• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    COATED BODIES MADE OF METAL, CARBED METAL, CERMET OR CERAMIC AND METHOD FOR COATING SUCH BODIES. The invention relates to coated bodies made of metal, carbide, cermet or ceramic, coated with a mono- or multilayer system, containing at least one composite layer of hard material, as well as the method of coating such bodies. The aim of the present invention is to develop for such bodies a layer system, containing one or more layers, having at least one composite layer of carbides, including cubic TiA1CN and hexagonal A1N as main phases, and characterized by a composite structure with smooth and homogeneous surface, high resistance to oxidation and great hardness. Included in this objective is the development of a cost-effective method for creating such coatings. The composite layer of hard material contains as main phases cubic TiA1CN and hexagonal A1N, in which the cubic TiA1CN is a microcrystalline fcc-Ti1 -x Al X C y N z , with x > 0.75; 0.25>y>0 and 1>z>0.75 with a crystallite size of >- 0.1 (Mi)m, in which the composite layer in the surface region of the grain also includes amorphous carbide with a fraction of ( ...).
    公开号:BR112012011071B1
    申请号:R112012011071-3
    申请日:2010-11-12
    公开日:2021-04-20
    发明作者:Ingolf Endler；Mandy Hohn
    申请人:Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V.；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The invention relates to metallic bodies made of metal, carbide, cermet or ceramic, coated with a monolayer or multilayer system, which contains at least one layer of hard composite material, as well as the method of coating such bodies. This layer is characterized by a composite structure with a smooth and homogeneous surface, resistant to oxidation and with high hardness, and is particularly applied as a protective coating on interchangeable cutting inserts and Si3N and WC/Co steel components. TECHNICAL STATUS
    [002] Machining tools must meet high standards of durability and abrasion resistance. Coatings based on titanium nitrides, carbides and carbonitrides have long been used as protective layers. In recent years, the trend has been to add these coatings by incorporating aluminum to provide greater resistance to oxidation.
    [003] TiAlN layers with cubic NaCl structure, as well as several processes for their manufacture are known. Thus, single-phase fcc-TiAlN layers or mixtures of fcc-TiAlN and hexagonal AlN are manufactured using the PVD, Plasma-CVD and thermal CVD method (WO 03/085152 A2; K. Kawata, H. Sugimura, O.Takai, Thin Solid Films, 390 (2001) pp. 64-69; DE 10 2005 032 860 B4).
    [004] By the incorporation of carbon and other metals, these layers are continuously improved, both with the use of the PVD method and the CVD.
    [005] Layer systems with pure fcc-TiAlCN layers are, for example, described in document CN101319302A, in which a method for PVD deposition of a linearly graded TiAlCN layer is described, in which the C/N gradient is produced through controlled dosage of N2 and C2H2.
    [006] Patent application WO98/10120 A1 refers to the part coated with PVD with at least two other successive layers, comprising of TiN, TiCN, TiAlN or TiAlCN.
    [007] A component with a wear-reducing layer consisting of a combination of Ti and Al nitrides, carbonitrides and carbides has been described in patent US2002/0136933 A1.
    [008] In JP05337705 A, a cutting body coated with a layer consisting of Ti, Al and N and/or C was claimed. This coating is produced by means of Plasma-CVD.
    [009] Layers with a mixture of fcc-TiAlN and h-AlN are also known (DE102007000512 B3), as well as layers with a mixture of fcc-(TiyAlxMe1-xy)N with h-AlN, in which Me comprises the metals Zr , Hf, V, Nb, Ta, Cr, Mo, W or Si (US2004/0115484 A1).
    [0010] Nanocomposite layers comprising fcc-TiAlCN and amorphous carbon are also known (US2003/143402 A1; J. Shieh and MH Hon, Plasma-enhanced chemical-vapor deposition of titanium aluminum carbonitride/amorpous-carbon nanocomposite thin films, J. Vac. Sci. Technol., Jan/Feb 2002, A20, (1), p.8792). These layers are produced by means of Plasma-CVD. Nanoscale TiAlCN grains are embedded in an amorphous carbon matrix.
    [0011] Furthermore, it is known to mix other metals for fcc-TiAlN layers.
    [0012] The document EP1574594 A1 describes layers of PVD and hard material, which contain the carbon described with a nanocrystalline structure of composition (AlxMe1yMe2z)CuE1VE2W where: Me1 and Me2 are metals and x > 0.4; x + y + z = 1 and y, z > 0, as well as 1 > u > 0 u + v + w = 1 and v, w > 0. Thus, the carbon content on the surface of the grain is greater than that of nanocrystals .
    [0013] A hard material coated body with a CVD layer based on (Ti,Me)1-xAlx(CyNz) where Me = Zr and/or Hf has been described in WO2009/112117 A1. These layers are characterized by high resistance to oxidation and high resistance to abrasion. SUMMARY OF THE INVENTION
    [0014] The objective of the present invention is to develop a layer system for metal, carbide, cermet or ceramic bodies, which is mono or multilayer, and has at least one layer of hard material composite, containing as main phases Cubic TiAlCN and hexagonal AlN, and is characterized by a composite structure with a smooth and homogeneous surface, superior resistance to oxidation and high hardness. Included in this objective is the development of a procedure for the creation of such coatings with good cost-benefit ratio.
    [0015] This objective is achieved through the characteristics of patent claims, in which the invention also includes combinations of dependent individual claims in the sense of a UN D relationship.
    [0016] The coated bodies of the invention are characterized by the fact that they are coated with a mono- or multilayer system, comprising at least one layer of hard material composite, which includes, as main phases, cubic TiAlCN and hexagonal AlN, where cubic TiAlCN is a microcrystalline fcc-Ti1-xAlxCyNz where x > 0.75, y ranges from 0 to 0.25 and z ranges from 0.75 to 1, with a crystallite size of > 0.1 µm, in which this composite layer in the surface region of the grain also includes amorphous carbon with a mass fraction of 0.01% to 20%.
    [0017] The TiAlCN layer, according to the invention, is characterized by a microcrystalline composite structure, in which both main phases fcc-Ti1-xAlxCyNz with x > 0.75 with hexagonal AlN provide a high hardness and resistance to oxidation , and amorphous carbon contributes to friction reduction. The high rigidity of the composite layer is found over a wide composition range up to 50 Ma.-% h-AlN.
    [0018] In the known technique, on the contrary, the TiAlCN nanocomposite layers have, due to the lower aluminum content and the incorporation of TiAlN crystals in the amorphous carbon, only a limited resistance to oxidation. The amorphous carbon matrix combusts at 400°C. Therefore, the cohesion in the nanocomposite layer is no longer present at elevated temperatures.
    [0019] The TiAlCN layer, according to the invention, presents, however, a surprisingly high resistance to oxidation up to 800°C. The high aluminum content of the main components fcc-TiAlCN and hexagonal AlN, as well as the microcrystalline structure, are obviously the basis for the addition of a specified amount of friction-reducing amorphous carbon, without the oxidation resistance being adversely influenced .
    [0020] The coating of the invention can be advantageously and conveniently designed as follows:
    [0021] In addition to the microcrystalline fcc-Ti1-xAlxCyNz, other Ti compounds may be contained in the composite layer of hard material, which exist from Ti1-xAlXN in a wurtzite and/or TiN structure.
    [0022] Amorphous carbon is preferably present as graphitic sp2 carbon.
    [0023] According to the invention, the multilayer system consists of several composite layers of hard TiAlCN material with different contents of amorphous carbon and/or hexagonal AlN.
    [0024] The composite layer of hard material can present a gradient relative to the mass fraction of hexagonal AlN between 0.1% and 50% and/or amorphous carbon between 0.1% and 20%.
    [0025] Conveniently, the composite layer of hard material of the invention has a layer thickness between 0.1 µm and 30 µm.
    The microcrystalline fcc-TiAlCN preferably has a crystallite size between 0.1 µm and 1 µm.
    [0027] For the manufacture of such coated bodies, the invention includes a method, in which the bodies are added with at least one composite layer of hard material, which has as main phases microcrystalline fcc-Ti1-xAlxCyNz with x > 0 .75; 0.25>y>0 and 1>z>0.75 and hexagonal AlN, containing additional amorphous C with a mass fraction of 0.01% to 20%, the composite layer being deposited using a gas mixture with precursors of Ti-, Al-, C- and N- in an LPCVD process at temperatures between 700°C and 900°C and with pressures between 102 Pa and 105 Pa without additional plasma excitation over the bodies.
    [0028] The coating of the invention can be advantageously and conveniently designed as follows:
    [0029] As precursors for the deposition of the composite layer of hard material, may be used in the gas mixture preferably titanium halides, aluminum halides, reactive nitrogen compounds, hydrocarbons and/or compounds containing carbon and nitrogen.
    [0030] Preferably, the reactive nitrogen compounds comprise NH3 and, as hydrocarbons, C2H or C2H2.
    [0031] Conveniently, they can be added to the gas mixture for deposition of the composite layer of hard material H2 and/or N2 and/or noble gas. EXAMPLES OF CARRYING OUT THE INVENTION
    [0032] The invention is explained in more detail below in the embodiment examples and in the corresponding figures. The figures indicate:
    [0033] Fig.1: XRD X-ray diffraction of the composite layer of hard material, as per embodiment 1, consisting of fcc-TiAlCN, h-AlN and amorphous carbon.
    [0034] Fig.2: The Raman spectrum of the composite layer of hard material, as per embodiment 1, consisting of fcc-TiAlCN, h-AlN and amorphous carbon.
    [0035] Fig.3: XRD X-ray diffraction of the composite layer of hard material, as per embodiment 2, consisting of fcc-TiAlCN, h-AlN and amorphous carbon. Example 1
    [0036] In WC/Co hard material cutting inserts, a layer of TiN composite with a thickness of 1 µm is additionally applied and then the layer of the invention, by means of a CVD process.
    [0037] The coating process takes place in a hot wall CVD reactor having an internal diameter of 75 mm. For the CVD coating, a gas mixture is used that includes 51.8% by volume of H2, 1.3% by volume of AlCl3, 0.3% by volume of TiCl4, 25.9% by volume of Ar and 4 .9% by volume of NH3, 1.3% by volume of C2H4, in addition to 14.5% by volume of N2. The deposition temperature is 850°C and the process pressure 0.8 kPa. After a coating time of 30 min., a 5 µm thick TiAlCN layer is obtained.
    [0038] By means of WDX investigation were determined inside the layer a C content of 0.5 At.-%, an aluminum content of 36.2 At.-%, a titanium content of 8.1 At. -%, a chlorine content of 0.3 At.-% and a nitrogen content of 54.9 At.-%.
    [0039] This layer was analyzed by means of thin-layer radiographic analysis (see X-ray diffraction of Fig.1). The diffraction pattern indicates a mixture of phases, which consists of fcc-TiAlCN and h-AlN. A Rietveld analysis indicated for the components of the crystalline layer a content of 3.5 Ma.-% h-AlN and 96.5 Ma.-% fcc-TiAlCN. Layer components may not be determined using X-ray research methods.
    [0040] For the detection of amorphous carbon researches were carried out by TEM and Raman. TEM examination indicates an accumulation of carbon in the superficial region of the grains. The Raman spectrum (see Fig.2) contains two broad bands: the first, between 1,200 and 1,400cm-1 and the second, between 1,500 and 1,700cm-1, corresponding to the D- and G bands of an amorphous sp2 carbon.
    [0041] The calculated crystallite size in the TEM investigation for the fcc-TiAlCN is 0.4 µm.
    [0042] Microhardness measurements with a Vickers indenter result in a hardness of 31.5 ± 0.6 GPa.
    [0043] The hard material layer of the invention is characterized by a composite structure, smooth and homogeneous surface, high resistance to oxidation and high hardness. Example 2
    [0044] On Si3N ceramic cutting inserts a TiN binding layer, 1 μm thick, is applied, and then the layer of the invention, by means of a CVD process.
    [0045] The coating process takes place in a hot wall CVD reactor with an internal diameter of 75 mm. For the CVD coating, a gas mixture is used, containing 51.7% by volume of H2, 1.2% by volume of AlCl3, 0.5% by volume of TiCl4, 25.9% by volume of Ar and 4 .9% by volume of NH3, 1.3% by volume of C2H4, in addition to 14.5% by volume of N2. The deposition temperature is 850°C and the process pressure 0.8 kPa. After a coating time of 25 min, a 5 µm thick TiAlCN layer is obtained.
    [0046] By means of WDX investigation, a C content of 0.6 At.-%, an aluminum content of 36.6 At.-%, a titanium content of 8.7 At.-%, a chlorine content of 0.3 At.-% and a nitrogen content of 53.8 At.-% inside the layer.
    [0047] This layer was analyzed by means of radiographic analysis of the final layer (see X-ray diffraction of Fig.3). X-ray diffraction indicates a phase mixture consisting of fcc-TiAlCN and h-AlN with a higher proportion of h-AlN, as in example 1. A Rietveld analysis showed a content of 29.0 for the crystalline layer components. Ma.-%h-AlN and 71.0 Ma.-%fcc-TiAlCN.
    [0048] The Raman analysis showed a spectrum identical to that of Fig.2 with a range D- and G for the amorphous sp2 carbon.
    [0049] The analysis of the lamellar structure by means of a scanning electron microscope indicates a grain structure with an fcc-TiAlCN crystallite size of the order of 0.1 μm.
    [0050] The hardness measured with a Vickers indenter is 30.3 ± 0.5 GPa.
    [0051] The hard material layer of the invention is characterized by a composite structure of very fine grains with smooth and homogeneous surface, excellent resistance to oxidation and high hardness.
    权利要求:
    Claims (12)
    [0001]
    1. Coated bodies made of metal, carbide, cermet or ceramic, coated with a monolayer or multilayer system comprising at least one layer of hard composite material, containing as main phases cubic TiAlCN and hexagonal AlN, characterized by the fact that cubic TiAlCN contains an fcc-Ti1-xAlxCyNz where x>0.75; 0<y<0.25 and 0.75<z<1 with a crystallite size >0.1μm, in which the composite layer on the surface of the carbon grains also includes amorphous carbon in a content of 0.01% at 20 % in large scale.
    [0002]
    2. Coated bodies, according to claim 1, characterized in that, in addition to the microcrystalline fcc-Ti1-xAlxCyNz, Ti compounds are included that comprise Ti1-xALXN, in a wurtzite and/or TiN structure.
    [0003]
    3. Coated bodies, according to claim 1, characterized in that the amorphous carbon is available as graphitic sp2 carbon.
    [0004]
    4. Coated bodies, according to claim 1, characterized in that the lamellar layer system can consist of several composite layers of hard TiAlCN material with different contents of amorphous carbon and/or hexagonal AlN.
    [0005]
    5. Coated bodies according to claim 1, characterized in that the composite layer of hard material has a gradient in relation to the hexagonal AlN mass fraction between 0.1% and 50% and/or the mass fraction of amorphous carbon between 0.1% and 20%.
    [0006]
    6. Coated bodies, according to claim 1, characterized in that the composite layer of hard material has a layer thickness between 0.1 μm and 30 μm.
    [0007]
    7. Coated bodies, according to claim 1, characterized in that the crystallite size of microcrystalline fcc-TiAlCN is in the range of 0.1 μm to 1.0 μm.
    [0008]
    8. Method for coating bodies made with metal, rigid metal, cermet or ceramic with a mono- or multi-layer system, as defined in any one of claims 1 to 7, characterized in that it comprises at least one composite layer of hard material, having as main microcrystalline phases fcc-Ti1-xAlxCyNz with x>0.75, y=0 to 0.25 and z=0.75 to 1 and hexagonal AlN and, additionally, amorphous carbon with a mass fraction of 0.01% to 20%, in which said composite layer is deposited using a gas mixture with Ti-, Al-, C- and N- precursors in an LPCVD process with temperature between 700°C and 900°C and pressure between 102 Pa and 105 Pa without additional plasma excitation over the body.
    [0009]
    9. Method according to claim 8, characterized in that the precursors used for the deposition of the composite layer of hard material, used in the gas mixture, preferably comprising titanium halide, aluminum halide, reactive nitrogen compounds , hydrocarbons and/or compounds containing carbon and nitrogen.
    [0010]
    10. Method according to claim 9, characterized in that it uses as a compound of nitrogen, NH3 and, as hydrocarbons, C2H or C2H2.
    [0011]
    11. Method according to claim 8, characterized in that in the gas mixture for deposition of the composite layer of hard material, H2 and/or N2 are added.
    [0012]
    12. Method according to claim 8, characterized in that in the gas mixture for deposition of the composite layer of hard material, an inert noble gas is added.
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-11-10| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-03-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-20| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 20/04/2021, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102009046667.3|2009-11-12|
    DE102009046667.3A|DE102009046667B4|2009-11-12|2009-11-12|Coated bodies of metal, hardmetal, cermet or ceramic, and methods of coating such bodies|
    PCT/EP2010/067371|WO2011058132A1|2009-11-12|2010-11-12|Coated bodies made of metal, hard metal, cermet or ceramic material and method for coating such bodies|
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