Oxide coated cutting tool
Abstract
A body such as a cutting tool coated with refractory single- or multilayers, wherein specific layers are characterized by a controlled microstructure and phase composition with crystal planes preferably grown in a preferential direction with respect to the surface of the coated body. The coating includes one or several refractory layers of which at least one layer is a dense, fine-grained layer of α-Al2O3 preferably textured in the (104) direction. The coated tool exhibits excellent surface finish and shows much improved wear and toughness properties compared to prior art objects when used for machining steel, cast iron and, particularly, when machining nodular cast iron. REEXAMINATION RESULTS The questions raised in reexamination proceedings Nos. 90/009,410 and 90/009,666, filed May 5, 2009 and Feb. 24, 2010 respectively, have been considered, and the results thereof are reflected in this reissue patent which constitutes the reexamination certificate required by 35 U.S.C. 307 as provided in 37 CFR 1.570(e) for ex parte reexaminations, and/or the reexamination certificate required by 35 U.S.C. 316 as provided in 37 CFR 1.997(e) for inter partes reexaminations.

Term
Term ended
Expired 12 January 2015, 11.7 years ago.
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2 claims: 2 independent, 0 dependent
- 1A cutting tool insert of cemented carbide, titanium based carbonitride or ceramics at least partially coated with refractory layers, of which at least one layer is alumina, characterized in, that said alumina layer has a thickness of d = 0.5-25 µm with average grain size (s):0.5 µm < s < 1 µm for 0.5 µm < d < 2.5 µm and 0.5 µm < s < 4 µm for 2.5 µm < d < 25 µm and consists of single phase α-structure textured in the (104)-direction with a texture coefficient larger than 2.5 and most preferably larger than 3.0, the texture coefficient being defined as below:TChkl=IhklIohkl1nΣIhklIohkl-1wherel(hkl) = measured intensity of the (hkl) reflectionlo(hkl) = standard intensity of the ASTM standard powder pattern diffraction arean = number of reflections used in the calculation(hkl) reflections used are: (012), (104), (110), (113), (024), (116), said alumina layer being an exposed outermost layer in contact with a TiCxNyOz-layer and having a surface roughness (Ra) of less than 0,3µm over a measured length of 0,25 mm. Plaquette pour outil coupant constituée de carbure fritté, de carbonitrure à base de titane ou de céramique, au moins revêtue partiellement avec des couches réfractaires, dont au moins une couche est de l'alumine, caractérisée en ce que la couche d'alumine a une épaisseur de d = 0,5-25 µm avec une dimension (s) moyenne des grains : 0.5 µm < s < 1 µm for 0.5 µm < d < 2.5 µm and 0.5 µm < s < 4 µm for 2.5 µm < d < 25 µm et est constituée d'une structure α monophasée texturée dans la direction (104) avec un coefficient de texture supérieur à 2,5 et, de manière préférée entre toutes, supérieur à 3,0, le coefficient de texture étant défini ci-dessous : TChkl=IhklIohkl1nΣIhklIohkl-1 où I(hkl) = intensité mesurée de la réflexion (hkl)Io(hkl) = intensité standard de la zone de diffraction du diagramme de poudre standard ASTMn = nombre de réflexions utilisées dans le calcul les réflexions (hkl) utilisées sont : (012), (104), (110), (113), (024), (116), ladite couche d'alumine étant une couche extérieure exposée, en contact avec une couche TiCxNyOz et possédant une rugosité de surface (Ra) de moins de 0,3 µm sur une longueur mesurée de 0,25 mm.2. Plaquette selon la revendication 1, caractérisée en ce que ladite couche TiCxNyOz est la couche la plus interne du revêtement. Schneidwerkzeugeinsatz aus Hartmetall, Carbonitrid auf Titanbasis oder Keramik, welcher zumindest teilweise mit hitzebeständigen Schichten überzogen ist, von denen wenigstens eine Schicht Aluminiumoxid ist, dadurch gekennzeichnet, dass die Aluminiumoxidschicht eine Dicke von d= 0,5 bis 25 µm mit einer mittleren Korngröße (s) von 0.5 µm < s < 1 µm for 0.5 µm < d < 2.5 µm and 0.5 µm < s < 4 µm for 2.5 µm < d < 25 µm hat und aus einphasiger α-Struktur besteht, die in der (104)-Richtung mit einem Texturkoeffizienten größer als 2,5, besonders bevorzugt größer als 3,0 texturiert ist, wobei der Texturkoeffizient wie folgt definiert ist: TChkl=IhklIohkl1nΣIhklIohkl-1 worin l(hkl) = gemessene Intensität der (hkl)-Reflexion,l0(hkl) = Standardintensität der ASTM-Standard-Pulverbeugungsdaten,n = Anzahl der in der Berechnung verwendeten Reflexionen, (hkl)-Reflexionen sind: (012), (104), (110), (113), (024), (116), wobei die Aluminiumoxidschicht eine als äußerste Schicht freiliegende Schicht in Berührung mit einer TiCxNyOz-Schicht ist und eine Oberflächenrauheit (Ra) von weniger als 0,3 µm über eine Meßstrecke von 0,25 mm hat.
- 2Einsatz nach Anspruch 1, dadurch gekennzeichnet, dass die TiCxNyOz-Schicht die innerste Schicht des Überzuges ist. Insert according to claim 1, characterized in, that said TiCxNyOz-layer is the innermost layer of the coating.
Independent claims2
40 paragraphs, as filed
The present invention relates to a coated cutting tool for chipforming machining.
Chemical Vapour Deposition (CVD) of alumina on cutting tools has been an industrial practice for more than 15 years. The wear properties of Al<sub>2</sub>O<sub>3</sub> as well as of other refractory materials have been discussed extensively in the literature.
The CVD-technique has also been used to produce coatings of other metal oxides, carbides and nitrides, the metal being selected from transition metals of the IVB, VB and VIB groups of the Periodic Table. Many of these compounds have found practical applications as wear resistant or protective coatings, but few have received as much attention as TiC, TiN and Al<sub>2</sub>O<sub>3</sub>.
Cemented carbide cutting tools coated with various types Al<sub>2</sub>O<sub>3</sub>-coatings, e.g., pure κ-Al<sub>2</sub>O<sub>3</sub>, mixtures of κ-and α-Al<sub>2</sub>O<sub>3</sub> and very coarse-grained α-Al<sub>2</sub>O<sub>3</sub> have been commercially available for many years. Al<sub>2</sub>O<sub>3</sub> crystallizes in several different phases: α, κ, γ, β, θ etc. The two most frequently occurring phases in CVD of wear resistant Al<sub>2</sub>O<sub>3</sub>-coatings are the thermodynamically stable, hexagonal α-phase and the metastable κ-phase. Generally, the κ-phase is fine-grained with a grain size in the range 0.5-2.0 µm and often exhibits a columnar coating morphology. Furthermore, κ-Al<sub>2</sub>O<sub>3</sub> coatings are free from crystallographic defects and free from micropores or voids.
The α-Al<sub>2</sub>O<sub>3</sub> grains are usually coarser with a grain size of 1-6 µm depending upon the deposition conditions. Porosity and crystallographic defects are in this case more common.
Often both α- and κ-phase are present in a CVD alumina coating deposited onto a cutting tool. In commercial cutting tools, Al<sub>2</sub>O<sub>3</sub> is always applied on TiC coated carbide or ceramic substrates (see, e.g. <patcit id="pcit0001" dnum="US3837896A"><text>U.S. Pat. No. 3,837,896</text></patcit>, now Reissue <patcit id="pcit0002" dnum="US29420A"><text>U.S. Pat. No. 29,420</text></patcit>) and therefore the interfacial chemical reactions between the TiC-surface and the alumina coating are of particular importance. In this context the TiC layer should also be understood to include layers having the formula TiC<sub>x</sub>N<sub>y</sub>O<sub>z</sub> in which the carbon in TiC is completely or partly substituted by oxygen and/or nitrogen.
The practice of coating cemented carbide cutting tools with oxides to further increase their wear resistance is in itself well known as is evidenced in e.g. <patcit id="pcit0003" dnum="US29420A"><text>U.S. Pat. Reissue No. 29,420</text></patcit> and <patcit id="pcit0004" dnum="US4399168A"><text>U.S. Pat. Nos. 4,399,168</text></patcit>, <patcit id="pcit0005" dnum="US4018631A"><text>4,018,631</text></patcit>, <patcit id="pcit0006" dnum="US4490191A"><text>4,490,191</text></patcit> and <patcit id="pcit0007" dnum="US4463033A"><text>4,463,033</text></patcit>. These patents disclose oxide coated bodies and how different pretreatments e.g. of TiC-coated cemented carbide, enhance the adherence of the subsequently deposited oxide layer. Alumina coated bodies are further disclosed in <patcit id="pcit0008" dnum="US3736107A"><text>U.S. Pat. No. 3,736,107</text></patcit>,<patcit id="pcit0009" dnum="US5071696A"><text> 5,071,696</text></patcit> and <patcit id="pcit0010" dnum="US5137774A"><text>5,137,774</text></patcit> wherein the Al<sub>2</sub>O<sub>3</sub> layers comprise α, κ resp α+κ combinations.
<patcit id="pcit0011" dnum="US4619866A"><text>US 4,619,866</text></patcit> describes a method for producing fast growing Al<sub>2</sub>O<sub>3</sub> layers by utilizing a hydrolysis reaction of a metal halide under the influence of a dopant e.g. hydrogen sulphide(H<sub>2</sub>S) in the concentration range 0.01-0.2 % at a CVD deposition temperature 1000-1050°C. Under these process conditions, essentially two phases of Al<sub>2</sub>O<sub>3</sub>, the α- and the κ phases, are produced. The resulting coating consists of a mixture of the smaller κ-grains and the larger α-grains. The process yields coatings with an even layer thickness distribution around the coated body.
<patcit id="pcit0012" dnum="EP0523021A"><text>EP-A-0 523 021</text></patcit> discloses a method of growing a finegrained κ-alumina coating.
In <patcit id="pcit0013" dnum="EP603144A"><text>EP-A-603 144 </text></patcit>a method is disclosed for obtaining a fine grained, (012)-textured α-Al<sub>2</sub>O<sub>3</sub>-coating. This particular Al<sub>2</sub>O<sub>3</sub>-coating applied on cemented carbide tools has been found particularly useful for machining of cast-iron.
<patcit id="pcit0014" dnum="EP659903A"><text>EP-A-659 903</text></patcit> discloses a body with a coating comprising one or more refractory layers of which at least one layer is a layer of α-Al<sub>2</sub>O<sub>3</sub> textured in the (110) direction. The alumina layer is essentially free of cooling cracks and comprises platelike grains with a length of 2-8 µm and a length/width-ratio of 1 - 10.
The object of the present invention is, thus, to provide onto a hard substrate having the afore-mentioned TiC<sub>x</sub>N<sub>y</sub>O<sub>z</sub> coating,at least one single phase Al<sub>2</sub>O<sub>3</sub> layer of the polymorph α with a desired microstructure and crystallographic texture using suitable nucleation and growth conditions such that said properties of the Al<sub>2</sub>O<sub>3</sub> layer are stabilized.
It is a further object of the invention to provide an alumina coated cutting tool insert with improved cutting performance in steel, stainless steel, cast iron and in nodular cast iron.
Fig 1 shows a Scanning Electron Microscope (SEM) top-view micrograph at 1000X magnification of a typical Al<sub>2</sub>O<sub>3</sub>-coating according to the invention.
According to the invention there is provided a cutting tool comprising a body of a hard alloy onto which a wear resistant coating has been deposited. The coating comprises one or several refractory layers of which at least one layer is a dense, fine-grained and preferably textured Al<sub>2</sub>O<sub>3</sub>-layer of the polymorph α.
A coated cutting tool according to the present invention exhibits improved wear and toughness properties compared to prior art tools when used for machining steel or cast iron particularly if the surface has been further smoothened by wet blasting.
More specifically, the coated tool comprises a substrate of a sintered cemented carbide body, cermet or a ceramic body preferably of at least one metal carbide in a metal binder phase. The individual layers in the coating structure may be TiC or related carbide, nitride, carbonitride, oxycarbide and oxycarbonitride of a metal selected from the group consisting of metals in the Groups IVB, VB, and VIB of the Periodic Table, B, Al and Si and/or mixtures thereof. At least one of said layers is in contact with the substrate. However, at least one of the layers in the coating structure comprises a fine-grained, dense, single phase α-Al<sub>2</sub>O<sub>3</sub> coating free of microporosity and crystallographic defects. This coating is preferentially textured with a thickness of d = 0.5-25 µm with an average grain size (s) of 0.5 µm < s < 1 µm for 0.5 µm < d < 2.5 µm and 0.5 µm < s < 4 µm for 2.5 µm < d < 25 µm
The fine-grained microstructure comprises a narrow grain size distribution. Most often 80 % of the Al<sub>2</sub>O<sub>3</sub> grains have a grain size of ± 50 % of the average grain-size.
The grain-size of the Al<sub>2</sub>O<sub>3</sub>-coating is determined from a SEM top view micrograph at 5,000X magnification. Drawing three straight lines in random directions, the average distances between grain boundaries along the lines, are taken as a measure of the grain-size.
The Al<sub>2</sub>O<sub>3</sub>-layer according to the invention has a preferred crystal growth orientation in the (104) direction which is determined by X-ray Diffraction (XRD) measurements. A Texture Coefficient, TC, can be defined as: <maths id="math0001" num=""><img file="EP0738336B2_D0001.tif" /></maths> where <ul id="ul0001" list-style="none" compact="compact"><li>I(hkl) = measured intensity of the (hkl) reflection</li><li>I<sub>o</sub>(hkl) = standard intensity of the ASTM standard powder pattern diffraction data</li><li>n = number of reflections used in the calculation, (hkl) reflections used are: (012), (104), (110), (113), (024), (116)</li></ul>
According to the invention TC for the set of (104) crystal planes is larger than 2.5, and most preferably larger than 3.0.
The coated body according to the invention is further characterized by a surface roughness (R<sub>a</sub>) of the refractory coating of less than 0.3 µm over a measured length of 0.25 mm. The Al<sub>2</sub>O<sub>3</sub>-layer is an exposed outermost layer.
The textured Al<sub>2</sub>O<sub>3</sub>-coating according to the invention is obtained by careful control of the oxidation potential of the CVD-reactor atmosphere prior to the nucleation of Al<sub>2</sub>O<sub>3</sub>. The total concentration level of H<sub>2</sub>O or other oxidizing species should be below 5 ppm. However, the nucleation of Al<sub>2</sub>O<sub>3</sub> is initiated by a controlled sequencing of the reactant gases as follows: CO<sub>2</sub> and CO are first entering the reactor in a H<sub>2</sub> free atmosphere e g in the presence of N<sub>2</sub> or/and Ar then H<sub>2</sub> and AlCl<sub>3</sub> are allowed into the reactor. The temperature shall be 950-1000°C, during the nucleation. However, the exact conditions depend to a certain extent on the design of the equipment used. It is within the purview of the skilled artisan to determine whether the requisite texture and coating morphology have been obtained and to modify the nucleation and the deposition conditions in accordance with the present specification, if desired, to effect the amount of texture and coating morphology.
Example 1
A) Cemented carbide cutting inserts with the composition 6.5 % Co, 8.5 % cubic carbides and balance WC were coated with a 5.5 µm thick layer of TiCN. In subsequent process steps during the same coating cycle, a 6 µm thick layer of α-Al<sub>2</sub>O<sub>3</sub> was deposited. Prior to the nucleation, the oxidation potential of the hydrogen carrier gas, i.e. the water vapour concentration, was explicitly set forth to a low level, less than 5 ppm (See also <patcit id="pcit0015" dnum="US5071696A"><text>U.S. Pat. No. 5,071,696</text></patcit>).
A hydrogen free reaction gas mixture comprising N<sub>2</sub>, CO<sub>2</sub> and CO was first introduced into the CVD-reactor. The reaction gases were sequentially added in the given order. After a preset time H<sub>2</sub> and AlCl<sub>3</sub> were allowed into the reactor. During the deposition of Al<sub>2</sub>O<sub>3</sub>, H<sub>2</sub>S was used as a dopant.
The gas mixtures and other process conditions during the Al<sub>2</sub>O<sub>3</sub> deposition steps comprised: <tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="3" rowsep="0"><colspec colnum="1" colname="col1" colwidth="24mm" /><colspec colnum="2" colname="col2" colwidth="17mm" /><colspec colnum="3" colname="col3" colwidth="18mm" /><tbody><row><entry>Step</entry><entry>1.</entry><entry>2</entry></row><row><entry>CO<sub>2</sub></entry><entry>4%</entry><entry>4%</entry></row><row><entry>AlCl<sub>3</sub></entry><entry>4%</entry><entry>4%</entry></row><row><entry>CO</entry><entry>2%</entry><entry>-</entry></row><row><entry>H<sub>2</sub>S</entry><entry>-</entry><entry>0.2%</entry></row><row><entry>HCl</entry><entry>1%</entry><entry>4%</entry></row><row><entry>H<sub>2</sub></entry><entry>balance</entry><entry>balance</entry></row><row><entry>Pressure</entry><entry>55 mbar</entry><entry>100 mbar</entry></row><row><entry>Temperature</entry><entry>1000°C</entry><entry>1000°C</entry></row><row rowsep="1"><entry>Duration</entry><entry>1 hr</entry><entry>7.5 hr</entry></row></tbody></tgroup></table></tables>
XRD-analysis showed a texture coefficient, TC(104), of 3.2 of the (104) planes in the single a phase of the Al<sub>2</sub>O<sub>3</sub> coating.
SEM-studies showed a fine grained, 6 µm thick Al<sub>2</sub>O<sub>3</sub>-coating with an average grain size of = 2.1 pm.
B) The cemented carbide substrate of A) was coated with TiCN (5.5 µm) and Al<sub>2</sub>O<sub>3</sub> (6 µm) as set forth in A) except that the Al<sub>2</sub>O<sub>3</sub> process was carried out according to prior art technique resulting in a mixture of coarse α- and fine κ-Al<sub>2</sub>O<sub>3</sub> grains in the coating.
Coated tool inserts from A), and B) were all wet blasted with 104 µm (150 mesh) Al<sub>2</sub>O<sub>3</sub> powder in order to smoothen the coating surface.
The cutting inserts were then tested with respect to edge line and rake face flaking in a facing operation in nodular cast iron (AISI 60-40-18, DIN GGG40). The shape of the machined work piece was such that the cutting edge is intermitted twice during each revolution.
Cutting data: <ul id="ul0002" list-style="none" compact="compact"><li>Speed = 150 m/min,</li><li>Cutting Depth = 2.0 mm and</li><li>Feed = 0.1 mm/rev.</li></ul>
The inserts were run one cut over the face of the work piece.
The results are expressed in the table below as percentage of the edge line in cut that obtained flaking as well as the rake face area subjected to flaking in relation to total contact area between the rake face and the work piece chip. <tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="4" rowsep="0"><colspec colnum="1" colname="col1" colwidth="10mm" /><colspec colnum="2" colname="col2" colwidth="47mm" /><colspec colnum="3" colname="col3" colwidth="35mm" /><colspec colnum="4" colname="col4" colwidth="37mm" /><thead valign="top"><row rowsep="1"><entry /><entry /><entry>Flaking (%) Edge line</entry><entry>Rake face</entry></row></thead><tbody><row><entry>A)</entry><entry>single phase/textured α-Al<sub>2</sub>O<sub>3</sub></entry><entry align="right">5</entry><entry>6 (acc. to the invention)</entry></row><row rowsep="1"><entry>B)</entry><entry>α+κ Al<sub>2</sub>O<sub>3</sub></entry><entry align="right">90</entry><entry>86</entry></row></tbody></tgroup></table></tables>
Example 2
The cutting inserts from A) and B) were also tested with respect to edge line flaking in a facing operation in an alloyed steel (AISI 1518, W-no. 1,0580). The shape of the machined work piece was such that the cutting edge is intermitted three times during each revolution.
Cutting data: <ul id="ul0003" list-style="none" compact="compact"><li>Speed = 130-220 m/min,</li><li>Cutting Depth = 2 mm and</li><li>Feed = 0.2 mm/rev.</li></ul>
The inserts were run one cut over the face of the work piece.
The result below is expressed as percentage of the edgeline in cut that obtained flaking. <tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="3" rowsep="0"><colspec colnum="1" colname="col1" colwidth="10mm" /><colspec colnum="2" colname="col2" colwidth="47mm" /><colspec colnum="3" colname="col3" colwidth="45mm" /><thead valign="top"><row rowsep="1"><entry /><entry /><entry>Flaking (%) Edge line</entry></row></thead><tbody><row><entry>D)</entry><entry>single phase/textured α-Al<sub>2</sub>O<sub>3</sub></entry><entry>0 (according to the invention)</entry></row><row rowsep="1"><entry>E)</entry><entry>α+κ Al<sub>2</sub>O<sub>3</sub></entry><entry>28</entry></row></tbody></tgroup></table></tables>
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| Reply of patent proprietor to notice(s) of oppositionOppositionORIGINAL CODE: EPIDOS OBSOPLBF | PLBF | EP | |
| Opposition filedOppositionORIGINAL CODE: 0009260PLBI | PLBI | EP | |
| Unpublished change to opponent dataORIGINAL CODE: EPIDOS OPPOPLBQ | PLBQ | EP | |
| Fr: translation filedET | ET | EP | |
| New agentNV | NV | CH | |
| Corresponds to:REF | REF | EP | |
| European patent takes effect as a national patent in ch/liEP | EP | CH | |
| Designated contracting statesAK | AK | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Corresponds to:REF | REF | EP | |
| It: translation for a ep patent filedITF | ITF | EP | |
| It: translation for a ep patent filedITF | ITF | EP | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOS IGRAGRAH | GRAH | EP | |
| Despatch of communication of intention to grantORIGINAL CODE: EPIDOS AGRAGRAG | GRAG | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOS IGRAGRAH | GRAH | EP | |
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| First examination report despatched17Q | 17Q | EP | |
| Request for examination filed17P | 17P | EP | |
| Designated contracting statesAK | AK | EP | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI | PUAI | EP |
Numbers
- Publication
- 0738336
- Publication, DOCDB
- 0738336
- Publication, EPODOC
- EP0738336
- Application
- 95907167
- Application, DOCDB
- 95907167
- Application, EPODOC
- EP19950907167
Titles3
- German
- OXIDBESCHICHTETES SCHNEIDWERKZEUG
- English
- OXIDE COATED CUTTING TOOL
- French
- OUTILS DE COUPE A REVETEMENT D'OXYDE
Classification
- CPC, 4
- C23C30/005
- C23C16/0272
- C23C16/403
- Y10T407/27
- IPC, 8
- C23C16 40
- C23C16 30
- B23B27 14
- C04B41 87
- C04B41 89
- C23C16 02
- C23C30 00
- C30B29 20
Designated states8
- Contracting states, 8
- Austria
- Switzerland
- Germany
- France
- United Kingdom
- Italy
- Liechtenstein
- Sweden