WO2015141743A1 - 被覆切削工具及びその製造方法 - Google Patents
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- 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
- C23C14/0664—Carbonitrides
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- 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
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- 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
- C23C14/0641—Nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
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- 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
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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- 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
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- 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
- C23C14/3435—Applying energy to the substrate during sputtering
- C23C14/345—Applying energy to the substrate during sputtering using substrate bias
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
Definitions
- the present disclosure relates to a coated cutting tool in which a hard film is coated on the surface of a base material and a method for manufacturing the same.
- Cutting tools are required to have higher durability, and coated cutting tools in which the surface of the cutting tool is coated with a hard film made of various ceramics having excellent heat resistance and wear resistance are applied.
- AlCrSi-based nitrides or carbonitrides that have been improved in wear resistance and heat resistance by adding Si to nitrides or carbonitrides mainly composed of Al and Cr, which are film types with excellent heat resistance.
- Coated cutting tools have been proposed (see JP 2006-239792, JP 2005-126736, and JP 2004-337988).
- Japanese Patent Laid-Open No. 2002-337007 discloses that an AlCrSi-based nitride having a microstructure composed of a relatively Si-rich amorphous phase and a relatively Si-poor crystal phase has improved film hardness and oxidation resistance. It is shown that the durability of the coated cutting tool is improved by applying this.
- Various conditions have been studied for film formation conditions when coating a nitride or carbonitride mainly composed of Al and Cr. For example, it has been shown that a pulse bias voltage is applied when a nitride mainly composed of Al and Cr is coated (see Japanese Patent Application Laid-Open Nos. 2010-12564 and 2010-284787).
- the present disclosure has been made in view of the above-described problems, and an object of an embodiment of the present invention is to provide a coated cutting tool that is superior in durability and a coating that can stably manufacture a coated cutting tool that is excellent in durability. It is providing the manufacturing method of a cutting tool.
- the first aspect of the present invention is: ⁇ 1> A base material, and a hard coating disposed on the surface of the base material,
- the hard coating has an aluminum (Al) content ratio of 50 atomic% or more and 68 atomic% or less, and a chromium (Cr) content ratio of 20 atomic% or more with respect to the total amount of metal (including metalloid) elements.
- a nitride or carbonitride having a content ratio of 46 atomic% or less and a silicon (Si) content of 4 atomic% or more and 15 atomic% or less, and a metal (including metalloid) element, nitrogen, oxygen, or carbon
- the atomic ratio (atomic%) A of the metal (including metalloid) element A and the atomic ratio (atomic%) B of nitrogen when the total amount is 100 atomic% is 1.03 ⁇ B / A ⁇ 1.07 Meet relationships, Coated cutting tool in which the peak intensity due to the (200) plane or the (111) plane of the face-centered cubic lattice structure shows the maximum intensity in the intensity profile obtained from the X-ray diffraction pattern or the limited field diffraction pattern of the transmission electron microscope It is.
- the hard film has an intensity profile obtained from a limited field diffraction pattern of a transmission electron microscope, and a peak intensity due to the (010) plane of AlN having a hexagonal close-packed structure is Ih, On the (111) face of AlN, the (111) face of CrN, the (200) face of AlN, the (200) face of CrN, the (220) face of AlN, and the (220) face of CrN in a face-centered cubic lattice structure
- the sum of the peak intensity due to the peak intensity due to the (010) plane of AlN, the (011) plane of AlN and the (110) plane of AlN in the hexagonal close-packed structure is Is, Ih It is preferable that the relationship of ⁇ 100 / Is ⁇ 25 is satisfied.
- the hard coating is a metal element of Group 4 (Group 4a), Group 5 (Group 5a), and Group 6 (Group 6a) (excluding Cr) in the periodic table
- the content ratio of one or more elements selected from the group consisting of boron (B) is preferably 15 atomic% or less with respect to the total amount of metal (including metalloid) elements.
- a protective film made of nitride or carbonitride having a composition different from that of the hard film is further formed on the hard film on the substrate. It is preferable to have.
- the protective coating disposed on the hard coating has a Ti content (atomic%) of 50% or more and a Si content of 1% with respect to the total amount of metal (including metalloid) elements.
- a film made of nitride or carbonitride having a content of 30% or less is preferable.
- the hard coating preferably has a nanoindentation hardness of 40 GPa to 55 GPa.
- the second aspect of the present invention includes ⁇ 6>
- the content ratio (atomic%) of aluminum (Al) is 55% to 70% with respect to the total amount of metal (including metalloid) elements
- the content ratio (atomic%) of chromium (Cr) is
- An alloy target having a silicon (Si) content ratio (atomic%) of not less than 20% and not more than 35% and not less than 7% and not more than 20% is set on the cathode, and a bias voltage applied to the substrate is ⁇ 220 V or more and ⁇ 60 V Arc ion plate under the conditions that the cathode voltage is 22 V or more and 27 V or less, or the bias voltage applied to the substrate is ⁇ 120 V or more and ⁇ 60 V or less and the cathode voltage is 28 V or more and 32 V or less.
- a method of manufacturing a coated cutting tool which includes a step of forming a hard film on a surface of a base material by coating the surface of the base material with nitride or carbonitride by
- a coated cutting tool having excellent durability is provided. Moreover, according to one Embodiment of this invention, the manufacturing method of the coated cutting tool which can manufacture stably the coated cutting tool excellent in durability is provided.
- the “X-ray diffraction pattern” refers to a diffraction peak curve measured using an X-ray diffractometer (manufactured by Rigaku Corporation, RINT2000; using a vertical goniometer and a fixed monochromator). Point to.
- the “restricted field diffraction pattern” refers to a diffraction pattern obtained by a transmission electron microscope when only an electron beam from a specific region is extracted using a limited field stop.
- the coated cutting tool which concerns on embodiment of this invention has a base material and the hard film
- Other films such as an intermediate film disposed between the film and the film may be provided.
- the hard coating in the present disclosure has an aluminum (Al) content ratio of 50 atomic% to 68 atomic% and a Cr content ratio of 20 atomic% to 46 with respect to the total amount of metal (including metalloid) elements. It is composed of a nitride or carbonitride having a content ratio of silicon (Si) of 4 atomic% or more and 15 atomic% or less, and containing metal (including metalloid) elements, nitrogen, oxygen and carbon.
- Relationship between atomic ratio (atomic%) A of metal (including metalloid) element A and atomic ratio (atomic%) B of nitrogen when the total is 100 atomic% is 1.03 ⁇ B / A ⁇ 1.07
- the peak intensity due to the (200) plane or (111) plane of the face-centered cubic lattice structure has the maximum intensity in the intensity profile obtained from the X-ray diffraction pattern or the limited field diffraction pattern of the transmission electron microscope.
- the inventor examined the damage factor of the coated cutting tool in the cutting of a hard material, and paid attention to a large columnar grain boundary existing in the hard coating. That is, it was confirmed that when a large columnar grain boundary that reaches the substrate from the surface of the film exists in the thickness direction of the hard film, the film breakage easily occurs.
- AlCr-based nitride or carbonitride which is a film type with excellent heat resistance and wear resistance, is used as the main composition, and the large grain boundaries that can be the starting point of fracture are reduced by refining the film structure. Confirmed that is valid. In addition, it was confirmed that it was effective to contain a certain amount of silicon (Si) element in order to refine the film structure.
- a metal metal (metalloid) It was found that it is important that the atomic ratio of nitrogen is controlled within a certain range with respect to the total amount of elements.
- the embodiment according to the present invention is achieved based on the event confirmed as described above and the obtained knowledge.
- the hard coating in the present disclosure is made of a nitride or carbonitride containing aluminum (Al), chromium (Cr), and silicon (Si).
- Nitride or carbonitride containing Al and Cr as main elements can form a film type that exhibits excellent wear resistance and heat resistance as a coated cutting tool.
- nitride is more preferable as the composition forming the hard film.
- it is effective to contain most Al by an atomic ratio (atomic%) with respect to the total amount of a metal (a semimetal is included) element.
- Al Al is an element that imparts heat resistance.
- the content ratio (atomic%) of elements other than Al is the largest with respect to the total amount of metal (including metalloid) elements, the heat resistance decreases.
- the Al content ratio (atomic%) is set to 50% or more with respect to the total amount of metal (including metalloid) elements. More preferably, the Al content ratio (atomic%) is 55% or more based on the total amount of metal (including metalloid) elements.
- the hard coating in the present disclosure has ZnS-type hexagonal close-packed packing (hcp; hereinafter simply abbreviated as “hcp”) that exists at the micro level.
- the structure has a large amount of AlN, and the durability of the coated cutting tool tends to decrease. Therefore, the hard coating in the present disclosure has an Al content ratio of 68 atomic% or less.
- the Al content ratio is preferably 65 atomic percent or less, and more preferably 60 atomic percent or less.
- the semimetal refers to boron (B), silicon (Si), germanium (Ge), and arsenic (As).
- the hard coating in the present disclosure contains 20 atomic% or more and 46 atomic% or less of Cr with respect to the total amount of metal (including metalloid) elements.
- the content ratio of Cr is within the above range, the wear resistance and heat resistance of the hard coating become more excellent.
- the content ratio (atomic%) of Cr in the hard coating is too small, the wear resistance is lowered and the AlN having an hcp structure existing at the micro level is increased, and the durability of the coated cutting tool is lowered.
- the content ratio (atomic%) of Cr increases too much, the heat resistance of the hard coating tends to decrease.
- the Cr content ratio is preferably 30 atomic% or more based on the total amount of metal (including metalloid) elements from the viewpoint of further improving both the wear resistance and heat resistance of the hard coating, Atomic% or more is more preferable. Furthermore, the Cr content ratio is preferably in the range of 40 atomic% or less.
- the total content ratio of Al and Cr is 85 atomic% or more with respect to the total amount of metal (including metalloid) elements. It is preferable. Furthermore, the total content ratio of Al and Cr is more preferably 88 atomic% or more, and further preferably 90 atomic% or more.
- silicon (Si) is an important element for refining the film structure.
- the hard coating in this indication makes silicon (Si) into the range of 4 atomic% or more and 15 atomic% or less with respect to the total amount of a metal (a semimetal is included) element.
- the nitride or carbonitride containing Al and Cr as main elements has a structure in which coarse columnar particles are clearly observed in the processed cross section of the hard coating. In a textured form in which coarse columnar particles are clearly observed, tool damage tends to increase during cutting of a hard material.
- a nitride or carbonitride containing a certain amount of Si and containing Al and Cr as main elements has a fine structure, and clear columnar particles are observed when the cross section of the hard coating is observed. It becomes difficult.
- the hard film having such a structure has less coarse crystal grain boundaries as starting points of fracture, and can suppress tool damage.
- the Si content increases, the amorphous phase existing at the micro level and the AlN having the hcp structure increase, and the durability of the coated cutting tool tends to be lowered.
- the hard coating in the present disclosure has a Si content ratio in the range of 4 atomic% to 15 atomic% with respect to the total amount of metal (including metalloid) elements.
- the content ratio of Si is less than 4 atomic%, the columnar particles are coarse and the durability tends to decrease.
- the Si content ratio exceeds 15 atomic% the film structure tends to be amorphous, and therefore a face-centered cubic lattice (fcc; hereinafter simply abbreviated as “fcc”) structure is mainly used.
- fcc face-centered cubic lattice
- the hard coating in the present disclosure preferably has a Si content (atomic%) of 5 atomic% or more, and preferably 6 atomic% or more.
- the Si content (atomic%) is preferably 12 atomic% or less.
- the fcc structure in the present disclosure is a crystal structure specified by X-ray diffraction.
- the fact that the fcc structure is an fcc structure is, for example, a commercially available X-ray diffractometer (manufactured by Rigaku Corporation, RINT2000; vertical goniometer and fixed monochromator).
- the peak intensity due to the hcp structure of AlN is not confirmed.
- the atomic ratio (atomic%) of each element in the hard film was measured using an electron probe microanalyzer (model number: JXA-8500F, manufactured by JEOL Ltd.) under the following conditions. This is obtained by (WDS-EPMA) measuring 5 points with an analysis depth of about 1 ⁇ m from the measurement surface and averaging the measured values.
- the peak intensity due to the (200) plane or the (111) plane of the fcc structure shows the maximum intensity in the intensity profile obtained from the X-ray diffraction pattern or the limited field diffraction pattern of the transmission electron microscope.
- the amount of hNp structure AlN contained in the hard coating increases, the hard coating becomes brittle and the durability as a coated cutting tool becomes poor.
- the crystal structure of the hard coating is an fcc structure
- the crystal plane other than the (200) plane or the (111) plane is When the maximum strength is exhibited, the durability tends to be poor.
- the crystal structure of the hard coating in the present disclosure can be confirmed from an intensity profile obtained from an X-ray diffraction pattern or a limited field diffraction pattern using a transmission electron microscope.
- the test area of the hard coating is small, it may be difficult to identify the crystal structure by X-ray diffraction. In such a case, the crystal structure can be identified by a limited field diffraction pattern using a transmission electron microscope.
- the hard coating in the present disclosure may contain an amorphous phase or hcp-structured AlN in part of the microstructure. In the hard film in the present disclosure, it is preferable that a diffraction pattern due to AlN having an hcp structure is not confirmed in a limited field diffraction pattern using a transmission electron microscope.
- a hard film with a nitride or carbonitride containing Al and Cr as main elements containing a certain amount of Si and refined film structure It is important to control the atomic ratio (atomic%) of nitrogen to the ratio (atomic%) within a certain range.
- a nitride or carbonitride containing Al and Cr as the main elements containing a certain amount of Si and having a refined coating structure is likely to increase the amorphous phase and the hcp-structured AlN, and thus a coated cutting tool. Even if it is applied to, it tends to be difficult to obtain excellent durability.
- the atomic ratio of nitrogen contained (atomic %) was confirmed to improve the crystallinity and heat resistance of the hard coating and to improve the durability of the coated cutting tool.
- the atomic ratio (atomic%) of nitrogen in the hard coating becomes too large, the residual compressive stress of the hard coating becomes too high, and as a result, the hard coating tends to cause self-destruction.
- the above B / A value is obtained by measuring the atomic ratios A and B by analyzing the composition of the hard film by wavelength dispersive electron probe microanalysis (WDS-EPMA).
- WDS-EPMA wavelength dispersive electron probe microanalysis
- the hard coating in the present disclosure inevitably contains oxygen and carbon. Therefore, for example, when analyzing the film composition of nitride, if the B / A is calculated without considering the unavoidable oxygen and carbon, the content ratio of nitrogen is relatively increased, and the B in the hard film is increased. In some cases, the value of / A cannot be accurately evaluated. Therefore, in the analysis of the hard coating, when obtaining the B / A value in the hard coating, the total of metal elements (including metalloids) and nitrogen, oxygen and carbon is 100 atomic%, of which the atoms of the metal elements Assuming that the ratio (atomic%) is A and the atomic ratio (atomic%) of nitrogen is B, the value of B / A is obtained.
- the atomic ratio in the hard coating is as follows.
- Oxygen is preferably in the range of 0.2 atomic% or more and 3.0 atomic% or less (more preferably 2.0 atomic% or less, and further 1.0 atomic% or less), metal elements (including metalloids) and nitrogen.
- carbon is 0.2 atomic% or more and 5.0 atomic% or less (more preferably 3.0 atomic% or less, and further 1.0 atomic%). The following range is preferable.
- the hard film aluminum (Al), chromium (Cr), silicon (Si), nitride composed of nitrogen (N) and inevitable components, or aluminum (Al), chromium (Cr), silicon (Si ), Nitrogen (N), carbon (C), and a film made of carbonitride composed of inevitable components.
- the hard coating in the present disclosure has the Al, Cr, and Si content ratios and B / A in a specific range as described above, and is caused by the (200) plane or the (111) plane of the face-centered cubic lattice structure. In the range where the peak strength shows the maximum strength, the durability of the coated cutting tool can be maintained well even if other metal elements other than Al, Cr and Si are contained. Therefore, the hard film in this indication may contain metallic elements other than Al, Cr, and Si.
- the hard coating in the present disclosure contains a metal element other than Al, Cr, Si, Group 4 (Group 4a), Group 5 (Group 5a), and Group 6 (Group 6a) (excluding Cr) in the periodic table
- B boron
- These elements are elements that impart wear resistance or heat resistance to the hard coating. When they are contained within a predetermined range with respect to the total amount of metal (including metalloid) elements, the durability of the coated cutting tool is remarkably increased. There is no reduction. However, when the hard coating contains a metal element other than Al, Cr, and Si, if the content in the hard coating is excessive, the durability of the coated cutting tool may be reduced.
- the hard coating in the present disclosure contains one or more elements selected from the group consisting of Group 4, Group 5 and Group 6 (excluding Cr) and boron (B) in the periodic table, and a metal ( It is preferably contained in the range of 15 atomic% or less with respect to the total amount of elements (including metalloid).
- the content ratio of elements selected from Group 4, Group 5 and Group 6 (excluding Cr) and boron (B) in the periodic table is more preferably 10 atomic% or less for the same reason, More preferably, it is 0 atomic percent (not contained).
- AlCrSi nitride composed of Al, Cr, Si, N and unavoidable elements or AlCrSi carbonitride composed of Al, Cr, Si, N, C and unavoidable elements is more preferable.
- AlCrSi nitride composed of Al, Cr, Si, N and inevitable elements.
- AlCrSi nitride and AlCrSi carbonitride are advantageous in terms of production cost.
- the hard coating in the present disclosure preferably has a nanoindentation hardness of 40 GPa to 55 GPa.
- Nitrides or carbonitrides containing a certain amount of Al, Cr and Si tend to increase the hcp-structured AlN and amorphous phase and decrease the hardness. Even if the composition of the hard coating and the nitrogen content ratio are controlled, the durability of the coated cutting tool is reduced if the hardness of the hard coating is low.
- the nano-indentation hardness of the hard coating is 40 GPa or more. Furthermore, the nanoindentation hardness is preferably 45 GPa or more.
- the hard coating in the present disclosure preferably has a nanoindentation hardness of 55 GPa or less.
- the nanoindentation hardness of the hard coating can be adjusted to the above range by controlling the negative bias voltage applied to the substrate, the deposition temperature, and the average magnetic flux density of the cathode to appropriate ranges in addition to the coating composition. And a high degree of durability is imparted by the coated cutting tool.
- the nanoindentation hardness satisfies the above range
- the elastic modulus of the hard coating is 390 GPa or more.
- the elastic modulus of the hard coating is preferably 450 GPa or less.
- the elastic modulus is more preferably in the range of 400 GPa to 430 GPa for the same reason as described above.
- the nano-indentation hardness and elastic modulus of the hard coating in the present disclosure are determined by using a nano-indentation device (Ultra Fine Indentation Hardness Tester ENT-1100a manufactured by Elionix Co., Ltd.) to indent the terminal from the surface of the hard coating.
- the maximum depth at which the indentation depth is maintained at 1/10 or less of the thickness of the hard coating is 10 points under the measurement conditions of 49 mN, maximum load holding time of 1 second, and removal rate after loading of 0.49 mN / second. Measured and obtained from an average value of 6 points excluding 2 points on the larger value side and 2 points on the smaller value side.
- the microstructure of the hard coating in the present disclosure is preferably a structure having a crystal phase having a relatively high Si content and a crystal phase having a relatively low Si content in the crystal structure.
- the microstructure of the hard coating has such a structure, high residual compressive stress is imparted by the hard coating to improve the coating hardness, and crack progress is easily suppressed at the micro level.
- the hard film in the present disclosure has a high Si content, and AlN having an hcp structure may exist in the microstructure.
- AlN having an hcp structure may exist in the microstructure.
- an intensity profile obtained from a limited field diffraction pattern of a transmission electron microscope can be used when a processed cross section of the hard coating is observed. Specifically, the relationship of Ih ⁇ 100 / Is is evaluated in the intensity profile of the limited field diffraction pattern of the transmission electron microscope.
- the hard film in the present disclosure preferably satisfies the relationship of Ih ⁇ 100 / Is ⁇ 25 by reducing the AlN having an hcp structure present in the microstructure. By satisfying the relationship of Ih ⁇ 100 / Is ⁇ 25, the durability of the coated cutting tool becomes more excellent. Furthermore, the hard coating in the present disclosure preferably satisfies the relationship of Ih ⁇ 100 / Is ⁇ 20.
- the thickness of the hard coating is preferably 1.0 ⁇ m or more, and more preferably 2.0 ⁇ m or more. Since the risk of film peeling tends to increase if the film thickness becomes too thick, the film thickness of the hard film is preferably 5.0 ⁇ m or less, and more preferably 4.0 ⁇ m or less.
- Another film may be further provided on the hard film disposed on the substrate. Even if another film is provided, the effect of the embodiment of the present invention is excellent.
- another film may form the outermost surface.
- another film made of metal, nitride, carbonitride, oxynitride, carbide, boride, or oxide may be provided as the upper layer of the hard coating in the present disclosure. It is preferable to have a protective film made of nitride or carbonitride having excellent heat resistance and wear resistance on the hard film disposed on the substrate, and more preferably to have a protective film made of nitride. preferable.
- the protective film is preferably a hard film having a residual compressive stress excellent in thermal shock resistance.
- a hard film having a high residual compressive stress As a protective film because the hard film is easily peeled off by a heating and cooling cycle.
- the atomic ratio of Ti is 50 atomic% or more (preferably 75 atomic% or more) and the atomic ratio of Si is 1 atomic% or more and 30 atomic% or less (preferably with respect to the total amount of metal (including metalloid) elements.
- a film made of nitride or carbonitride that is 15 atom% or more and 30 atom% or less) is a protective film disposed on a hard film from the viewpoint of being a film type having excellent wear resistance and high residual compressive stress. As preferred.
- the hard film in the present disclosure is preferably the thickest film among the hard film and the other film in the present disclosure. Since the hard film in the present disclosure is formed into the thickest film as the main film, the coated cutting tool is more excellent in durability.
- the coated cutting tool according to the present embodiment may be provided with an intermediate film using metal, nitride, carbonitride, carbide or the like between the base material and the hard film.
- an intermediate film using metal, nitride, carbonitride, carbide or the like between the base material and the hard film.
- the coated cutting tool according to the present embodiment includes a base material.
- the substrate is not particularly limited, and for example, cemented carbide, cermet, ceramics, high speed steel, etc. can be appropriately applied according to cutting conditions.
- the base material is preferably a WC-based cemented carbide.
- WC represents tungsten carbide.
- the coated cutting tool according to the present embodiment exhibits particularly excellent durability when applied to a ball end mill. Unlike a square end mill that processes a workpiece with the outer peripheral edge of the tool, the ball end mill performs processing while the chisel portion is always in contact with the workpiece. Therefore, in the chisel portion of the ball end mill, more excellent heat resistance and wear resistance are required, and it is effective to apply the AlCrSi-based nitride or carbonitride to exhibit superior durability. .
- the coated cutting tool according to the present embodiment is particularly preferable in that the effect of improving the durability is more effectively exhibited when applied to a small-diameter ball end mill having a tool diameter of 4 mm or less.
- the Al, Cr, and Si content ratios and B / A are in a specific range, and the (200) plane or (111) of the face-centered cubic lattice structure is used. As long as the peak intensity due to the surface shows the maximum intensity, it may be produced by any method. Among them, from the viewpoint of stably producing a coated cutting tool having excellent durability, the content ratio (atomic%) of aluminum (Al) is preferably 55% with respect to the total amount of metal (including metalloid) elements. An alloy target having a chromium (Cr) content ratio (atomic%) of 20% to 35% and a silicon (Si) content ratio (atomic%) of 7% to 20%.
- Cr chromium
- Si silicon
- the bias voltage applied to the substrate is ⁇ 220 V or more and ⁇ 60 V or less and the cathode voltage is 22 V or more and 27 V or less, or the bias voltage applied to the substrate is ⁇ 120 V or more and ⁇ 60 V or less.
- a target containing a metal component necessary for film formation is placed on the cathode (cathode), and a vacuum arc discharge is generated between the cathode and the anode (anode), so that the metal component from the surface of the target.
- a vacuum arc discharge is generated between the cathode and the anode (anode), so that the metal component from the surface of the target.
- Is evaporated and ionized and a film is formed by depositing the ionized metal component on the surface of the substrate to which a negative bias voltage is applied.
- the electrons discharged from the cathode by the arc discharge move toward the anode, and the moved electrons collide with the reaction gas such as the supplied nitrogen gas, so that the gas component is ionized and the ionized gas component. Reacts with the target component to form a hard film on the surface of the substrate.
- the electron energy (eV) is proportional to the voltage
- the electron energy is increased by increasing the cathode voltage, and ionization of the reaction gas is further promoted.
- the cathode voltage is adjusted to a certain range
- the atomic ratio (atomic%) of nitrogen contained in the hard film that is, the atomic ratio (atomic%) of the metal (including metalloid) element nitrogen atoms
- the ratio (atomic%) B increases and the durability of the coated cutting tool tends to be improved.
- the cathode voltage is increased, if the absolute value of the bias voltage applied to the substrate decreases, the atomic ratio of nitrogen contained in the hard coating does not exceed a certain level, and the hNp structure AlN present in the microstructure also It tends to be difficult to reduce. Further, when the cathode voltage becomes too high, the load on the apparatus becomes large and the film formation becomes difficult to stabilize. Therefore, it is important to adjust the bias voltage applied to the base material within a certain range.
- the negative bias voltage applied to the substrate and the cathode voltage are balanced in the film forming process for forming a hard film in the present disclosure. It is preferable to carry out a membrane. Specifically, the bias voltage applied to the substrate is set to ⁇ 220V to ⁇ 60V and the cathode voltage is set to 22V to 27V (hereinafter, Condition 1), or the bias voltage applied to the substrate is set to The film is formed under the condition of ⁇ 120V to ⁇ 60V and the cathode voltage is set to 28V to 32V (hereinafter, Condition 2).
- the cathode voltage is adjusted to 22 V or more, so that the atomic ratio (primary%) of nitrogen in the hard coating is increased, the AlN of the hcp structure existing in the microstructure is reduced, and the hard coating has a high resistance to resistance. Abrasion can be imparted.
- the cathode voltage is 27 V or less, not only does the AlN of the hcp structure existing in the microstructure decrease, but the nitrogen atomic ratio of the hard coating increases, the load on the device is reduced, and The film can also be stably formed.
- the cathode voltage in condition 1 is preferably 24V or more and 26V or less.
- the cathode voltage is in the above range, if the bias voltage applied to the base material is larger than -60V (positive side than -60V), the atomic ratio of the metal element even if the cathode voltage is set high It is difficult to increase the atomic ratio of nitrogen with respect to the film, the durability of the coated cutting tool tends to decrease, and film peeling tends to occur. In addition, AlN having an hcp structure present in the microstructure of the hard coating tends to increase. On the other hand, when the bias voltage applied to the base material is smaller than ⁇ 220 V (becomes negative with respect to ⁇ 220 V), the atomic ratio of nitrogen to the atomic ratio of the metal element becomes too high, and the durability of the coated cutting tool is increased.
- the negative bias voltage applied to the substrate is preferably in the range of ⁇ 190 V to ⁇ 70 V, more preferably in the range of ⁇ 150 V to ⁇ 80 V, and more preferably in the range of ⁇ 150 V to ⁇ 100 V.
- the cathode voltage in condition 2 is preferably 30 V or more and 32 V or less.
- the bias voltage applied to the substrate is adjusted to a range that is not too low.
- the bias voltage applied to the substrate is lower than ⁇ 120V (the range on the negative side of ⁇ 120V)
- the atomic ratio of nitrogen with respect to the atomic ratio of the metal element tends to be too high.
- the durability tends to decrease.
- the load on the apparatus increases, and film formation may not be stable.
- the bias voltage is higher than ⁇ 60V (the range on the positive side than ⁇ 60V)
- the durability of the coated cutting tool tends to decrease, and the film tends to peel off.
- AlN having an hcp structure present in the microstructure of the hard coating tends to increase.
- the negative bias voltage applied to the substrate is preferably in the range of ⁇ 100V to ⁇ 70V.
- the coating by the arc ion plating method in the present disclosure can be performed using a general arc ion plating apparatus.
- the composition of the alloy target and the content ratio of the metal element in the hard film coated on the surface of the substrate may differ depending on the film forming conditions. According to the inventor's study, in the range of the cathode voltage and the bias voltage described above, the content of Al and Si in the hard coating is more likely to decrease than the composition of the alloy target, and the content of Cr in the hard coating is It tends to increase more than the composition of the alloy target. Therefore, when the hard coating is coated on the surface of the substrate, the Al content is 55 atomic% to 70 atomic% and the Cr content is 20 atoms with respect to the total amount of metal (including semimetal) elements.
- a hard film is formed by introducing nitrogen gas into the furnace during film formation (preferably under the above condition 1 or 2) and adjusting the gas pressure in the furnace to a range of 3 Pa to 10 Pa. It is preferable to coat.
- the gas pressure in the furnace during film formation is high, the atomic ratio of nitrogen with respect to the atomic ratio of metal elements in the hard film to be formed tends to be high.
- the gas pressure in the furnace is preferably 3 Pa to 7 Pa.
- the hard film of the coated cutting tool tends to decrease the hardness and toughness of the film and decrease the durability of the coated cutting tool by increasing the amorphous phase present in the microstructure and AlN having an hcp structure.
- a cathode whose magnetic field arrangement is adjusted so that the lines of magnetic force reach from the vicinity of the center of the alloy target to the vicinity of the base material.
- the crystallinity of the film is further increased, the hardness and toughness of the film are improved, and the amorphous phase present in the microstructure and the AlN of the hcp structure are further reduced.
- the durability of the coated cutting tool can be further improved.
- Example 1 a film forming apparatus using an arc ion plating method was used.
- This film forming apparatus includes a plurality of cathodes (arc evaporation sources), a vacuum vessel, and a substrate rotation mechanism.
- cathode one cathode (hereinafter referred to as “C1”) in which a coil magnet is disposed on the outer periphery of the target, and permanent magnets are disposed on the back surface and the outer periphery of the target, and the magnetic flux density in the direction perpendicular to the target surface is set.
- C2 cathode having a vertical magnetic flux density of 14 mT in the vicinity of the center of the target.
- a metal Ti target Ti target
- an AlCrSi alloy target hereinafter referred to as an AlCrSi target
- the inside of the vacuum vessel is evacuated by a vacuum pump, and gas is introduced from the supply port.
- a bias power source is connected to each substrate installed in the vacuum vessel, and a negative DC bias voltage can be applied to each substrate independently.
- the substrate rotation mechanism includes a planetary, a plate-shaped jig disposed on the planetary, and a pipe-shaped jig disposed on the plate-shaped jig, and the planetary has a speed of 3 revolutions per minute. Now, the plate-shaped jig and the pipe-shaped jig each rotate and revolve.
- Each substrate was fixed to a pipe-shaped jig in a vacuum vessel, and the following process was performed before film formation.
- the inside of the vacuum vessel was evacuated to 8 ⁇ 10 ⁇ 3 Pa or less.
- the substrate was heated to a temperature of 500 ° C. by a heater installed in the vacuum vessel, and evacuated.
- the set temperature of the base material was 500 ° C.
- the pressure in the vacuum vessel was 8 ⁇ 10 ⁇ 3 Pa or less.
- argon (Ar) gas was introduced into the vacuum vessel, and the pressure in the vacuum vessel was set to 0.67 Pa.
- a current of 20 A was supplied to the filament electrode, a bias voltage of ⁇ 200 V was applied to the substrate, and Ar bombardment was performed for 4 minutes.
- ⁇ Ti bombardment process> Thereafter, vacuum evacuation was performed so that the pressure in the vacuum vessel was 8 ⁇ 10 ⁇ 3 Pa or less. Subsequently, a bias voltage of ⁇ 800 V was applied to the substrate, an arc current of 150 A was supplied to C1, and Ti bombarding was performed for 3 minutes.
- Table 1 shows the film forming conditions of the hard coatings of the obtained coated samples 1 to 13.
- the AlCrSi target in Table 1 was used with an elemental composition in which the total atomic ratio (atomic%) of Al, Cr, and Si was 99.9% or more.
- ⁇ Evaluation of coated sample> (1) Coating composition Using an electron probe microanalyzer (model number: JXA-8500F, manufactured by JEOL Ltd.), the element of the hard coating of each coating sample by the attached wavelength dispersion electron probe microanalysis (WDS-EPMA) A ball end mill, which is a base material for evaluating physical properties, was processed under the following conditions, and measured at five points with an analysis depth of about 1 ⁇ m in the processed cross section, and obtained from an average value of the measured values. ⁇ Measurement conditions> ⁇ Acceleration voltage: 10 kV ⁇ Irradiation current: 5 ⁇ 10 ⁇ 8 A ⁇ Intake time: 10 seconds ⁇ Analysis area diameter: 1 ⁇ m
- Nanoindentation hardness Using a nanoindentation device (model number: ultra-fine indentation hardness tester ENT-1100a, manufactured by Elionix Co., Ltd.), the hardness and elastic modulus of the hard film of each coated sample are as follows. It was measured. Specifically, the ball end mill, which is a substrate for evaluating physical properties, is tilted 5 degrees, and after mirror polishing, the indentation depth is maintained within 1/10 or less of the thickness of the hard coating within the polishing surface of the hard coating. The maximum depth was defined as nanoindentation hardness. The indentation depth was measured by the following method.
- the terminal is pushed in from the surface of the hard coating under the measurement conditions of an indentation load of 49 mN, a maximum load holding time of 1 second, and a removal speed after loading of 0.49 mN / second, and the indentation depth is 1/10 or less of the thickness of the hard coating.
- the maximum depth maintained was measured.
- Ten measurements were performed on each coated sample. For each coated sample, two points from the larger value side and two points from the smaller value side were removed, and the average value of the indentation depth at 6 points was determined. All the coated samples had a nanoindentation hardness of 40 GPa or more and 50 GPa or less.
- FIG. 1 shows an SEM photograph (40,000 times) showing a processed cross section of Example 1 of the present invention.
- the hard coating in the coated sample 1 of the present invention example in which the Si content was optimized was in a structure form in which no clear columnar particles were confirmed.
- the coated samples 2 to 5 of the examples of the present invention also had a structure in which no clear columnar particles were confirmed.
- the hard film in the coated sample 13 of Comparative Example 8 having a low Si content had a textured form in which coarse and clear columnar particles were confirmed.
- the hard coatings in the coated samples 6 to 12 of Comparative Examples 1 to 7 containing a certain amount of Si had a structure in which no clear columnar particles were confirmed.
- Cutting test A cutting test was performed using each of the prepared coated samples (coated cutting tools). Table 2 shows the analysis results and the cutting test results.
- the cutting conditions are as follows. ⁇ Cutting conditions> ⁇ Processing method: Wet processing ⁇ Tool: 2-flute carbide ball end mill ⁇ Model number: EPDBE2010-6, ball radius 0.5mm, neck length 6mm ⁇ Cutting method: Bottom cutting ⁇ Work material: HPM38 (52HRC) (manufactured by Hitachi Metals, Ltd.) ⁇ Incision: 0.04mm in the axial direction, 0.04mm in the radial direction ⁇ Cutting speed: 78.5 m / min ⁇ Single-blade feed amount: 0.0189 mm / blade ⁇ Cutting oil: Pressurized supply of water-soluble emulsion ⁇ Cutting distance: 60 m ⁇ Evaluation method: After cutting, the coated sample is observed at a magnification of 150 times using a scanning electron microscope, the width of the coated sample and the work material is rubbed, and the portion with the largest rubbed width
- Each of the formed hard coatings has an elemental composition including Al, Cr, Si, and N having atomic ratios shown in Table 2, about 1 atomic% of oxygen as an inevitable element, and about 1 atomic% of carbon. It was.
- the coated samples 1 to 5 of the examples of the present invention showed a damage form stable against wear, and the maximum wear width tended to be suppressed.
- the ratio of nitrogen to metal element (B / A) was smaller than 1.03, and the maximum wear width was larger than that of the coated sample of the present invention.
- the ratio of nitrogen to metal element (B / A) is larger than 1.07, the residual stress of the hard film becomes too high, and the film causes self-destruction.
- the maximum wear width was larger than that of the coated sample of the example of the present invention. Since the coated sample 13 of Comparative Example 8 contained less Si in the hard film, the columnar particles of the hard film became coarse, and the maximum wear width was larger than that of the coated sample of the present invention.
- Example 2 In Example 1, a coated sample was prepared and evaluated in the same manner as in Example 1 except that the hard film was coated by changing the cathode voltage and the bias voltage applied to the substrate in the film forming step. The same material as in Example 1 was used as the base material, and each process up to the Ar bombard process in Example 1 was the same as in Example 1.
- the gas pressure in the furnace was set to 5 Pa.
- the bias voltage applied to the substrate and the cathode voltage of C2 on which the AlCrSi target is installed are changed as shown in Table 3 below, and nitride or carbonitride is coated on the surface of the substrate by the arc ion plating method.
- a hard film having a thickness of about 2.0 ⁇ m was formed on the substrate.
- the set temperature of the base material during film formation was set to 520 ° C.
- the substrate was cooled to about 250 ° C. or less, and taken out of the vacuum vessel to obtain a coated sample.
- Table 3 shows the film forming conditions of the hard coating of the obtained coated samples 20 to 35.
- the AlCrSi target in Table 3 includes Al, Cr, and Si as the elemental composition, and in the present invention example 26, the total ratio of Nb further includes 99.9 atomic% or more of the total amount of metal (including metalloid) elements. Was used.
- Example 2 For each coated sample, the same evaluation as in Example 1 was performed. As in Example 1, the elastic coefficient of the hard film of each coated sample was measured using a nanoindentation device (model number: ultra-fine indentation hardness tester ENT-1100a, manufactured by Elionix Co., Ltd.). The ball end mill, which is a material, was tilted by 5 degrees, and after mirror polishing, the indentation depth was determined as the maximum elastic modulus that was maintained at 1/10 or less of the thickness of the hard coating. The method for measuring the indentation depth is as described above.
- Each of the formed hard films is composed of Al, Cr, Si, and N (further Nb in the film sample 26) having the atomic ratios shown in Table 4, oxygen of about 1 atomic% as an inevitable element, and carbon of about 1 atomic%.
- the coated samples 20 to 26 of the present invention example showed a stable damage form against wear, and the maximum wear width tended to be suppressed.
- the hard coating in the coated sample of the present invention example was confirmed to have a tissue form in which no clear columnar particles were confirmed by cross-sectional observation (40,000 times) using a scanning electron microscope. Since the hard film in the coated sample of the present invention has few large crystal grain boundaries that are the starting points of film destruction, it is presumed that the film showed a damage form that was stable against wear without sudden film peeling. .
- the coated sample 26 of the present invention is an example containing Nb (group 5a element of the periodic table) as a metal element other than Al, Cr and Si.
- the Al, Cr, and Si content ratios and B / A are in a specific range, and the peak intensity due to the (200) plane or (111) plane of the face-centered cubic lattice structure is maximum. As long as the strength is exhibited, it was confirmed that even a composition containing a metal element other than Al, Cr, and Si exhibits excellent durability.
- the cathode voltage was increased to 32V and the negative bias voltage applied to the substrate was set to -200V to -150V, so that the hard coating contained excessive nitrogen and the metal
- the ratio of nitrogen to element (B / A) was greater than 1.07.
- the coated samples 27 and 28 of Comparative Examples 20 and 21 had a structure similar to that of the coated sample of the present invention in cross-sectional observation (40,000 times) using a scanning electron microscope.
- the residual stress of the film became too high, the film was liable to self-destruct, and the maximum wear width tended to be larger than that of the examples of the present invention.
- the coated samples 29 to 34 of Comparative Examples 22 to 27 had the same structure morphology as that of the coated sample of the present invention in cross-sectional observation (40,000 times) with a scanning electron microscope.
- the nitrogen ratio (B / A) was smaller than 1.03, and did not show a stable damage form against abrasion as in the coated sample of the present invention example, and large film peeling occurred.
- the ratio of nitrogen to metal element (B / A) is in the same range as that of the coated sample of the present invention example, but since the Si content is small, the columnar particles become coarse, The maximum wear width was larger than the coated sample of the inventive example.
- FIG. 2 is an example of a cross-sectional observation photograph (500,000 times) of the hard film in the coated sample 23 of the example of the present invention using a transmission electron microscope.
- FIG. 3 is an example of a cross-sectional observation photograph (500,000 times) of the hard film in the coated sample 33 of Comparative Example 26 using a transmission electron microscope.
- the portion that appears relatively dark is a portion having a relatively large amount of Si in the crystal structure.
- the portion that appears relatively white is a portion having a relatively small amount of Si in the crystal structure.
- the microstructure of the hard coating in the coated sample of the present invention example has a crystal phase having a relatively large amount of Si dispersed in a crystal phase having a relatively small amount of Si in the crystal structure. The organization form is shown.
- the microstructure of the hard coating in the coated sample 23 of the present invention example has a crystal phase with a relatively small amount of Si and a crystal phase with a relatively large amount of Si in the crystal structure. It was confirmed.
- the hard film in the coated sample of the example of the present invention a relatively dark crystal phase (crystal phase with a relatively large amount of Si) having an equivalent circle diameter of 20 nm to 100 nm was dispersed.
- the hard film in the coated sample 33 of Comparative Example 26 had a finer crystal phase (crystal phase with a relatively large amount of Si) that appeared darker than the coated sample of the present invention.
- the hard film in the coated sample 23 of the present invention example and the coated sample 33 of the comparative example 26 had substantially the same film composition, they showed different microstructures.
- AlN having an hcp structure was evaluated for the hard coating in the coated sample of the present invention and the coated sample of the comparative example.
- the hard film is processed, and in the processed cross section of the hard film, each of the limited-field diffraction pattern on the substrate side and the limited-field diffraction pattern on the surface side has an acceleration voltage of 120 V, a limited visual field region of 750 nm, and a camera length. It calculated
- FIG. 4 is an intensity profile of the limited field diffraction pattern obtained by converting the luminance of the limited field diffraction pattern of the hard film in the coated sample of Example 23 of the present invention.
- the horizontal axis represents the distance (radius r) from the (000) plane spot center
- the vertical axis represents the integrated intensity (arbitrary unit) for one circle at each radius r.
- an arrow 1 is a peak due to the (010) plane of AlN having the hcp structure, and is the maximum intensity of AlN having the hcp structure.
- Arrow 2 is a peak due to the (011) plane of AlN having the hcp structure, the (111) plane of AlN having the fcc structure, and the (111) plane of CrN.
- An arrow 3 is a peak due to the (200) plane of AlN and the (200) plane of CrN having an fcc structure.
- the arrow 4 is a peak due to the (110) plane of AlN having an hcp structure.
- Arrows 5 are peaks caused by the (220) plane of AlN and the (220) plane of CrN having an fcc structure.
- Ih represents the peak intensity due to the (010) plane of AlN having a hexagonal close-packed structure.
- Is is a (111) plane of AlN, (111) plane of CrN, (200) plane of AlN, (200) plane of CrN, (220) plane of AlN, and CrN having a face-centered cubic lattice structure.
- the hard film in the coated sample 23 had a value of Ih ⁇ 100 / Is on the substrate side and a value of Ih ⁇ 100 / Is on the surface side in the processed cross section of the hard film of 17.
- the hard film in the coated sample 33 of Comparative Example 26 has a higher peak intensity of AlN having an hcp structure than the coated sample of the present invention, and the Ih ⁇ 100 / on the substrate side in the processed cross section of the hard film.
- Example 2 in any of the hard coatings in the coated sample of the present invention and the coated sample of the comparative example, no peak intensity due to AlN having an hcp structure has been confirmed by X-ray diffraction. As described above, in order to quantitatively evaluate the hNp structure AlN existing at the micro level that cannot be confirmed by X-ray diffraction, it is effective to apply the intensity profile obtained from the limited field diffraction pattern. All of the hard coatings in the coated samples 20 to 26 of the example of the present invention satisfied the relationship of Ih ⁇ 100 / Is ⁇ 25.
- the cathode voltage was set as high as 32 V, and the negative bias voltage applied to the substrate was set to ⁇ 200 V to ⁇ 100 V. Therefore, Ih ⁇ 100 The relationship / Is ⁇ 25 was satisfied.
- the negative bias voltage applied to the base material was set to ⁇ 50 V, so the value of Ih ⁇ 100 / Is was larger than 25.
- the cathode voltage was as low as 21 V, so the value of Ih ⁇ 100 / Is was larger than 25.
- the coated sample 31 of Comparative Example 24 in which the bias voltage applied to the substrate was ⁇ 50 V showed the largest value of Ih ⁇ 100 / Is.
- Example 3 Ti 75 Si 25 N having a thickness of about 1.0 ⁇ m (the numerical value is an atomic ratio (atomic%)) is used as a hard coating protective film in the coated sample 23 of the present invention and the coated sample 33 of Comparative Example 26.
- a coated sample of Invention Example 30 and a coated sample of Comparative Example 30 were prepared. About each produced coated sample (coated cutting tool), the cutting test was done on the cutting conditions shown below. Table 5 shows the cutting test results. Details of the cutting conditions are as follows.
- the coated sample of Inventive Example 30 provided with a TiSiN film as a protective film having a composition different from that of the hard film showed a stable damage form against wear and showed excellent durability.
- the ratio of the nitrogen to metal element (B / A) of the coated sample of Comparative Example 30 is smaller than 1.03, even if a TiSiN film is provided as a protective film, the coated sample of the present invention example Thus, large film peeling occurred without showing a stable form of damage against wear.
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Abstract
Description
また、AlとCrを主体とする窒化物又は炭窒化物を被覆する際の成膜条件について、様々な条件が検討されている。例えば、AlとCrを主体とする窒化物を被覆する際にパルスバイアス電圧を印加することが示されている(特開2010-12564号公報、特開2010-284787号公報参照)。
本発明の第1の態様は、
<1> 基材と、前記基材の表面に配置された硬質皮膜と、を有し、
前記硬質皮膜は、金属(半金属を含む)元素の総量に対して、アルミニウム(Al)の含有比率が50原子%以上68原子%以下であり、クロム(Cr)の含有比率が20原子%以上46原子%以下であり、ケイ素(Si)の含有比率が4原子%以上15原子%以下である窒化物又は炭窒化物からなり、かつ、金属(半金属を含む)元素、窒素、酸素および炭素の合計を100原子%とした場合の金属(半金属を含む)元素の原子比率(原子%)Aと窒素の原子比率(原子%)Bとが1.03≦B/A≦1.07の関係を満たし、
X線回折パターンまたは透過型電子顕微鏡の制限視野回折パターンから求められる強度プロファイルにおいて、面心立方格子構造の(200)面または(111)面に起因するピーク強度が最大強度を示す、被覆切削工具である。
硬質皮膜の上に配される保護皮膜は、金属(半金属を含む)元素の総量に対して、Tiの含有比率(原子%)が50%以上であり、かつ、Siの含有比率が1%以上30%以下である窒化物又は炭窒化物からなる膜であることが好ましい。
<6> 金属(半金属を含む)元素の総量に対して、アルミニウム(Al)の含有比率(原子%)が55%以上70%以下であり、クロム(Cr)の含有比率(原子%)が20%以上35%以下であり、ケイ素(Si)の含有比率(原子%)が7%以上20%以下である合金ターゲットをカソードに設置し、基材に印加するバイアス電圧が-220V以上-60V以下、かつ、カソード電圧が22V以上27V以下である条件、または、基材に印加するバイアス電圧が-120V以上-60V以下、かつ、カソード電圧が28V以上32V以下である条件にて、アークイオンプレーティング法により、窒化物又は炭窒化物を基材の表面に被覆することで、基材の表面に硬質皮膜を形成する工程を有する、被覆切削工具の製造方法である。
また、本発明の一実施形態によれば、耐久性に優れた被覆切削工具を安定的に製造することができる被覆切削工具の製造方法が提供される。
なお、本明細書において、「X線回折パターン」は、X線回折装置(株式会社リガク製、RINT2000;縦型ゴニオメーターおよび固定モノクロメーターを使用)を用いて測定された回折ピーク曲線のことを指す。
また、「制限視野回折パターン」は、制限視野絞りを使って特定の領域からの電子線だけを取り出した際の、透過型電子顕微鏡による回折パターンのことを指す。
本発明の実施形態に係る被覆切削工具は、基材と、基材の表面に配置された硬質皮膜と、を有し、必要に応じて、硬質皮膜を保護する保護皮膜、または基材と硬質皮膜との間に配置される中間皮膜、等の他の膜が付与されていてもよい。
本開示における硬質皮膜は、金属(半金属を含む)元素の総量に対して、アルミニウム(Al)の含有比率が50原子%以上68原子%以下であり、Crの含有比率が20原子%以上46原子%以下であり、ケイ素(Si)の含有比率が4原子%以上15原子%以下である窒化物又は炭窒化物からなり、かつ、金属(半金属を含む)元素、窒素、酸素および炭素の合計を100原子%とした場合の金属(半金属を含む)元素の原子比率(原子%)Aと窒素の原子比率(原子%)Bとが1.03≦B/A≦1.07の関係を満たし、かつ、X線回折パターンまたは透過型電子顕微鏡の制限視野回折パターンから求められる強度プロファイルにおいて、面心立方格子構造の(200)面または(111)面に起因するピーク強度が最大強度を示す。
そして、一定量のSi元素を含有した皮膜組織を微細化したAlとCrが主元素の窒化物又は炭窒化物からなる被覆切削工具が優れた耐久性を発揮するには、金属(半金属を含む)元素の総量に対して、窒素の原子比率が一定範囲に制御されていることが重要であるとの知見を得た。
本発明に係る実施形態は、上記のように確認された事象および得られた知見に基づいて達成されたものである。
Alは、耐熱性を付与する元素であり、金属(半金属を含む)元素の総量に対して、Al以外の元素の含有比率(原子%)が最も多くなると耐熱性が低下する。硬質皮膜に優れた耐熱性を付与する観点から、金属(半金属を含む)元素の総量に対して、Alの含有比率(原子%)を50%以上とする。より好ましくは、Alの含有比率(原子%)は、金属(半金属を含む)元素の総量に対して55%以上である。
本開示における硬質皮膜は、金属(半金属を含む)元素の総量に対して、20原子%以上46原子%以下のCrを含有する。Crの含有比率が上記範囲であると、硬質皮膜の耐摩耗性と耐熱性がより優れたものとなる。硬質皮膜中におけるCrの含有比率(原子%)が少なくなり過ぎると、耐摩耗性が低下するとともに、ミクロレベルで存在するhcp構造のAlNが多くなり、被覆切削工具の耐久性が低下する。また、Crの含有比率(原子%)が多くなり過ぎると、硬質皮膜の耐熱性が低下する傾向にある。
Crの含有比率(原子%)としては、硬質皮膜の耐摩耗性および耐熱性をともに更に向上させる観点から、金属(半金属を含む)元素の総量に対して、30原子%以上が好ましく、35原子%以上がより好ましい。更に、Crの含有比率は、40原子%以下の範囲が好ましい。
本開示における硬質皮膜において、ケイ素(Si)は、皮膜組織を微細化するために重要な元素である。本開示における硬質皮膜は、ケイ素(Si)を、金属(半金属を含む)元素の総量に対して4原子%以上15原子%以下の範囲とする。Siの含有量が少ないと、AlとCrを主元素として含有する窒化物又は炭窒化物は、硬質皮膜の加工断面において、粗大な柱状粒子が明確に観察される組織形態となる。粗大な柱状粒子が明確に観察される組織形態では、高硬度材の切削加工において、工具の損傷が大きくなる傾向にある。一方、一定量のSiを含有しかつAlおよびCrが主元素の窒化物又は炭窒化物は、組織が微細化しており、硬質皮膜の加工断面を観察した場合に、明確な柱状粒子が観察され難くなる。このような組織形態の硬質皮膜は、破壊の起点となる粗大な結晶粒界が少なくなり、工具損傷を抑制することができる。但し、Siの含有量が多くなると、ミクロレベルで存在する非晶質相およびhcp構造のAlNが増加し、被覆切削工具の耐久性が低下し易くなる。
Siの含有比率が4原子%未満であると、柱状粒子が粗大となって耐久性が低下する傾向にある。Siの含有比率が15原子%を超えると、皮膜構造が非晶質となり易くなるため、面心立方格子(fcc;以下、単に「fcc」と略記することがある。)構造を主体とすることが困難となり、耐久性が低下する傾向にある。
中でも、本開示における硬質皮膜は、Siの含有比率(原子%)が5原子%以上であることが好ましく、6原子%以上であることが好ましい。また、Siの含有比率(原子%)は、12原子%以下であることが好ましい。
<測定条件>
・加速電圧:10kV
・照射電流:5×10-8A
・取り込み時間:10秒
・分析領域直径:1μm
硬質皮膜の被験面積が小さい場合には、X線回折による結晶構造の同定が困難な場合がある。このような場合には、透過型電子顕微鏡を用いた制限視野回折パターン等によって結晶構造の同定を行うことができる。本開示における硬質皮膜は、ミクロ組織の一部に非晶質相やhcp構造のAlNを含有する場合がある。本開示における硬質皮膜は、透過型電子顕微鏡を用いた制限視野回折パターンにおいて、hcp構造のAlNに起因する回折パターンが確認されないことが好ましい。
通常、一定量のSiを含有して皮膜組織が微細化したAlおよびCrを主元素とした窒化物又は炭窒化物は、非晶質相およびhcp構造のAlNが増加し易くなり、被覆切削工具に適用しても、優れた耐久性が得られ難い傾向がある。このような状況のもと、一定量のSiを含有して皮膜組織が微細化したAlおよびCrを主元素とした窒化物又は炭窒化物からなる硬質皮膜において、含まれる窒素の原子比率(原子%)を高めることで、硬質皮膜の結晶性および耐熱性がより向上し、被覆切削工具の耐久性が向上することを確認した。
一方、硬質皮膜中における窒素の原子比率(原子%)が大きくなり過ぎると、硬質皮膜の残留圧縮応力が高くなり過ぎ、結果、硬質皮膜が自己破壊を起しやすくなる。
以上の知見をもとに、一定量のSiを含有して皮膜組織が微細化したAlおよびCrを主元素とした窒化物又は炭窒化物について、被覆切削工具に優れた耐久性を付与できる最適な窒素含有比率を検討したところ、硬質皮膜中における金属元素の原子比率(原子%)Aと窒素の原子比率(原子%)Bとが、1.03≦B/A≦1.07の関係を満足する場合に被覆切削工具の耐久性が優れたものとなることを見出した。
B/Aのより好ましい範囲は、1.04≦B/A≦1.07であり、更に好ましい範囲は、1.04≦B/A≦1.05である。
本開示における硬質皮膜がAl、Cr、Si以外の金属元素を含有する場合、周期律表の4族(4a族)、5族(5a族)、および6族(6a族)(Crを除く)並びにホウ素(B)からなる群より選択される1種または2種以上の元素を含有することが好ましい。これらの元素は、硬質皮膜に耐摩耗性又は耐熱性を付与する元素であり、金属(半金属を含む)元素の総量に対して所定の範囲で含有する場合、被覆切削工具の耐久性を著しく低下させることはない。但し、硬質皮膜がAl、CrおよびSi以外の金属元素を含有する場合、硬質皮膜中における含有量が多くなり過ぎると被覆切削工具の耐久性が低下する場合がある。そのため、本開示における硬質皮膜は、周期律表の4族、5族および6族(Crを除く)並びにホウ素(B)からなる群より選択される1種または2種以上の元素を、金属(半金属を含む)元素の総量に対して、15原子%以下の範囲で含有することが好ましい。中でも、周期律表の4族、5族および6族(Crを除く)の金属元素並びにホウ素(B)から選択される元素の含有比率は、同様の理由から、10原子%以下がより好ましく、0原子%であること(含有しないこと)が更に好ましい。
特に、本開示における硬質皮膜としては、AlとCrとSiとNと不可避元素とからなるAlCrSi窒化物、またはAlとCrとSiとNとCと不可避元素とからなるAlCrSi炭窒化物が更に好ましく、特に好ましくはAlとCrとSiとNと不可避元素とからなるAlCrSi窒化物である。AlCrSi窒化物およびAlCrSi炭窒化物は、製造コストの点で有利である。
硬質皮膜のナノインデンテーション硬度は、皮膜組成に加えて、基材に印加する負のバイアス電圧、成膜温度、カソードの平均磁束密度を適切な範囲に制御することにより上記範囲に調節することができ、被覆切削工具により高度の耐久性が付与される。
Ih=hcp構造のAlNの(010)面に起因するピーク強度
Is=fcc構造の、AlNの(111)面、CrNの(111)面、AlNの(200)面、CrNの(200)面、AlNの(220)面、およびCrNの(220)面に起因するピーク強度と、hcp構造の、AlNの(010)面、AlNの(011)面、およびAlNの(110)面に起因するピーク強度と、の合計
上記の関係を評価することで、X線回折によりhcp構造のAlNに起因するピーク強度が確認されない硬質皮膜において、ミクロレベルで含まれるhcp構造のAlNを定量的に評価することができる。
本開示における硬質皮膜は、ミクロ組織に存在するhcp構造のAlNをより少なくして、Ih×100/Is≦25の関係を満たしていることが好ましい。Ih×100/Is≦25の関係を満たすことで、被覆切削工具の耐久性がより優れたものとなる。
更には、本開示における硬質皮膜は、Ih×100/Is≦20の関係を満たしていることが好ましい。
基材の上に配された硬質皮膜の上には、更に、別の膜を設けてもよい。別の膜を有しても、本発明の実施形態における効果は良好に奏される。本実施形態の被覆切削工具においては、AlCrSi系の窒化物又は炭窒化物が最表面を形成する形態以外に、別の膜が最表面を形成する形態でもよい。例えば、本開示における硬質皮膜の上層として、金属、窒化物、炭窒化物、酸窒化物、炭化物、硼化物、または酸化物からなる別膜を設けてもよい。基材の上に配された硬質皮膜の上には、耐熱性と耐摩耗性に優れる窒化物又は炭窒化物からなる保護皮膜を有することが好ましく、窒化物からなる保護皮膜を有することがより好ましい。
本実施形態に係る被覆切削工具は、基材を備えている。
基材は、特に制限されるものではなく、例えば、超硬合金、サーメット、セラミックス、高速度鋼等を、切削条件に合わせて適宜適用することができる。基材は、WC基超硬合金であることが好ましい。特に、硬度が93.0HRA以上95.0HRA以下のWC基超硬合金を基材に適用することで、高硬度鋼の切削加工において優れた耐久性が発揮され易い点で好ましい。WCは、炭化タングステンを表す。
本実施形態に係る被覆切削工具は、特に、工具径が4mm以下である小径のボールエンドミルに適用されることで、耐久性の向上効果がより一層効果的に発揮される点で好ましい。
本実施形態に係る被覆切削工具は、既述のように、Al、CrおよびSiの含有比率およびB/Aが特定の範囲にあり、かつ、面心立方格子構造の(200)面または(111)面に起因するピーク強度が最大強度を示す限り、いずれの方法で作製されてもよい。
中でも、耐久性に優れた被覆切削工具を安定的に製造する観点から、好ましくは、金属(半金属を含む)元素の総量に対して、アルミニウム(Al)の含有比率(原子%)が55%以上70%以下であり、クロム(Cr)の含有比率(原子%)が20%以上35%以下であり、ケイ素(Si)の含有比率(原子%)が7%以上20%以下である合金ターゲットをカソードに設置し、基材に印加するバイアス電圧が-220V以上-60V以下、かつ、カソード電圧が22V以上27V以下である条件、または、基材に印加するバイアス電圧が-120V以上-60V以下、かつ、カソード電圧が28V以上32V以下である条件にて、アークイオンプレーティング法により、窒化物又は炭窒化物を基材の表面に被覆することで、基材の表面に硬質皮膜を形成する工程を有する方法(本発明の一実施形態に係る被覆切削工具の製造方法)によって製造される。
本開示においては、一定量のSiを含有しかつAlおよびCrを主元素とした窒化物又は炭窒化物からなる硬質被覆を形成する場合に、カソード電圧を一定の範囲に調整することで、硬質皮膜のミクロ組織に存在するhcp構造のAlNが減るとともに、硬質皮膜に含まれる窒素の原子比率(原子%)、すなわち金属(半金属を含む)元素の原子比率(原子%)Aに対する窒素の原子比率(原子%)Bが高くなり、被覆切削工具の耐久性が向上する傾向にあることを見出した。
但し、カソード電圧を高めても、基材に印加されるバイアス電圧の絶対値が小さくなると、硬質皮膜に含まれる窒素の原子比率が一定以上にならず、ミクロ組織に存在するhcp構造のAlNも低減し難い傾向がある。また、カソード電圧が高くなり過ぎると、装置への負荷が大きくなり、成膜が安定し難くなる。そのため、基材に印加するバイアス電圧を一定の範囲に調整することも重要となる。
カソード電圧が上記範囲にある場合、基材に印加されるバイアス電圧が-60Vよりも大きくなる(-60Vよりもプラス側になる)と、カソード電圧を高く設定しても、金属元素の原子比率に対する窒素の原子比率を高めることが困難であり、被覆切削工具の耐久性が低下傾向を示し、皮膜剥離を起こしやすい。また、硬質皮膜のミクロ組織に存在するhcp構造のAlNが増加する傾向になる。一方、基材に印加されるバイアス電圧が-220Vよりも小さくなる(-220Vよりもマイナス側になる)と、金属元素の原子比率に対する窒素の原子比率が高くなり過ぎ、被覆切削工具の耐久性が低下傾向を示す。また、装置への負荷が大きくなり、成膜が安定しない場合がある。中でも、基材に印加される負のバイアス電圧としては、-190V以上-70V以下の範囲が好ましく、-150V以上-80V以下の範囲がより好ましく、-150V以上-100V以下の範囲がより好ましい。
カソード電圧が上記のように比較的高い範囲にある場合、基材に印加されるバイアス電圧は低すぎない範囲に調整する。基材に印加されるバイアス電圧が-120Vよりも低い範囲(-120Vよりもマイナス側の範囲)では、金属元素の原子比率に対する窒素の原子比率が高くなり過ぎる傾向がみられ、被覆切削工具の耐久性が低下傾向を示すようになる。また、装置への負荷が大きくなり、成膜が安定しない場合がある。一方、バイアス電圧が-60Vよりも高い範囲(-60Vよりもプラス側の範囲)では、カソード電圧を高く設定しても、金属元素の原子比率に対する窒素の原子比率を高めることが困難であり、被覆切削工具の耐久性が低下傾向を示し、皮膜剥離を起こしやすい。また、硬質皮膜のミクロ組織に存在するhcp構造のAlNが増加する傾向になる。中でも、基材に印加される負のバイアス電圧としては、-100V以上-70V以下の範囲が好ましい。
そのため、硬質皮膜を基板の表面に被覆する場合、金属(半金属を含む)元素の総量に対して、Alの含有比率が55原子%以上70原子%以下であり、Crの含有比率が20原子%以上35原子%以下であり、Siの含有比率が7原子%以上20原子%以下である合金ターゲットをカソードに設置して成膜することが好ましい。上述した組成範囲の合金ターゲットをカソードに用いることで、被覆後の硬質皮膜を目的とする組成範囲に制御し易くなる。
このようなカソードを用いて硬質皮膜を被覆することで、皮膜の結晶性がより高まり、皮膜の硬度と靱性が向上するとともに、ミクロ組織に存在する非晶質相およびhcp構造のAlNがより低減され、被覆切削工具の耐久性をより向上させることができる。
<成膜装置>
成膜には、アークイオンプレーティング法を利用した成膜装置を用いた。この成膜装置は、複数のカソード(アーク蒸発源)、真空容器、および基材回転機構を備えている。カソードとしては、ターゲットの外周にコイル磁石が配備されたカソードを1基(以下、「C1」という。)と、ターゲットの背面および外周に永久磁石が配備され、ターゲット表面に垂直方向の磁束密度を有し、ターゲット中央付近における垂直方向の磁束密度が14mTであるカソードを1基(以下、「C2」という。)と、が搭載されている。
C1には、金属Tiのターゲット(Tiターゲット)を設置した。また、C2には、AlCrSi合金のターゲット(以下、AlCrSiターゲット)を設置した。
以下に示す2種類の基材を準備した。
(1)物性評価用の基材および切削試験用の基材として、下記の超硬合金製の2枚刃ボールエンドミル(日立ツール株式会社製)を準備した。
<2枚刃ボールエンドミルの特性>
・組成:WC(bal.)-Co(8質量%)-Cr(0.5質量%)-VC(0.3質量%)
・WCの平均粒度:0.6μm
・硬度:93.9HRA
・ボール半径:0.5mm
<試験片の特性>
・組成:WC(bal.)-Co(13.5質量%)-Cr(0.5質量%)-TaC(0.3質量%)
・寸法:幅8mm×長さ25mm、厚さ0.7mm
各基材をそれぞれ真空容器内のパイプ状冶具に固定し、成膜前に以下のプロセスを実施した。まず、真空容器内を8×10-3Pa以下に真空排気した。その後、真空容器内に設置したヒーターにより、基材を温度500℃まで加熱し、真空排気を行った。そして、基材の設定温度を500℃とし、真空容器内の圧力を8×10-3Pa以下とした。
その後、真空容器内にアルゴン(Ar)ガスを導入し、真空容器内の圧力を0.67Paとした。次いで、フィラメント電極に20Aの電流を供給し、基材に-200Vのバイアス電圧を印加して、Arボンバードを4分間実施した。
その後、真空容器内の圧力が8×10-3Pa以下になるように真空排気した。続いて、基材に-800Vのバイアス電圧を印加して、C1に150Aのアーク電流を供給してTiボンバード処理を3分間実施した。
Tiボンバード処理後、直ちにC1への電流供給を中断した。そして、真空容器内に窒素ガスを導入して、使用するAlCrSiターゲットごとに、真空容器内のガス圧力と、基材に印加する負のバイアス電圧と、を下記表1に示すように変化させ、C2に150Aの電流を供給することで、アークイオンプレーティング法により窒化物又は炭窒化物を基材の表面に被覆し、基材上に厚み約1.5μmの硬質皮膜を形成した。ここで、成膜時の基材の設定温度は520℃とし、カソード電圧は、下記表1に示すように変化させた。
その後、略250℃以下に基材を冷却し、真空容器から取り出して被覆試料とした。得られた被覆試料1~13の硬質皮膜の成膜条件を表1に示す。
なお、表1中のAlCrSiターゲットには、元素組成としてAlとCrとSiの合計の原子比率(原子%)が99.9%以上であるものを用いた。
(1)被膜組成
電子プローブマイクロアナライザー装置(型番:JXA-8500F、株式会社日本電子製)を用いて、付属の波長分散型電子プローブ微小分析(WDS-EPMA)により各被覆試料の硬質皮膜の元素組成を、以下の条件下、物性評価用の基材であるボールエンドミルを加工し、加工断面において分析深さを略1μmとして5点測定し、測定値の平均値から求めた。
<測定条件>
・加速電圧:10kV
・照射電流:5×10-8A
・取り込み時間:10秒
・分析領域直径:1μm
金属(半金属を含む)元素の原子比率Aに対する窒素の原子比率Bの比(B/A)の値は、金属元素(半金属を含む)と窒素と酸素と炭素との合計を100%として求めた。なお、いずれの被覆試料も、酸素および炭素の前記合計100%中に占める含有比率は、1%程度であった。
硬質皮膜の組成とB/A値とを表2に示す。
X線回折を用い、各被覆試料の硬質皮膜の結晶構造を評価した。具体的には、X線回折装置(株式会社リガク製、RINT2000;縦型ゴニオメーターおよび固定モノクロメーターを使用)を用い、管電圧40kV、管電流300mA、X線源Cukα(λ=0.15418nm)、2θが20°~70°の測定条件で実施した。
結果、硬質皮膜は、fcc構造の(200)面又は(111)面に起因するピーク強度が最大強度を示していることが確認された。この結果を表2に示す。また、いずれの被覆試料も、X線回折においては、hcp構造のAlNに起因するピーク強度は確認されなかった。
ナノインデンテーション装置(型番:超微小押し込み硬さ試験機ENT-1100a、株式会社エリオニクス製)を用い、各被覆試料の硬質皮膜の硬度及び弾性係数を以下の条件で測定した。
具体的には、物性評価用の基材であるボールエンドミルを、5度傾けて、鏡面研磨後、硬質皮膜の研磨面内で押し込み深さが硬質皮膜の厚みの1/10以下に維持される最大深さをナノインデンテーション硬度とした。
押し込み深さは、次の方法で測定した。すなわち、
硬質皮膜の表面から端子を、押込み荷重49mN、最大荷重保持時間1秒、荷重負荷後の除去速度0.49mN/秒の測定条件にて押し込み、押し込み深さが硬質皮膜の厚みの1/10以下に維持される最大深さを測定した。各被覆試料に対して、この測定を10点実施した。各被覆試料ごとに、値の大きい側から2点および値の小さい側から2点を除き、それぞれ6点の押し込み深さの平均値を求めた。
いずれの被覆試料も、ナノインデンテーション硬度は40GPa以上50GPa以下であった。
各被覆試料のうち、物性評価用の基材であるボールエンドミルを加工し、加工断面を透過型電子顕微鏡により観察し、硬質皮膜を分析した。制限視野回折パターンから、本発明例の被覆試料1~5における硬質皮膜は、fcc構造の(200)面又は(111)面に起因するピーク強度が最大強度を示すことを確認した。
また、本発明例の被覆試料1~5における硬質皮膜を、透過型電子顕微鏡(TEM)にて500,000倍に拡大して観察した。この際のTEM写真を確認したところ、結晶構造中、相対的にSi含有量が少ない結晶相と相対的にSi含有量の多い結晶相とを有する組織形態となっていた。
さらに、各被覆試料のうち、物性評価用の基材であるボールエンドミルを加工し、硬質皮膜の加工断面を走査型電子顕微鏡(SEM)により観察した。代表例として、図1に本発明例1の加工断面を表すSEM写真(40,000倍)を示す。
図1に示されるように、Siの含有量を最適化した本発明例の被覆試料1における硬質皮膜は、明確な柱状粒子が確認されない組織形態であることを確認した。また、本発明例の被覆試料2~5も、明確な柱状粒子が確認されない組織形態であった。
一方、Siの含有量が少ない比較例8の被覆試料13における硬質皮膜は、粗大で明確な柱状粒子が確認される組織形態であった。また、一定量のSiを含有した比較例1~7の被覆試料6~12における硬質皮膜は、明確な柱状粒子が確認されない組織形態であった。
作製した各被覆試料(被覆切削工具)を用いて切削試験を行った。表2に分析結果および切削試験結果を示す。なお、切削条件は、以下の通りである。
<切削条件>
・加工方式:湿式加工
・工具:2枚刃超硬ボールエンドミル
・型番:EPDBE2010-6、ボール半径0.5mm、首下長さ6mm
・切削方法:底面切削
・被削材:HPM38(52HRC)(日立金属株式会社製)
・切り込み:軸方向0.04mm、径方向0.04mm
・切削速度:78.5m/min
・一刃送り量:0.0189mm/刃
・切削油:水溶性エマルション加圧供給
・切削距離:60m
・評価方法:切削加工後、走査型電子顕微鏡を用いて倍率150倍で被覆試料を観察し、被覆試料と被削材とが擦過した幅を実測し、そのうちの擦過幅が最も大きい部分を最大摩耗幅として求めた。最大摩耗幅は、値が小さいほど耐久性に優れることを示す。
比較例1~5の被覆試料6~10は、金属元素に対する窒素の比率(B/A)が1.03よりも小さく、本発明例の被覆試料よりも最大摩耗幅が大きくなった。また、比較例6~7の被覆試料11~12は、金属元素に対する窒素の比率(B/A)が1.07よりも大きく、硬質皮膜の残留応力が高くなり過ぎ、皮膜が自己破壊を起しやすくなり、本発明例の被覆試料よりも最大摩耗幅が大きくなった。比較例8の被覆試料13は、硬質皮膜に含まれるSiが少ないため、硬質皮膜の柱状粒子が粗大となり、本発明例の被覆試料よりも最大摩耗幅が大きくなった。
実施例1において、成膜工程におけるカソード電圧と基材に印加するバイアス電圧とを変化させて硬質皮膜を被覆したこと以外は、実施例1と同様にして、被覆試料を作製し、評価した。基材として実施例1と同じものを用い、実施例1におけるArボンバード工程までの各工程は、実施例1と同じとした。
その後、略250℃以下に基材を冷却し、真空容器から取り出して被覆試料とした。得られた被覆試料20~35の硬質皮膜の成膜条件を表3に示す。
なお、表3中のAlCrSiターゲットは、元素組成としてAl、CrおよびSi並びに本発明例26では更にNbの合計比率が、金属(半金属を含む)元素の総量の99.9原子%以上含むものを用いた。
<切削条件>
・加工方式:湿式加工
・工具:2枚刃超硬ボールエンドミル
・型番:EPDBE2010-6、ボール半径0.5mm、首下長さ6mm
・切削方法:底面切削
・被削材:STAVAX(52HRC)(ウッデホルム社製)
・切り込み:軸方向、0.04mm、径方向、0.04mm
・切削速度:78.5m/min
・一刃送り量:0.0189mm/刃
・切削油:水溶性エマルション加圧供給
・切削距離:60m
・評価方法:切削加工後、走査型電子顕微鏡を用いて倍率150倍で被覆試料を観察し、被覆試料と被削材とが擦過した幅を実測し、そのうちの擦過幅が最も大きい部分を最大摩耗幅として求めた。最大摩耗幅は、値が小さいほど耐久性に優れることを示す。
本発明例の被覆試料26は、Al、CrおよびSi以外の金属元素としてNb(周期律表の5a族元素)を含有する一例である。被覆試料26のように、Al、CrおよびSiの含有比率およびB/Aが特定の範囲にあり、かつ、面心立方格子構造の(200)面または(111)面に起因するピーク強度が最大強度を示す限り、Al、CrおよびSi以外の金属元素を含有する組成であっても、優れた耐久性を示すことが確認された。
比較例22~27の被覆試料29~34は、走査型電子顕微鏡による断面観察(40,000倍)では、本発明例の被覆試料と同じような組織形態を有していたが、金属元素に対する窒素の比率(B/A)が1.03よりも小さく、本発明例の被覆試料のように摩耗に対して安定した損傷形態を示さず、大きな皮膜剥離が発生した。
また、比較例28の被覆試料35は、金属元素に対する窒素の比率(B/A)は本発明例の被覆試料と同じ範囲にあるが、Si含有量が少ないため、柱状粒子が粗大となり、本発明例の被覆試料に比べて最大摩耗幅が大きくなった。
このように、本発明例の被覆試料23における硬質皮膜のミクロ組織は、結晶構造中、相対的にSi量が少ない結晶相と、相対的にSi量が多い結晶相と、を有していることを確認した。本発明例の被覆試料における硬質皮膜のミクロ組織では、円相当径が20nm以上100nm以下の相対的に暗く見える結晶相(相対的にSi量が多い結晶相)が分散していた。
一方、比較例26の被覆試料33における硬質皮膜は、相対的に暗く見える結晶相(相対的にSi量が多い結晶相)が本発明例の被覆試料に比べて微細であった。
本発明例の被覆試料23と比較例26の被覆試料33とにおける硬質皮膜は、ほぼ同様の皮膜組成を有するものの、ミクロ組織が異なる組織形態を示した。
具体的には、硬質皮膜を加工し、硬質皮膜の加工断面において、基材側の制限視野回折パターンと表面側の制限視野回折パターンとのそれぞれを、加速電圧120V、制限視野領域φ750nm、カメラ長100cm、入射電子量5.0pA/cm2(蛍光板上)の条件にて求めた。求めた制限視野回折パターンの輝度を変換し、強度プロファイルを求めた。
図4において、矢印1は、hcp構造のAlNの(010)面に起因するピークであり、hcp構造のAlNの最大強度である。矢印2は、hcp構造のAlNの(011)面、並びにfcc構造のAlNの(111)面およびCrNの(111)面に起因するピークである。矢印3は、fcc構造のAlNの(200)面およびCrNの(200)面に起因するピークである。矢印4は、hcp構造のAlNの(110)面に起因するピークである。矢印5は、fcc構造のAlNの(220)面およびCrNの(220)面に起因するピークである。
ここで、Ihは、六方最密充填構造のAlNの(010)面に起因するピーク強度を表す。また、Isは、面心立方格子構造の、AlNの(111)面、CrNの(111)面、AlNの(200)面、CrNの(200)面、AlNの(220)面、およびCrNの(220)面に起因するピーク強度と、六方最密充填構造の、AlNの(010)面、AlNの(011)面、およびAlNの(110)面に起因するピーク強度と、の合計を表す。
結果、被覆試料23における硬質皮膜は、硬質皮膜の加工断面における基材側のIh×100/Isの値、および表面側のIh×100/Isの値はいずれも、17であった。
これに対して、比較例26の被覆試料33における硬質皮膜は、本発明例の被覆試料よりもhcp構造のAlNのピーク強度が大きくなり、硬質皮膜の加工断面における基材側のIh×100/Isの値、および表面側のIh×100/Isの値はいずれも、28であった。
実施例2において、本発明例の被覆試料および比較例の被覆試料における硬質皮膜のいずれも、X線回折ではhcp構造のAlNに起因するピーク強度は確認されていない。
このように、X線回折では確認できないミクロレベルで存在するhcp構造のAlNを定量的に評価するには、制限視野回折パターンから求められる強度プロファイルを適用することが有効である。
本発明例の被覆試料20~26における硬質皮膜は、いずれもIh×100/Is≦25の関係を満たしていた。比較例20、21および28の被覆試料27、28および35における硬質皮膜は、カソード電圧を32Vと高く設定し、基材に印加する負のバイアス電圧を-200V~-100Vとしたため、Ih×100/Is≦25の関係を満たした。一方、比較例22、23の被覆試料29、30における硬質皮膜では、基材に印加する負のバイアス電圧を-50Vとしたため、Ih×100/Isの値は25よりも大きい値を示した。比較例24、25および27の被覆試料31、32および34における硬質皮膜では、カソード電圧が21Vと低いため、Ih×100/Isの値は25よりも大きい値を示した。特に、基材に印加するバイアス電圧を-50Vとした比較例24の被覆試料31は、Ih×100/Isの値が最も大きい値を示した。
実施例2において、本発明例の被覆試料23と比較例26の被覆試料33における硬質皮膜の保護皮膜として、厚み約1.0μmのTi75Si25N(数値は原子比率(原子%))を被覆した本発明例30の被覆試料および比較例30の被覆試料を作製した。作製した各被覆試料(被覆切削工具)について、以下に示す切削条件にて切削試験を行った。表5に切削試験結果を示す。切削条件の詳細は、以下の通りである。
<切削条件>
・加工方式:湿式加工
・工具:2枚刃超硬ボールエンドミル
・型番:EPDBE2010-6、ボール半径0.5mm、首下長さ6mm
・切削方法:底面切削
・被削材:STAVAX(52HRC)(ウッデホルム社製)
・切り込み:軸方向、0.04mm、径方向、0.04mm
・切削速度:78.5m/min
・一刃送り量:0.0189mm/刃
・切削油:水溶性エマルション加圧供給
・切削距離:60m
・評価方法:切削加工後、走査型電子顕微鏡を用いて倍率150倍で被覆試料を観察し、被覆試料と被削材とが擦過した幅を実測し、そのうちの擦過幅が最も大きい部分を最大摩耗幅として求めた。最大摩耗幅は、値が小さいほど耐久性に優れることを示す。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (7)
- 基材と、前記基材の表面に配置された硬質皮膜と、を有し、
前記硬質皮膜は、金属(半金属を含む)元素の総量に対して、アルミニウム(Al)の含有比率が50原子%以上68原子%以下であり、クロム(Cr)の含有比率が20原子%以上46原子%以下であり、ケイ素(Si)の含有比率が4原子%以上15原子%以下である窒化物又は炭窒化物からなり、かつ、金属(半金属を含む)元素、窒素、酸素および炭素の合計を100原子%とした場合の金属(半金属を含む)元素の原子比率(原子%)Aと窒素の原子比率(原子%)Bとが1.03≦B/A≦1.07の関係を満たし、
X線回折パターンまたは透過型電子顕微鏡の制限視野回折パターンから求められる強度プロファイルにおいて、面心立方格子構造の(200)面または(111)面に起因するピーク強度が最大強度を示す、被覆切削工具。 - 前記硬質皮膜は、透過型電子顕微鏡の制限視野回折パターンから求められる強度プロファイルにおいて、六方最密充填構造のAlNの(010)面に起因するピーク強度をIhとし、面心立方格子構造の、AlNの(111)面、CrNの(111)面、AlNの(200)面、CrNの(200)面、AlNの(220)面、およびCrNの(220)面に起因するピーク強度と、六方最密充填構造の、AlNの(010)面、AlNの(011)面、およびAlNの(110)面に起因するピーク強度と、の合計をIsとした場合、Ih×100/Is≦25の関係を満たす請求項1に記載の被覆切削工具。
- 前記硬質皮膜は、周期律表の4族、5族、および6族(Crを除く)の金属元素並びにホウ素(B)からなる群より選択される1種または2種以上の元素の含有比率が、金属(半金属を含む)元素の総量に対して、15原子%以下である請求項1又は請求項2に記載の被覆切削工具。
- 前記基材上の前記硬質皮膜の上に、前記硬質皮膜と組成の異なる窒化物又は炭窒化物からなる保護皮膜を有する請求項1~請求項3のいずれか1項に記載の被覆切削工具。
- 硬質皮膜と組成の異なる窒化物又は炭窒化物からなる前記保護皮膜は、金属(半金属を含む)元素の総量に対して、Tiの含有比率が50原子%以上であり、Siの含有比率が1原子%以上30原子%以下である窒化物又は炭窒化物からなる膜である請求項4に記載の被覆切削工具。
- 前記硬質皮膜は、ナノインデンテーション硬度が40GPa以上55GPa以下である請求項1~請求項5のいずれか1項に記載の被覆切削工具。
- 金属(半金属を含む)元素の総量に対して、アルミニウム(Al)の含有比率が55原子%以上70原子%以下であり、クロム(Cr)の含有比率が20原子%以上35原子%以下であり、ケイ素(Si)の含有比率が7原子%以上20原子%以下である合金ターゲットをカソードに設置し、基材に印加するバイアス電圧が-220V以上-60V以下、かつ、カソード電圧が22V以上27V以下である条件、または、基材に印加するバイアス電圧が-120V以上-60V以下、かつ、カソード電圧が28V以上32V以下である条件にて、アークイオンプレーティング法により、窒化物又は炭窒化物を基材の表面に被覆することで、基材の表面に硬質皮膜を形成する工程を有する、被覆切削工具の製造方法。
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