11-06 SE SE9704066A patent/SE520802C2/en unknown
-
1998
- 1998-11-06 RU RU2000114171/02A patent/RU2206432C2/en not_active IP Right Cessation
- 1998-11-06 US US09/187,006 patent/US6210726B1/en not_active Expired - Lifetime
- 1998-11-06 PL PL98340602A patent/PL340602A1/en unknown
- 1998-11-06 CN CN98810834A patent/CN1278307A/en active Pending
- 1998-11-06 EP EP98954899A patent/EP1029105B1/en not_active Expired - Lifetime
- 1998-11-06 AT AT02013750T patent/ATE286155T1/en active
- 1998-11-06 BR BR9813186-9A patent/BR9813186A/en not_active IP Right Cessation
- 1998-11-06 AT AT98954899T patent/ATE259003T1/en active
- 1998-11-06 JP JP2000519623A patent/JP2001522725A/en active Pending
- 1998-11-06 DE DE69821516T patent/DE69821516T2/en not_active Expired - Lifetime
- 1998-11-06 DE DE69828453T patent/DE69828453T2/en not_active Expired - Lifetime
- 1998-11-06 EP EP02013750A patent/EP1253215B1/en not_active Expired - Lifetime
- 1998-11-06 WO PCT/SE1998/002009 patent/WO1999024634A1/en not_active Ceased
- 1998-11-06 KR KR1020007003870A patent/KR100614961B1/en not_active Expired - Fee Related
-
2001
- 2001-02-14 US US09/782,226 patent/US6423403B2/en not_active Expired - Lifetime
-
2002
- 2002-05-22 US US10/151,821 patent/US6673430B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5516588A (en) * | 1991-03-27 | 1996-05-14 | Widia Gmbh | Composite body, its use and a process for its production |
| US5674564A (en) * | 1991-06-25 | 1997-10-07 | Sandvik Ab | Alumina-coated sintered body |
| EP0744473A1 (en) * | 1995-05-22 | 1996-11-27 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Vacuum coated composite body and method of its production |
Non-Patent Citations (4)
| Title |
|---|
| INTERNATIONAL SYMPOSIUM ON TRENDS AND NEW APPLICATIONS IN THIN FILMS, TATF'96, 5TH SYMPOSIUM, Colmar, France, 1-3 April 1996, F. FIETZKE et al., "Pulsed Magnetron Sputtering of Alumina Films: Crystalline Phases at Low Temperatures", p. 218-220. * |
| SURFACE AND COATINGS TECHNOLOGY, Volume 82, 1996, O. ZYWITZKI et al., "Effect of the Substrate Temperature on the Structure and Properties of A1203 Layers Reactively Deposited by Pulsed Magnetron Sputtering", pages 169-175. * |
| SURFACE AND COATINGS TECHNOLOGY, Volume 86-87, 1996, O. ZYWITZKI et al., "Influence of Coating Parameters on the Structure and Properties of A1203 Layers Reactively Deposited by Means of Pulsed Magnetron Sputtering", pages 640-647. * |
| SURFACE AND COATINGS TECHNOLOGY, Volume 94-95, 1997, O. ZYWITZKI et al., "Correlation Between Structure and Properties of Reactively Deposited A1203 Coatings by Pulsed Magnetron Sputtering", pages 303-308. * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6383624B1 (en) | 1999-05-06 | 2002-05-07 | Sandvik Ab | PVD Al2O3 coated cutting tool |
| US6572991B1 (en) | 2000-02-04 | 2003-06-03 | Seco Tools Ab | Deposition of γ-Al2O3 by means of CVD |
| DE10314929B4 (en) * | 2002-04-17 | 2010-01-28 | Cemecon Ag | Body with a coating in R-3c Structure, method and apparatus for PVD coating |
| DE10314929B9 (en) * | 2002-04-17 | 2010-12-23 | Cemecon Ag | Body with a coating in R-3c Structure, method and apparatus for PVD coating |
| US8309161B2 (en) | 2005-09-30 | 2012-11-13 | Depuy Products, Inc. | Aluminum oxide coated implants and components |
| EP1916007A1 (en) * | 2006-10-18 | 2008-04-30 | DePuy Products, Inc. | Aluminium oxide coated implants and components |
| US8691378B2 (en) | 2009-03-19 | 2014-04-08 | Walter Ag | Cutting tool |
| WO2011020739A1 (en) | 2009-08-17 | 2011-02-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Aluminium oxide coated body and method for the production thereof |
| DE102009028577A1 (en) | 2009-08-17 | 2011-03-03 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Coated bodies of metal, cemented carbide, cermet, ceramic or semiconductor material, and methods of coating such bodies |
| EP3461928A1 (en) * | 2017-09-29 | 2019-04-03 | Walter Ag | Tacno coatings and production process |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9813186A (en) | 2000-08-22 |
| DE69821516D1 (en) | 2004-03-11 |
| DE69821516T2 (en) | 2004-07-01 |
| DE69828453D1 (en) | 2005-02-03 |
| ATE259003T1 (en) | 2004-02-15 |
| US6423403B2 (en) | 2002-07-23 |
| DE69828453T2 (en) | 2005-06-02 |
| US6210726B1 (en) | 2001-04-03 |
| EP1253215B1 (en) | 2004-12-29 |
| US6673430B2 (en) | 2004-01-06 |
| SE520802C2 (en) | 2003-08-26 |
| KR20010072535A (en) | 2001-07-31 |
| CN1278307A (en) | 2000-12-27 |
| EP1253215A2 (en) | 2002-10-30 |
| JP2001522725A (en) | 2001-11-20 |
| EP1253215A3 (en) | 2003-01-02 |
| US20010049011A1 (en) | 2001-12-06 |
| RU2206432C2 (en) | 2003-06-20 |
| US20030027015A1 (en) | 2003-02-06 |
| KR100614961B1 (en) | 2006-08-25 |
| PL340602A1 (en) | 2001-02-12 |
| SE9704066D0 (en) | 1997-11-06 |
| ATE286155T1 (en) | 2005-01-15 |
| EP1029105B1 (en) | 2004-02-04 |
| SE9704066L (en) | 1999-05-07 |
| EP1029105A1 (en) | 2000-08-23 |
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