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    • 专利摘要:
    COATED CUTTING TOOL AND METHOD OF MANUFACTURING THE SAME. The present invention is related to the provision of a coated cutting tool, comprising a substrate and a surface coating, wherein said coating comprises a layer of Ti (C, N, O), comprising at least one columnar layer of T ( C, N) finely granulated, deposited by the technique of chemical vapor deposition at moderate temperature - Chemical Vapor Deposition in Moderate Temperature (MTCVD), with an average grain width of 0.05-0, 4 (Mi) m and an atomic proportion of carbon to the sum of carbon and nitrogen (C / C + N)) contained in said layer of Ti (C, N), deposited by the MTCVD technique, with an average value of 0.50-0.65. The invention also provides a method for manufacturing said coated cutting tool, depositing the Ti layer (C, N) by the MTCVD technique.
    公开号:BR112014014484B1
    申请号:R112014014484-2
    申请日:2012-12-14
    公开日:2021-01-19
    发明作者:Carl Björmander
    申请人:Sandvik Intellectual Property Ab；
    IPC主号:
    专利说明:

    Technical Field
    [001] The present invention is related to a coated cutting tool for machining chips with metal formation, comprising a substrate having a surface coated with a coating produced by chemical vapor deposition (CVD) and a method of manufacturing the same . Specifically, the present invention relates to a coated cutting tool having a coating produced by CVD, comprising at least one layer of finely granulated titanium carbonitride. Description of the state of the art
    [002] Cutting tools for machining metal with chip formation, such as round tools, that is, endmills, drills, etc., and inserts, made of durable materials, for example, carbide, cermet, Cubic boronitride or high-speed steel typically has a wear-resistant coating to extend the life of the cutting tool. Wear-resistant coatings are normally coated using the chemical vapor deposition (CVD) technique, as this technique has several advantages. Thus, it enables great productivity in the production process of cutting tools, a coating conformed with complex geometries, and can be easily used to deposit layers of insulating coating, such as, for example, alumina.
    [003] In particular, carbide cutting tools for turning procedures are normally coated with coatings produced by CVD, comprising a layered structure of different materials to provide sufficient wear resistance, where the composition, microstructure, texture, etc. , of the individual layers are chosen to improve certain coating properties for a specific application. The predominant coating currently used comprises a Ti-based layer, hereinafter referred to as a Ti layer (C, N, O), comprising one or more selected layers of titanium carbide, titanium nitride, titanium carbonitride, oxycarbide titanium, and titanium oxycarbonitride, hereinafter referred to as layers of (TiC, TiN, Ti (C, N), Ti (C, O), Ti (C, N, O) respectively, deposited on a substrate surface and a alumina layer, hereinafter referred to as Al2O3 layer, deposited on the Ti (C, N, O) layer. Chemical vapor deposition (CVD) processes at moderate temperature (MTCVD) have been proven to be advantageous for layer deposition of Ti (C, N), when compared to chemical vapor deposition (CVD) processes under high temperatures (HTCVD).
    [004] Larsson and Ruppi, “Thin Solid Films”, 402 (2002), 203-210, disclose a study on the microstructure and properties of Ti (C, N) coatings deposited on cutting tool substrates using the technique of MTCVD, if compared to Ti (C, N) coatings deposited using the HTCVD technique. The Ti (C, N) coating deposited by HTCVD exhibits equal axis grains, with no preferred growth direction and with an average grain size of less than 0.2 μm. In contrast, Ti (C, N) coatings deposited by [MTCVD] exhibit a relatively large TC value (422) when measuring X-ray diffraction, hereinafter referred to as a texture (422), and columnar grains having a width of about 0.5 μm. The difference in microstructure is attributed to the lower temperature and aggressive precursors, such as, for example, acetonitrile (CH3CN). The Ti (C, N) coating deposited by [MTCVD] has a better resistance to chip formation from the edge, but a worse resistance to crater wear compared to the Ti (C, N) coating deposited by [ HTCVD]. However, chip resistance is still critical for Ti (C, N) coatings deposited by [MTCVD], specifically, in applications of a certain degree of demand, such as nodular cast iron turning comprising intermittent cutting operations .
    [005] Patent document EP 1 187 970 A1 discloses a columnar layer of Ti (C, N), with a texture (422), deposited using a MTCVD process with precursors comprising acetonitrile, titanium tetrachloride, nitrogen and hydrogen, as in the above MTCVD process, and, in addition, a hydrocarbon, such as C2H4 or C3H6, which is disclosed to provide a high atomic proportion of carbon to the sum of carbon and nitrogen (C / C + N) contained in columnar layer of Ti (C, N), that is, at least 0.70, thereby providing high hardness and improved wear resistance, compared to a standard process using acetonitrile. The columnar layer of Ti (C, N) formed using these precursors is finely granulated, with an average grain width of 0.05 to 0.5 μm and has a high fracture resistance. Although presenting an improved hardness, the oxidation resistance of this columnar layer of Ti (C, N) may be insufficient, specifically, for cutting operations that generate a large amount of heat in the coating. Summary of the Invention
    [006] It is an objective of the present invention to provide a coated cutting tool with improved properties in cutting operations. A further objective of the invention is to provide a coated cutting tool with improved wear resistance, for example, greater resistance to chip formation. Another objective of the invention is to provide a high performance cutting tool for turning nodular cast iron with high speed cutting.
    [007] These objectives are achieved through a cutting tool, and a method to produce a cutting tool.
    [008] The present invention relates to a coated cutting tool comprising a substrate and a coating, wherein said coating comprises a layer of Ti (C, N, O), comprising at least one columnar layer of Ti (C, N) deposited by the MTCVD technique, with an average grain width of 0.05-0.4 μm, preferably 0.05-0.25 μm, more preferably 0.1-0.2 μm, measured in one cross section, with a normal surface perpendicular to a normal substrate surface, on an inclined face of the coated cutting tool, along a straight line, in a direction parallel to a substrate surface, in a centralized position between a lower interface and a more superior interface of said layer of Ti (C, N) deposited by the MTCVD technique. The atomic ratio of carbon to the sum of carbon and nitrogen (C / (C + N)) contained in said layer of Ti (C, N) deposited by the MTCVD technique is 0.50-0.65, preferably from 0.55-0.62, more preferably, 0.56-0.60, even more preferably, 0.57-0.59, when measured by electron probe analysis, using a 10 position spaced electronic probe 50 μm along said line.
    [009] In an embodiment of the invention, an average thickness of said columnar layer of Ti (C, N) deposited by the MTCVD technique is 5-15 μm.
    [010] An advantage of the Ti (C, N) layer deposited by the finely granulated MTCVD technique of the present invention is that it provides a smooth surface, when compared to a conventional layer deposited by MTCVD. Preferably, the Ti (C, N) layer deposited by the MTCVD technique of the present invention may have a smoothness effect, that is, the outer surface of the Ti (C, N) layer deposited by the MTCVD technique has a roughness of surface (Rz) lower than the substrate surface.
    [011] In one embodiment of the present invention, the coating further comprises an outer layer, such as an Al2O3 layer or other layers suitable for obtaining high wear resistance in cutting operations, deposited on the Ti layer (C, N , O), optionally, with one or more additional layers arranged between or on said layer of Ti (C, N, O), such as, for example, a colored layer deposited as the outermost layer.
    [012] In one embodiment of the invention, the Ti layer (C, N, O) further comprises additional layers, such as, for example, a layer of TiN that serves as a diffusion barrier deposited on the substrate before said layer of Ti (C, N) deposited by the MTCVD technique. Another example of an additional layer includes one or more layers deposited on said layer of Ti (C, N) deposited by the MTCVD technique, before the deposition of an outer layer, such as said layer of Al2O3. These layers can, for example, provide an improved adhesion of the outer layer by mechanical fixation.
    [013] In one embodiment of the invention, the Ti layer (C, N, O) comprises an inner layer of TiN with a thickness sufficient to provide a diffusion barrier, preferably a thickness of 0.3 to 0.6 μm.
    [014] In one embodiment of the invention, the Ti layer (C, N, O) comprises an outer layer of Ti (C, O), to provide a large surface area for growth of an Al2O3 layer.
    [015] In one embodiment of the invention, the layer of Ti (C, N, O) comprises a layer of Ti (C, N) deposited by [HTCVD], disposed on the layer of Ti (C, N) deposited by the technique of MTCVD.
    [016] In one embodiment of the invention, the coating comprises a layer of Ti (C, N, O), consisting of a sequence of layers, in accordance with the layers of TiN / Ti (C, N) [MTCVD] / Ti (C, O) deposited on the substrate. Optionally, there is a layer of Ti (C, N) deposited by [HTCVD] disposed between the layer of Ti (C, N) deposited by the MTCVD technique and the layer of Ti (C, O). Preferably, the thickness of the TiN layer is 0.3 μm to 0.6 μm. Preferably, the thickness of the Ti (C, N) layer deposited by the MTCVD technique is 5-15 μm, more preferably, 8 μm to 12 μm, to provide sufficient resistance to abrasive flank wear. Preferably, the thickness of the Ti layer (C, N) deposited by [HTCVD] is 0.2 μm to 0.4 μm. Preferably, the thickness of the Ti layer (C, O) is 0.3 μm to 0.8 μm. Preferably, the coating further comprises an Al2O3 layer deposited on the Ti (C, O) layer. Depending on the application, the Al2O3 layer can be either α-Al2O3 or K-AI2O3, or a mixture of them. Thus, for example, in the case of use in a nodular cast iron turning application, the Al2O3 layer is preferably α-Al2O3.
    [017] In one embodiment of the invention, the coating comprises a layer of α-Al2O3 with a thickness of 2-6 μm, preferably 3-5 μm.
    [018] In one embodiment of the invention, the coating comprises a layer of α-Al2O3 with a relatively large TC value (012) in an X-ray diffraction measurement, hereinafter referred to as texture (012), such as the layer of α-Al2O deposited according to the description of US Patent 7,163,735 B2, and a thickness of 2-6 μm, preferably 3-5 μm, suitable for use in turning nodular iron. In this application, the α-Al2O3 layer is mainly used as a thermal barrier and wear resistance is essentially provided by the Ti (C, N) layer deposited by the MTCVD technique. If the thickness of the Al2O3 layer is further increased, the resistance to splintering will be decreased, this may provide a rougher top surface, which results in more adhesive forces on the coating during cutting, which can increase wear due to splintering.
    [019] In another embodiment of the present invention, said Al2O3 layer is a layer of α-Al2O3 with a relatively large TC value (006) in an X-ray diffraction measurement, hereinafter referred to as texture (001), a Since the normal (C axis) of the plane (0001) of the crystals of the α-Al2O3 layer are aligned in the normal direction of the substrate surface, such as a layer of α-Al2O deposited according to the description of the US Patent 7,993,742 B2, and a thickness of 2-6 μm, preferably 3-5 μm. The wear resistance of the α-Al2O3 layer (001) is improved by increasing the thickness, however, an excessively large thickness of the Al2O3 layer decreases the resistance to splintering.
    [020] The columnar grains of the Ti layer (C, N) deposited by the MTCVD technique are elongated in relation to length and width and with a longitudinal axis along a direction of growth of the Ti layer (C, N) deposited by the MTCVD technique being perpendicular to a substrate surface. The grain width is not a single axis, and may differ in different directions. In addition, the grains are not perfectly aligned with the direction of growth. Consequently, the width of the grain is not easily measured. For the purpose of this application, the width of the columnar grains is considered to extend in a direction parallel to the surface of the substrate, which is disposed in a direction perpendicular to the direction of growth of the Ti layer (C, N) deposited by the MTCVD technique, and that is measured in a scanning electron microscopy (SEM) micrograph, of a polished cross section of the Ti layer (C, N) deposited by the MTCVD technique, with a magnification of 15,000 times. The grain boundaries are identified by the differences in contrast between adjacent grains, and the grain width is measured as the distance between the adjacent grain boundaries along a straight line, as will be explained below.
    [021] In a cutting tool embodiment according to the present invention, the Ti (C, N) layer deposited by the MTCVD technique exhibits an X-ray diffraction pattern, in which the texture coefficients TC (hkl) are defined by:
    where: I (hkl) = measured intensity of reflection (hkl); I0 (hkl) = standard intensity according to PDF card, No. 42-1489 of the ICDD; n = number of reflections used in the calculation; and the reflections (hkl) used in the calculation are: (111), (200), (220), (311), (331), (420), (422) and (511), and in which a sum of TC (422) and TC (311) is> 5.5, that is, TC (422) + TC (311)> 5.5. The sum of TC (422) and TC (311) is preferably greater than 6. In addition, preferably, TC (422)> TC (311).
    [022] In one embodiment of the present invention, the Ti layer (C, N) deposited by the MTCVD technique exhibits an X-ray diffraction pattern having the reflection (422) in a 2θ position of 123.15-123.25. The 2θ position of the reflection (422) refers to the carbon content in the coating, so that a higher carbon content correlates to a lower 2θ position of the reflection (422).
    [023] In an embodiment of the present invention, a total width value in the maximum half (FWHM) of the peak attributed to the reflection (422) of the Ti layer (C, N) deposited by the MTCVD technique is 0.4-0 , 5 preferably 0.42-0.46. The FWHM is correlated to the grain size, so that a higher value of FWHM correlates to the smaller grains.
    [024] In an embodiment of the present invention, the average thickness of the Ti layer (C, N) deposited by the MTCVD technique is 5-15 μm, preferably 7-12 μm for turning inserts.
    [025] In an embodiment of the present invention, the average thickness of the Ti layer (C, N) deposited by the MTCVD technique is 3-7 μm for milling and drilling tools.
    [026] Thanks to the improved wear resistance of the Ti (C, N) layer deposited by the MTCVD technique, the roughness of the substrate can be increased in the event of an increase in hardness. In one embodiment of the present invention, the substrate is made of carbide comprising WC grains in a binder phase comprising Co. Preferably, the Co content is 5.6 to 6.4% by weight.
    [027] Although the modalities of the present invention have been described with Ti as the only metallic element in the Ti layer (C, N, O), the Ti layer (C, N, O) or individual layers thereof, in addition to Ti , can comprise elements selected from one or more of Zr, Hf, V, Nb, Ta, Cr, Mo, W and Al, in an amount that does not significantly change the grain width or the C (C + N) ratio of the layer of Ti (C, N) deposited by the MTCVD technique. Also, in addition to one or more of the elements of C, O and N, the Ti layer (C, N, O) or one or more of the individual layers may also comprise the element boron (B). In addition, said layer of Ti (C, N) deposited by the MTCVD technique can comprise small amounts of oxygen, without significantly affecting the properties of the layer of Ti (C, N) deposited by the MTCVD technique. In one embodiment of the invention, the Ti layer (C, N, O) comprises one or more of these additional elements.
    [028] In an embodiment of the invention, said other layer suitable for high wear resistance in cutting operations deposited on said Ti layer (C, N, O) comprises a compound selected from a carbide, a nitride and an oxide and boride of an element belonging to Gripo 4a (Ti, Zr, Hf), 5a (V, Nb, Ta), or 6a (Cr, Mo, W) of the Periodic Table or Al or a mutually solid solution thereof.
    [029] Although the Al2O3 layer above is described as a binary layer, it should be noted that in alternative embodiments of the invention, the Al2O3 layer can comprise one or more elements, such as, for example, Zr to form a ternary compound or multiple, such as, (Al, Zr) O. The Al2O3 layer can also consist of two or more phases, of different composition and microstructure.
    [030] The present invention also relates to a method for producing a coated cutting tool, comprising the use of a chemical vapor deposition (CVD) process, wherein said process comprises the steps of: - providing a substrate in a vacuum chamber; - providing the addition of precursors to said vacuum chamber; - depositing a layer of Ti (C, N, O) comprising at least one columnar layer of Ti (C, N) deposited by the MTCVD technique on said substrate, in which the columnar layer of Ti (C, N) deposited by MTCVD technique is deposited at a temperature in the range of 700-910 ° C, preferably 800-850 ° C, more preferably, 820-840 ° C, and using precursor agents comprising at least TiCl4, CH3CN or other nitrile, and H2 , and with a ratio of Ti / CN, based on a percentage by volume of TiCl4 and CH3CN or other nitrile provided to the vacuum chamber, from 4-10, preferably from 5-8, more preferably from 6-7.
    [031] The substrate may include a surface coating as an intermediate layer, deposited before the deposition of the Ti layer (C, N, O).
    [032] The Ti / CN ratio is used within the above range to efficiently control the grain size of the columnar layer of Ti (C, N) deposited by the MTCVD technique.
    [033] In one embodiment of the present invention, the Ti (C, N) layer deposited by the MTCVD technique is deposited with TiCl4, a nitrile and H2 as the only gas during deposition. Preferably, the nitrile is CH3CN.
    [034] In an embodiment of the invention, the flow of TiCl4 is 2-4% by volume of a total flow of precursor gas, when depositing the layer of Ti (C, N) deposited by the MTCVD technique.
    [035] In one embodiment of the invention, a gas flow of said CH3CN or other nitrile is less than 0.5% by volume, preferably from 0.2 to 0.5% by volume, more preferably from 0.4 to 0.5% by volume.
    [036] By having a comparatively high proportion of Ti / CN and no additional hydrocarbons, soot formation in the deposition process can be avoided. With a high carbon content provided by the use of hydrocarbons, such as C2H4 and C3H6 in precursor gases, soot can be a problem.
    [037] In one embodiment of the present invention, the method further comprises N2 as a precursor agent. This is advantageous, due to the fact that adhesion can be improved and the small grain width and low carbon content are preserved. In addition, the coating deposited with precursor agents containing N2 shows a tendency to decrease variations in thickness in the chamber. An advantage of not using N2 as a precursor agent, but using only CH3CN or other nitrile is that the deposition rate is potentially higher.
    [038] In one embodiment of the invention, the gas flow N2 is less than 40% by volume, with respect to the total flow of precursor gas.
    [039] In an embodiment of the invention, the gas flow N2 is less than 10% by volume, preferably less than 5% by volume, with respect to the total flow of precursor gas.
    [040] Another possible precursor agent that can be used in conjunction with the aforementioned agent is HCl. HCl is advantageous due to its ability to decrease variations in thickness in the chamber. A disadvantage of HCl is the reduced deposition speed, as well as the tendency to increase the grain width of the Ti grains (C, N). When depositing the Ti (C, N) layer deposited by the [MTCVD] technique according to the invention, under a comparatively low temperature of 800-850 ° C, preferably 820-840 ° C, the thickness variations are smaller and HCl can be avoided, thereby avoiding the increase in grain size following the addition of HCl.
    [041] In one embodiment of the invention, the columnar layer of Ti (C, N) deposited by the [MTCVD] technique is deposited at a temperature of 800,850 ° C, preferably 820-840 ° C, using flow of precursor gases consisting of: 2 to 4% by volume of TiCl4; from 0.2 to 0.5% by volume, preferably from 0.4 to 0.5% by volume of nitrile, preferably CH3CN; and H2 balance; with a ratio of Ti / CN, based on a percentage by volume of TiCl4 and nitrile, provided in the vacuum chamber, of 6-7.
    [042] In one embodiment of the invention, the columnar layer of Ti (C, N) deposited by the MTCVD technique is deposited at a temperature of 800,850 ° C, preferably 820-840 ° C, using precursor gas flow of: 2 to 4% by volume of TiCl4; from 0.2 to 0.5% by volume, preferably from 0.4 to 0.5% by volume of nitrile, preferably CH3CN; less than 10% by volume of N2 and H2 balance; with a ratio of Ti / CN, based on a percentage by volume of TiCl4 and nitrile, provided in the vacuum chamber, of 6-7.
    [043] An advantage of the invention is that a small grain width in the layer of Ti (C, N) deposited by the MTCVD technique can be provided, without having an excessive amount of carbon in the process or in the coating layers formed.
    [044] Other objectives, advantages and characteristics of the invention will become evident from the following detailed description of the invention, when considered in conjunction with the drawings. Brief Description of Drawings
    [045] The modalities of the invention will now be described with reference to the accompanying drawings, in which: - figure 1a is a cross-sectional view of a coating according to an embodiment of the invention; figure 1b is an enlarged part of figure 1a, schematically illustrating the measurement of grain width in the Ti coating layer (C, N) deposited by the MTCVD technique; figure 2 is a histogram representing the distribution of grain width in the Ti coating layer (C, N) deposited by the MTCVD technique, shown in figure 1a; figure 3 is a cross-sectional view of a coating, according to an embodiment of the invention, in which the coated cutting tool has been subjected to a heat treatment to diffuse the heavy elements of the substrate within the coating; and - figure 4 is a cross-sectional view of a coating according to the state of the art. Detailed Description of the Invention Example 1
    [046] Coated cutting tools, according to an embodiment of the invention were manufactured. First, CNMG120412-KM carbide substrates, with a composition of 6.0% by weight of Co and WC balance, a Hc value of 17.52 kA / m (using a Foerster Koerzimat CS1.096 device, according to with DIN IEC 60404-7) and a hardness of HV3 = 1.6 GPa were manufactured by pressing powder and sintering the pressed bodies. Before the deposition of the coating, the substrates had the edges rounded to about 35 μm, by means of wet blasting. A coating consisting of a layer of Ti (C, N, O) with a total thickness of about 10.3 μm, which consists of the sequence of 0.4 μm TiN layers, Ti (C, N) deposited by the technique of MTCVD of 9.1 μm, Ti (C, N) deposited by the HTCVD technique of 0.2 μm and Ti (C, O) of 0.6 μm, a layer of α-Al2O3 with a texture (012) and a thickness of about 3.8 μm and a colored layer of TiC / TiN of 0.7 μm, was deposited by the CVD technique on the substrates. The coating was deposited in a chemical vapor deposition (CVD) reactor, with a radial gas flow, using deposition conditions for the growth of the Ti (C, N) layers deposited by the MTCVD technique and the α-Al2O3 layer, as described in Table 1. The oxidation and nucleation steps were performed before the growth of the α-alumina layer. After deposition, the coated cutting tools were subjected to a wet blasting procedure to remove the colored layer on the inclined faces.
    [047] Figure 1a shows a scanning electron microscopy (SEM) image in cross section of the coating and the outermost part of the substrate on the inclined face of one of the coated cutting tools, with a magnification of 15,000 times. The layer of Ti (C, N) deposited by the MTCVD technique presents a columnar structure with fine columnar grains. In order to evaluate the grain size of the Ti layer (C, N) deposited by the MTCVD technique, the grain width was measured in the image provided by the SEM procedure, as schematically shown in figure 1b and later explained below. The minimum grain width was 26 nm, the maximum grain width was 474 nm, the average grain width was 140 nm and the median grain width was 118 nm. With reference to figure 2, a histogram representing the grain width distribution of the Ti layer (C, N) deposited by the MTCVD technique was made based on this measurement. The widths of the measured grains are distributed in discrete intervals with a width of 40 nm, in the range of 30 to 470 nm, and of 20 nm, in the range of 470 to 570 nm. The maximum frequency of the measured grain widths is within the range of 70 to 110 nm.
    [048] With reference to figure 3, the coated cutting tool used to determine the grain width was subjected to a heat treatment in a gaseous flow of H2 at 55 mbar and temperature of 1100 ° C for 1.5 hours, at in order to diffuse the heavy elements of the substrate, that is, W and / or Co, within the grains interfaces of the Ti layer (C, N) deposited by the MTCVD technique, to provide contrast in an SEM image. With a magnification of 30000 times, the internal diffusion can be seen in the form of shiny lines between the grains, and the width of the grain is determined as the distance between these shiny lines (see figure 3). The grain width was measured along a 10 μm line, parallel to a substrate in a 4-5 μm position, starting from the substrate surface. The minimum grain width was 73 nm, the maximum grain width was 390 nm, the average grain width was 162 nm and the median grain width was 146 nm. The maximum frequency of the measured grain widths is within the range of 110 to 150 nm.
    [049] The texture coefficients TC (hkl) indicate preferential growth directions of the columnar grains of the Ti layer (C, N) deposited by the MTCVD technique (see Table 2), and the α-Al2O3 layer was determined by X-ray diffraction medium over coated cutting tools, manufactured according to Example 1, as explained below. The layer of Ti (C, N) deposited by the MTCVD technique presents a strong texture (422) with great value also for (311). The α-Al2O3 layer has a texture (012).
    [050] The Ti layer (C, N) deposited by the MTCVD technique exhibits an X-ray diffraction pattern with the reflection peak (422) at 2θ = 123.22 °, which was determined as explained below. This peak position corresponds to a C / (C + N) ratio in the Ti (C, N) layer deposited by the MTCVD technique of 0.57. A second method used to determine the carbon content by X-ray diffraction is by using the Rietveld refinement. The result of this approximation is the same as that resulting from the peak position. The FWHM of the reflection peak (422) is 0.44 °. An elementary analysis was also performed on the coated cutting tool used to determine the grain width by means of an electron probe analysis, as explained below, which demonstrated a proportion of C / (C + N) in the Ti layer (C, N) deposited by the 0.58 MTCVD technique. Example 2
    [051] A coated cutting tool was manufactured according to the state of the art, in order to serve as a reference when performing the test of the coated cutting tool presented in Example 1. First, cemented carbide substrates CNMG120412-KM, with a composition of 5.2% by weight of Co, 0.23% by weight of Cr carbides and WC balance, with a Hc value of 22.91 kA / m (using a Foerster Koerzimat CS1.096 device, of according to DIN IEC 60404-7) and a HV3 hardness = 1.8 GPa were manufactured by pressing powder and sintering the pressed bodies. Before the deposition of the coating, the substrates had the edges rounded to about 35 μm, by means of wet blasting. A coating consisting of a layer of Ti (C, N, O), which consists of the sequence of 0.4 μm TiN layers, Ti (C, N) deposited by the 9.8 μm MTCVD technique, Ti (C, N ) deposited by the HTCVD technique of 0.2 μm and Ti (C, O) of 0.6 μm, with a total thickness of 10.3 μm, a layer of α-Al2θa with a texture (012) and a thickness of about 4.0 μm and a colored layer of TiN / TiC of 1.2 μm, was deposited by the CVD technique on the substrates. The deposition conditions for growth of the Ti (C, N) layer deposited by the MTCVD technique are described in Table 1. After deposition, the coated cutting tools were subjected to a wet blasting procedure to remove the colored layer on the slanted faces.
    [052] The texture coefficients TC (hkl) indicate preferential growth directions for the columnar grains of the Ti layer (C, N) deposited by the MTCVD technique (see Table 2) and the α-Al2O3 layer was determined as explained Next. The layer of Ti (C, N) deposited by the MTCVD technique presents a strong texture (422), with great value also for (311). The α-Al2O3 layer has a texture (012). The Ti layer (C, N) deposited by the MTCVD technique exhibits an X-ray diffraction pattern with the reflection peak (422) at 2θ = 123.47 °, which was determined as explained below. This peak position corresponds to a C / (C + N) ratio in the Ti (C, N) layer deposited by the MTCVD technique of 0.52. The FWHM of the reflection peak (422) is 0.27 °. An elementary analysis was also performed by means of an electronic probe analysis, as explained below, which demonstrated a ratio of C / (C + N) in the Ti layer (C, N) deposited by the MTCVD technique of 0.56.
    [053] Figure 4 shows an image made by the SEM procedure in cross section of the reference coating and the outermost part of the substrate on the inclined face of the coated cutting tool. The layer of Ti (C, N) deposited by the MTCVD technique has a columnar structure with thick columnar grains that extend through said layer of Ti (C, N) deposited by the MTCVD technique. Example 3
    [054] Coated cutting tools were manufactured according to Example 1, with the same layer of Ti (C, N, O), but with a different layer of α-Al2O3, with a layer thickness of 4.2 mm and using a different production process of the α-Al2O3 layer, providing a greater TC (006) than in the α-Al2O3 layer of Example 1, as measured by X-ray diffraction. Example 4
    [055] Coated cutting tools were manufactured according to Example 1, with the same Ti layer (C, N, O) and α-Al2O3 layer as in Example 3, however, where the Ti layer (C, N) deposited by the MTCVD technique was deposited at a temperature of 870 ° C, instead of 830 ° C. The higher deposition temperature resulted in a layer of Ti (C, N) deposited by the MTCVD technique with a much finer particle size than that of Example 1 and Example 3, as seen in SEM procedure images in cross section. Table 1

    Table 2
    Example 5
    [056] Coated cutting tools, according to Examples 1 and 2, were tested in 09.2 GGG60 nodular cast iron turning without agent and cooling, including external axial intermittent cutting operations and face-type cutting operations, under the following conditions: - cutting speed (Vc): 350 m / min; - feed (Fn): 0.3 mm / turn - depth of cut (ap): 4 mm; - time / component (Tc): 1.25 min / piece.
    [057] The service life criterion for the tested tools has been deviated from the dimensional tolerances of the workpiece. The coated cutting tool of Example 2 represented the state of the art, being adapted to cut 12 pieces. The coated cutting tool of Example 1 represented an example of an embodiment of the present invention, adapted to cut 18 pieces. Intermittent dry cutting of nodular cast iron is a highly demanding cutting operation, so scaling and other discontinuous wear mechanisms, as well as insufficient oxidation resistance, usually limit tool life. In this test, both tool variants exhibit satisfactory oxidation resistance, but the tool in Example 1 outperforms the tool in Example 2, due to a higher resistance to chip or scale formation. The coated cutting tools of Example 3, which differ from the coated cutting tools, essentially only with respect to the texture of the α-Al2O3 layer, exhibited the same advantageous performance as the coated cutting tools of Example 1, in the present performance test . Example 6
    [058] The coated cutting tools of Examples 1 and 2 were tested in a nodular cast iron turning procedure (09.2 GS500 HB220), with a cooling agent, including continuous cutting operations, of internal axial roughness, under the following conditions: - cutting speed (Vc): 160 m / min; - feed (Fn): 0.35 mm / turn - depth of cut (ap): 3 mm; - time / component (Tc): 1.5 min / piece
    [059] The service life criterion for the tested tools has been deviated from the dimensional tolerances of the workpiece. The coated cutting tool of Example 2 represented the state of the art, being adapted to cut 15 pieces. The coated cutting tool of Example 1 represented an example of an embodiment of the present invention, adapted to cut 22 pieces. Unlike the wear mechanism of Example 3, the service life in this test is limited by the wear resistance of the flanks, which is superior to the coated cutting tool of Example 1. The coated cutting tools of Example 3, which differ from the cutting tools of Example 3. coated shears, essentially only with respect to the texture of the α-Al2O3 layer, exhibited the same advantageous performance as the coated cutting tools of Example 1, in the present performance test. Example 7
    [060] The coated cutting tools of Examples 3 and 4 were tested in longitudinal turning of nodular cast iron, SS0717, including intermittent cutting operations with cooling agent, under the following conditions: - cutting speed (Vc): 250 m / min; - feed (Fn): 0.2 mm / turn - depth of cut (ap): 2.5-2.0 mm;
    [061] The cutting tool of Example 3 was superior to the cutting tool of Example 4, with respect to the resistance to the formation of chips or scales.
    [062] For the purpose of the present application, and in particular for the examples above, the methods of determining the properties of the coating are defined below.
    [063] In order to evaluate the thickness and grain size of the individual layers of the coating, the coated cutting tool is cut, ground and polished, in order to obtain a polished cross section, with a normal surface perpendicular to a surface of the substrate, on the slanted face of the coated cutting tool.
    [064] Layer thicknesses are measured using an optical microscope.
    [065] In order to allow the measurement of grain width, it is necessary to obtain a smooth surface that provides sufficient contrast between the grains of different orientation, in the Ti layer (C, N) deposited by the MTCVD technique, through the formation of channels of electrons. Thus, for the purpose of measuring grain width, polishing the cross section comprises the steps of: - coarse polishing on paper, using an oil-based diamond suspension (from Microdiamant AG), with an average diamond particle size 9 μm, and 0.7 g of diamond particles per 2 dl of oil (Mobil Velocite no. 3); - fine polishing on paper, using an oil-based diamond suspension (from Microdiamant AG), with an average diamond particle size of 1 μm, and 0.7 g of diamond particles per 2 dl of oil (Mobil Velocite No. 3); e - polishing of oxide using a soft cloth and immersed in a suspension comprising a mixture of particles of SiO2 (10-30%) and Al2O3 (1 20%), with an average particle size of 0.06 μm (Masterpolish 2 , Buehler), at 150 rpm and pressure of 35N for 220 s.
    [066] The grain width is measured with a scanning electron microscope (SEM) micrograph, of a polished cross section with a 15,000-fold magnification in the SEM procedure, obtained at a voltage of 5.0 kV and with a distance 5 mm processing time, as schematically shown in figure 1b. The grain boundaries are identified by the differences in contrast between adjacent grains and the grain widths are measured as the distance between the identified adjacent grain boundaries, along a straight 10 μm line, in a direction parallel to a substrate surface, in a centralized position between a lower interfacial surface and a higher upper interfacial surface of the Ti (C, N) layer deposited by the MTCVD technique. Grain widths less than 20 nm are not easily identified by the SEM process image and are not considered.
    [067] The columnar layer of Ti (C, N) deposited by the MTCVD technique comprises double columnar grains and can also comprise other defects or inter-granular displacements, which are not idealized to be counted as grain boundaries in the present method. Double borders can be identified and excluded, since the symmetry and orientation of the double grains may not generate any substantial difference in contrast when crossing the double borders. Consequently, the double columnar grain is idealized to be treated as a grain when determining the width of the grain. However, it can sometimes be difficult to verify this and counting a double boundary as an inter-granular boundary will decrease the average grain width value. To overcome this difficulty in measuring the width of the grain, a method comprising the diffusion of heavy elements of the substrate within the grain boundaries can be used, by way of example according to the method used in Example 1. This is advantageous in the fact that the heavy elements cannot diffuse within the aforementioned defects or displacements. In order to prepare the cross section for visualization of the internally diffused binder, the cross sections are submitted only to the coarse polishing step and the fine polishing step, omitting the oxide polishing step. This provides a greater surface roughness than that obtained by polishing with oxide, so the contrast will be completely different and a backscatter contrast composition mode is used to visualize the grain boundaries with heavier elements diffused internally.
    [068] In order to investigate the texture of the Ti (C, N) layer deposited by the MTCVD technique, an X-ray diffraction is conducted on the flank face, using a PANalytical CubiX3 diffractometer, equipped with a PIXcel detector. The coated cutting tools are mounted on sample holding devices, which guarantee that the flank surface of the samples will be parallel to the reference surface of said sample holding device, and even though the flank face has an appropriate height. Cu-Kα X-rays are used for measurements, with a voltage of 45 kV and a current of 40 mA. Anti-diffusers and slots of ^ degree and slots of divergence of ^ degree are still used. The diffracted intensity of the coated cutting tool is measured around 2θ angles, where TiCN peaks occur, ranging from approximately 20 ° to 140 °, that is, over an incident angle θ ranging from 10 to 70 °.
    [069] Data analysis, including subtraction of antecedent factors and extraction of Cu-Kα is performed using a PANalytical's X'Pert HighScore program, and the integrated peak areas that originate from this use are used to calculate the texture coefficients TC (hkl) of the Ti layer (C, N) deposited by the MTCVD technique, using the X'Pert Industry program, by comparing the proportion of the measured intensity data with the standard intensity data, according to the equation:
    where: I (hkl) = intensity of the measured reflection area (hkl); I0 (hkl) = standard intensity according to PDF card, No. 42-1489 of the ICDD; n = number of reflections used in the calculation; and the reflections (hkl) used in the calculation are: (111), (200), (220), (311), (331), (420), (422) and (511).
    [070] Since the Ti (C, N) layer deposited by the MTCVD technique is a finitely thick film, the relative intensities of a peak pair of the same compound are different from that provided for bulky samples, due to differences in length of the path through the Ti layer (C, N). Therefore, a thin film correction is applied to the integrated intensities of peak areas, also taking into account the linear absorption coefficient of Ti (C, N), when calculating the TC values. Since the substrates used in the examples were WC, a further correction is applied to correct the overlap of the TiCN peak (311) by the WC peak (111). This is done by deducting 25% of the intensity of the area from another WC peak, notably WC (101), from the intensity of the TiCN area (311). Since possible layers above the layer of Ti (C, N) deposited by the MTCVD technique can affect the intensities of X-rays that enter the layer of Ti (C, N) deposited by the MTCVD technique and that leave the entire coating , corrections also need to be made for these, taking into account the linear absorption coefficient for the respective compound in one layer.
    [071] In order to estimate the carbon content, the 2θ diffraction angle of the reflection (422) in the X-ray diffraction pattern obtained using CuKα radiation is determined. The position of the reflection (422) refers to the carbon content in the coating, so that a higher carbon content correlates with a lower angle of reflection (422). The C / N ratio in the TiC0N1 to TiC1N0 range shows a linear dependence for the 2θ diffraction angle, making it possible to extract information about the C / N ratio by measuring the position of the reflection (422).
    [072] A second method for determining the carbon content is through the use of the Rietveld refinement, for the complete collected diffraction pattern, as discussed above. From this refining, it is possible to extract data from the truss structure parameters for the TiCN phase. The truss structure parameter also varies linearly with the C / N ratio, as discussed above. The result of this approximation is also correlated with the results in which the diffraction angle was the parameter used to perform the carbon content survey.
    [073] Reflection (422) is also used to estimate the width of the grain. This is achieved by determining the peak FWHM in the diffractogram. The FWHM is correlated to the grain size, so that a larger width value correlates with smaller grains.
    [074] The elementary analysis is carried out by electronic probe analysis using a JEOL electronic probe, JXA-8900R, equipped with dispersive wavelength spectrometers (WDS), in order to determine the proportion of C / (C + N) of the Ti (C, N) layer deposited by the MTCVD technique. The analysis of the average composition of the Ti layer (C, N) deposited by the MTCVD technique is conducted in a polished cross section of the flank face, inside the Ti layer (C, N) deposited by the MTCVD technique, in 10 points with 50 μm spacing along a straight line, in a direction parallel to a substrate surface, in a centralized position between a lower interfacial surface and a higher upper interfacial surface of the Ti (C, N) deposited by the MTCVD technique , using 10 kV, 29 nA, a standard TiCN, and with corrections for atomic number, absorption and fluorescence. In example 1, the dots were placed inside the Ti coating (C, N) deposited by the MTCVD technique, at a distance of 4-6 μm from the interface between the substrate and the Ti layer (C, N) deposited by the technique of MTCVD.
    [075] Although the invention has been described in connection with several exemplary modalities, it should be understood that the invention should not be limited to the exemplary modalities disclosed, on the contrary, the invention is idealized to cover several modifications and equivalent provisions.
    权利要求:
    Claims (13)
    [0001]
    1. Coated cutting tool, having a chemical vapor deposition (CVD) coating, the tool comprising a substrate and a surface coating, the coating comprising a layer of Ti (C, N, O), the layer of Ti (C, N, O) consists of a sequence of layers according to TiN / MTCVD Ti (C, N) / Ti (C, O), optionally provided an HTCVD Ti (C, N) layer deposited between the layers MTCVD Ti (C, N) and Ti (C, O), the MTCVD Ti (C, N) layer is one or more of C, N and O, comprising at least one columnar layer of Ti (C, N) deposited by chemical vapor deposition technique at moderate temperature (MTCVD), with an average grain width of 0.05-0.4 μm on an inclined face of the coated cutting tool, along a straight line in a direction parallel to a substrate surface, in a centralized position between a lower and a higher interface, characterized by the fact that, in a cross section with a normal perpendicular surface home to a normal substrate surface, an atomic ratio of carbon to the sum of carbon and nitrogen (C / (C + N)) contained in the Ti (C, N) layer deposited by the MTCVD technique is, on average, 0.50-0.65, measured by electron probe analysis in 10 positions spaced 50 μm along the straight line, an average thickness of the columnar layer of Ti (C, N) deposited by the MTCVD technique being 5-15 μm.
    [0002]
    2. Coated cutting tool according to claim 1, characterized by the fact that the average grain width is 0.1-0.2 μm.
    [0003]
    3. Coated cutting tool according to claim 1 or 2, characterized by the fact that the ratio of C / (C + N) is 0.560.60.
    [0004]
    4. Coated cutting tool according to any one of the preceding claims, characterized by the fact that the Ti (C, N) layer deposited by the MTCVD technique exhibits an X-ray diffraction pattern, measured through the use of radiation Cu-Kα, where the texture coefficients (TC (hkl) are defined by:
    [0005]
    5. Coated cutting tool according to any one of the preceding claims, characterized in that it additionally comprises an Al2O3 layer.
    [0006]
    6. Coated cutting tool according to claim 5, characterized by the fact that the Al2O3 layer is a layer of α-AI2O3 with an average thickness of 2-6 μm.
    [0007]
    7. Method for producing a coated cutting tool, of the type defined in claim 1, the method being characterized by the fact that it comprises the steps of: - providing a substrate in a vacuum chamber; - provide precursors to the vacuum chamber; - deposit a layer of Ti (C, N, O) comprising at least one columnar layer of Ti (C, N) deposited by the technique of chemical vapor deposition at moderate temperature (MTCVD) on the substrate, in which the columnar layer of Ti (C, N) deposited by the MTCVD technique is deposited at a temperature in the range of 800-850 ° C, using precursors consisting of TiCl4, CH3CN or other nitrile, and H2, and with a Ti / CN ratio of 410 reflecting a percentage by volume of TiCl4 and CH3CN or other nitrile provided to the vacuum chamber.
    [0008]
    8. Method, according to claim 7, characterized by the fact that the Ti / CN ratio is 6-7.
    [0009]
    9. Method according to claim 7 or 8, characterized by the fact that the precursors consist of TiCl4, CH3CN and H2.
    [0010]
    10. Method according to claim 7, characterized by the fact that a gas flow of TiCl4 is 2-4% by volume of a total gas flow of precursors during the deposition of the Ti layer (C, N) deposited by the MTCVD technique.
    [0011]
    11. Method according to claim 7, characterized by the fact that a gaseous flow of one or more nitriles is 0.2 to 0.5% by volume of a total gaseous flow of precursors during the deposition of the Ti layer (C, N) deposited by the MTCVD technique.
    [0012]
    12. Method according to claim 7, characterized by the fact that it deposits a layer comprising Ti (C, N, O), from a TiN substrate, Ti (C, N) deposited by MTVCD, Ti (C, N) deposited by HTCVD and Ti (C, O).
    [0013]
    13. Method according to claim 7, characterized in that it additionally comprises depositing a layer of α-Al2O3.
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    同族专利:
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    EP2791387B1|2018-02-21|
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    EP2791387B8|2018-03-28|
    JP2015500148A|2015-01-05|
    BR112014014484A2|2018-05-22|
    EP2604720A1|2013-06-19|
    US20140308083A1|2014-10-16|
    KR20140105754A|2014-09-02|
    KR102068855B1|2020-01-21|
    IN2014KN01232A|2015-10-16|
    WO2013087848A1|2013-06-20|
    JP6238904B2|2017-11-29|
    RU2014128598A|2016-02-10|
    EP2791387A1|2014-10-22|
    US9945029B2|2018-04-17|
    RU2623547C2|2017-06-27|
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    法律状态:
    2018-06-05| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-07-07| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-11-10| B09A| Decision: intention to grant|
    2021-01-19| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11009859.7|2011-12-14|
    EP11009859.7A|EP2604720A1|2011-12-14|2011-12-14|Coated cutting tool and method of manufacturing the same|
    PCT/EP2012/075569|WO2013087848A1|2011-12-14|2012-12-14|Coated cutting tool and method of manufacturing the same|
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