JP5144850B2 - Hard coating and hard coating tool - Google Patents

Description

  The present invention relates to a hard coating, and more particularly to a hard coating that is excellent in heat resistance, wear resistance, and welding resistance, and that has high adhesion strength and is suitably used for tools, wear-resistant parts, and the like. is there.

Various tools such as cutting tools such as drills, end mills, milling tools, cutting tools, build-up taps, rolling tools, non-cutting tools such as press dies, or friction parts that require wear resistance It has been proposed to improve wear resistance and durability by coating a hard film on the surface of a substrate. Patent Document 1 describes a tool provided with DLC (Diamond Like Carbon) as a hard coating. DLC has a dense amorphous structure and is crystallographically different from diamond, but has a higher hardness than compound coatings such as TiAlN and CrN. Patent Documents 2 and 3 describe the use of carbon nitride as a hard coating and a method for producing the carbon nitride film. Carbon nitride has a low friction coefficient, a smooth surface and high hardness, and provides excellent wear resistance, welding resistance, and heat resistance.
JP 2005-22073 A JP 2002-38269 A JP 2006-69856 A

However, the above DLC is not always satisfactory in terms of heat resistance and wear resistance. For example, dry processing by air blow that does not use any lubricant, or cutting by mist spray that uses a minimum amount of lubricant. In the semi-dry processing in which the dampening is performed, sufficient durability cannot be obtained, and the unbonded hands of C (carbon) are easily bonded to the work material to cause welding, which is particularly unsuitable for iron-based materials. Although it has been proposed to add H (hydrogen) to the C dangling bonds to prevent bonding with the work material, other problems such as a reduction in toughness occur. Carbon nitride, on the other hand, has a structure in which N (nitrogen) is bonded to the dangling bonds of C, which is a problem of the above DLC, and provides excellent welding resistance. There is a problem that sufficient durability cannot always be obtained in a cutting tool or the like.

  The present invention has been made against the background of the above circumstances, and the object thereof is excellent in heat resistance, wear resistance, and welding resistance, and high adhesion strength is obtained. Another object of the present invention is to provide a long-life hard coating that can provide excellent durability.

In order to achieve this object, the first invention is a hard coating provided on the surface of a predetermined substrate, and (a) a DLC layer provided on the surface of the substrate, and (b) a nitrogen content. And a carbon nitride layer provided on the uppermost layer so as to constitute the outer surface, and (c) thickness Ri der range of 0.01 to 3 [mu] m, and characterized by comprising; (d) a carbon nitride layer together a single bond and a double bond of carbon nitride.

  The second invention has a two-layer structure in which the carbon nitride layer is provided directly on the DLC layer in the hard coating of the first invention, and the total film thickness is within a range of 0.01 to 2 μm. It is characterized by being.

  3rd invention is the hard film of 1st invention or 2nd invention, The nanoindentation hardness of the said DLC layer is in the range of 40-50 GPa, The nanoindentation hardness of the said carbon nitride layer is 15-55 GPa It is within the range.

According to a fourth invention, in any one of the hard coating films according to the first to third inventions, the thicknesses of the DLC layer and the carbon nitride layer are both in the range of 0.005 to 1 μm. .

A fifth invention is a hard film-coated tool in which a hard film is provided on the surface of a substrate, and the hard film is any one of the hard films of the first to fourth inventions. .

In the hard coating of the first invention, a DLC layer is provided on the surface of the base material, and a carbon nitride layer having a nitrogen content of 3 to 40 at% is provided in the uppermost layer so as to constitute the outer surface, and Since the entire film thickness is in the range of 0.01 to 3 μm, the uppermost carbon nitride layer provides excellent heat resistance, wear resistance, and welding resistance, while the surface of the substrate is Since a DLC layer is provided, high adhesion strength is obtained, peeling and the like are suppressed, and even when used as a hard film such as a cutting tool, durability is excellent. Thereby, for example, it is suitably used as a hard coating of a hard coating coated tool as in the fifth invention, and improves the welding resistance of processing in an environment where welding is likely to occur (such as in a vacuum), and also against an iron-based material. While machining is possible and an excellent tool life is obtained, dry machining and semi-dry machining are possible for non-ferrous materials such as aluminum alloys.
In addition, since the carbon nitride layer is composed of both single bond and double bond carbon nitride, the hardness of the carbon nitride layer is adjusted by changing the film formation conditions and changing their ratio. can do. That is, single bond carbon nitride is harder than double bond carbon nitride, so if the film formation conditions are set so that the proportion of the single bond carbon nitride is higher, the hardness of the entire carbon nitride layer On the other hand, toughness can be improved by increasing the proportion of double-bonded carbon nitride. Carbon nitride has a triple bond, but it only serves as a terminal end of the bond and is not related to mechanical properties.

  In addition, since both the DLC layer and the carbon nitride layer can be easily adjusted in hardness by changing the film formation conditions, the hardness, toughness, etc. according to the object or purpose of providing the hard coating The film characteristics can be set as appropriate. If the nanoindentation hardness of the DLC layer is in the range of 40 to 50 GPa and the nanoindentation hardness of the carbon nitride layer is in the range of 15 to 55 GPa as in the third invention, excellent wear resistance can be obtained. It is obtained and is suitably applied to a hard film of a cutting tool.

  Since the hard film of the second invention has a two-layer structure in which a carbon nitride layer is provided directly on the DLC layer, and the entire film thickness is in the range of 0.01 to 2 μm, While exfoliation etc. are suppressed and the outstanding durability is acquired, a structure is simple and it is comprised at low cost.

In the fourth invention, since the thickness of the DLC layer and the carbon nitride layer are both in the range of 0.005 to 1 μm, the carbon nitride layer is improved while improving the adhesion strength of the carbon nitride layer in the presence of the DLC layer. As a result, excellent heat resistance, wear resistance, and welding resistance can be obtained.

Hard coating coated tool of the fifth invention, because it is covered by any of the hard coating of the first invention to the fourth invention, substantially first invention to fourth invention and same effects are obtained.

  The present invention is suitably applied to various hard coating coated tools such as rotary cutting tools such as drills and milling cutters, non-rotating cutting tools such as cutting tools, or non-cutting tools such as raised taps, rolling tools, and press dies. However, it can be applied to hard coatings of various members that require wear resistance and durability, such as bearing members, other than such processing tools.

  The DLC layer and the carbon nitride layer can be suitably formed by PVD methods such as arc ion plating, ion beam assisted deposition, and sputtering, but other film formation methods can also be employed.

  The nitrogen content of the carbon nitride layer can be adjusted by changing the film formation conditions.For example, in the arc ion plating method, it can be adjusted by controlling the nitrogen gas flow rate. In the case of the ion beam assisted deposition method, the plasma concentration can be adjusted. Can be adjusted by controlling. If the nitrogen content is less than 3 at%, the effect of improving the welding resistance by binding nitrogen to C (carbon) dangling bonds cannot be sufficiently obtained. On the other hand, if the nitrogen content exceeds 40 at%, single bond carbon nitride is not obtained. Therefore, it is desirable to set within a range of 3 to 40 at%, and particularly within a range of 5 to 35 at%.

  If the total film thickness is less than 0.01 μm, the function as a hard film cannot be obtained sufficiently, but if it exceeds 3 μm, it tends to peel or chip, so it is set within the range of 0.01 to 3 μm. It is desirable to do. In the case of a two-layer structure in which a carbon nitride layer is provided directly on the DLC layer as in the second invention, a range of 0.01 to 2 μm is appropriate.

  In the second invention, the two-layer structure of the DLC layer and the carbon nitride layer is used. However, the nitrogen content is increased until the multilayer structure is formed by repeatedly stacking them, or until the carbon nitride layer having a predetermined nitrogen content is reached from the DLC layer. Various modes are possible, such as providing a graded layer that increases continuously. That is, in carrying out the first invention, it is sufficient to provide a DLC layer at least at the interface with the base material and a carbon nitride layer as the uppermost layer. It is also possible to intervene the layer (s).

  In the third invention, the nanoindentation hardness of the DLC layer is in the range of 40 to 50 GPa, and the nanoindentation hardness of the carbon nitride layer is in the range of 15 to 55 GPa, which is suitably applied to the hard coating of the cutting tool. However, the hardness thereof can be appropriately changed according to the object to be provided with the hard coating, the purpose, and the like.

In the present invention , the carbon nitride layer is configured to include both single bond (sp3 bond) and double bond (sp2 bond) carbon nitride, but it may also include triple bond carbon nitride. . Such a carbon nitride layer, Ru amorphous der not having a regular crystal structure.

In the fourth invention, the thicknesses of the DLC layer and the carbon nitride layer are both in the range of 0.005 to 1 μm. However, when the other inventions are implemented, the thickness of the DLC layer and the carbon nitride layer is 0.005 μm. Or less than 1 μm.

As the base material of the hard film-coated tool of the fifth invention, cemented carbide or high-speed tool steel is preferably used. Cermet, ceramics, polycrystalline diamond, single crystal diamond, polycrystalline CBN, single crystal CBN, etc. Various tool materials can be employed.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a view showing a drill 10 which is an example of a hard film coated tool of the present invention, where (a) is a front view seen from a direction perpendicular to the axis O, and (b) is provided with a cutting edge 12. It is an enlarged bottom view seen from the front end side. The drill 10 is a two-blade twist drill, and is integrally provided with a shank 14 and a body 16 in the axial direction. The body 16 is formed with a pair of grooves 18 twisted clockwise around the axis O. . A pair of cutting edges 12 are provided at the tip of the body 16 corresponding to the grooves 18, and holes are cut by the cutting edges 12 by being driven to rotate clockwise around the axis O as viewed from the shank 14 side. While processing, chips are discharged through the groove 18 to the shank 14 side.

  FIG. 1C is an enlarged sectional view of the vicinity of the surface of the body 16, and the hard coating 24 is coated on the surface of the tool base 22 made of cemented carbide. The hard coating 24 has a two-layer structure including a DLC layer 26 provided on the surface of the tool base 22 and a CN (carbon nitride) layer 28 provided on the DLC layer 26. The outer surface is configured. The CN layer 28 is configured to include both single bond (sp3) and double bond (sp2) CN in a nitrogen content range of 3 to 40 at%, and its nanoindentation hardness is 15 to It is within the range of 55 GPa. The nanoindentation hardness of the DLC layer 26 is in the range of 40 to 50 GPa. Further, the entire film thickness D of the hard coating 24 is in the range of 0.01 to 2 μm, and the film thickness D1 of the DLC layer 26 alone and the film thickness D2 of the CN layer 28 alone are both in the range of 0.005 to 1 μm. Is within. In addition, the hatched area in FIG. 1A represents the coating range of the hard coating 24.

  2A is a schematic diagram of the bonding structure of the CN layer 28. C represents a carbon atom, N represents a nitrogen atom, and is represented by a single bond (sp3) shown in (b) and (c). It is an amorphous structure in which double bonds (sp2) are randomly distributed. FIG. 3 shows an example of the Raman spectrum of the CN layer 28, where “D-peak” is due to single-bonded CN and “G-peak” is due to double-bonded CN, and has both peaks. This indicates that both single bonds and double bonds are included. The film characteristics such as hardness can be controlled by the ratio of the bonds. For example, if the ratio of the single bond of high hardness is increased, the hardness of the CN layer 28 is increased and the double bond is increased. If the ratio is increased, the toughness of the CN layer 28 is improved.

In addition, a test piece coated with three types of hard coatings of CN (single bond + double bond), DLC, and TiN was prepared, and friction was performed under the following test conditions using the pin-on-disk test apparatus shown in FIG. When the abrasion test was performed, the results shown in FIGS. 5 and 6 were obtained. The CN in this case is substantially the same as the No. 11 CN layer 28 in the product of the present invention in FIG. 8, the nitrogen content is about 20 at%, the nanoindentation hardness is about 29 GPa, and the base material of the test piece (carbide) Alloy) directly coated on.
(Test conditions)
-Partner material: SUS304 (stainless steel)
・ Load: 0.5N
・ Linear speed: 25mm / s
-Time: 500 seconds-Test environment: Air-Room temperature: 25 ° C
・ Humidity: 60%

  FIG. 5 is a result of obtaining the friction coefficient from the above test. CN is about 0.09, DLC is about 0.08, TiN is about 0.27, and CN has a very small friction coefficient like DLC. Since the values of DLC and CN are very close, these graphs are substantially overlapped in FIG. FIG. 6 is a photograph showing wear marks at the tips of CN and DLC test pieces, where (a) shows wear marks generated on CN and (b) shows wear marks generated on DLC. Welding of the counterpart material was observed in each. The ratio of the amount of Fe deposited on CN and the amount of Fe deposited on DLC is about 3:10, and CN has much better welding resistance to iron than DLC.

On the other hand, the DLC layer 26 and the CN layer 28 are suitably formed by a PVD method such as an arc ion plating method, an ion beam assisted deposition method, or a sputtering method. FIG. 7 is a schematic configuration diagram (schematic diagram) for explaining the arc ion plating apparatus 30. The tool base 22 on which a plurality of workpieces, that is, the cutting edges 12, grooves 18 and the like before coating the hard coating 24 is formed. A workpiece holder 32 that is held, a rotating device 34 that rotationally drives the workpiece holder 32 around a substantially vertical rotation center, a bias power source 36 that applies a negative bias voltage to the tool base 22, and a tool base 22 A chamber 38 serving as a processing container, a reaction gas supply device 40 for supplying a predetermined reaction gas into the chamber 38, an exhaust device 42 for discharging the gas in the chamber 38 with a vacuum pump or the like, and reducing the pressure. A first arc power supply 44, a second arc power supply 46, and the like are provided. The workpiece holder 32 has a cylindrical shape or a polygonal column shape centered on the rotation center, and holds a large number of tool bases 22 in a radial manner with the tip projecting outward substantially horizontally. The reactive gas supply device 40 includes a tank of argon gas (Ar) and nitrogen gas (N ₂ ). When the DLC layer 26 is formed, only the argon gas is supplied, and when the CN layer 28 is formed, argon gas (Ar ₂ ) is supplied. Gas and nitrogen gas are supplied at a predetermined ratio.

  The first arc power supply 44 and the second arc power supply 46 both conduct a predetermined arc current between the anodes 50 and 54 with the first evaporation source 48 and the second evaporation source 52 made of carbon (C) as cathodes. Then, carbon is evaporated from the evaporation sources 48 and 52 by arc discharge, and the evaporated carbon becomes positive ions and is applied to the tool base 22 to which a negative (−) bias voltage is applied. Be attached. Thereby, the DLC layer 26 is formed when only the argon gas is supplied, and the CN layer 28 is formed when both the argon gas and the nitrogen gas are supplied. In that case, film formation conditions such as arc current and bias voltage are determined so that the DLC layer 26 and the CN layer 28 having a predetermined hardness and composition can be obtained. The film thickness can be adjusted by the film formation time.

  When the CN layer 28 is formed, film formation conditions are determined so as to include both single bonds (sp3) and double bonds (sp2), and the processing temperature is in the range of 20 to 250 ° C., for example, about 150 ° C., The bias voltage is set to, for example, about 100 V within a range of 15 to 300 V. The supply flow rate of the nitrogen gas is determined so that the nitrogen content in the CN layer 28 is in the range of 3 to 40 at%.

FIG. 8 shows the results of examining the durability by drilling under the following processing conditions using the products of the present invention (No. 7 to No. 18) and comparative products (No. 1 to No. 6) configured as described above. It is a figure explaining. The shaded columns in the comparative products are items that are out of the requirements of the present invention (Claims 1 and 2). The nanoindentation hardness of the DLC layer 26 is in the range of 40 to 50 GPa for both the product of the present invention and the comparative product.
(Processing conditions)
・ Tool shape: φ8 carbide twist drill ・ Work material: A5052 (aluminum alloy)
・ Cutting speed: 80 m / min
・ Feeding speed: 0.14mm / rev
・ Processing depth: 24mm through hole ・ Cutting oil: Mist ・ Step amount: Non-step

  As is clear from the test results in FIG. 8, in the comparative products No. 1 and No. 2 provided with only the DLC layer 26, the flank wear widths of the cutting edge 12 when drilling 1000 holes are 0.32 mm and 0.35 mm, respectively. On the other hand, all the products of the present invention are smaller than the acceptance criterion of 0.2 mm. Further, for the comparative products No. 3 to No. 6 in which the CN layer 28 is provided on the DLC layer 26, in the case of the comparative product No. 3 in which the nitrogen content of the CN layer 28 is 47 at%, the coating hardness (nanoindene) (Attachment hardness) becomes too high and becomes brittle, and wear is promoted by chipping or peeling. On the other hand, in comparative product No. 6 with a nitrogen content of 1 at%, the film hardness (nanoindentation hardness) is low and wears. Is promoted. In the comparative product No. 4 in which the film thickness D of the entire hard coating 24 is 3 μm, wear is accelerated by peeling or the like, and in the comparative product No. 5 in which the film thickness D is 0.005 μm, the effect of improving the wear resistance by the hard coating 24 is sufficient. I can't get it.

  Further, the hard coating 60 in FIG. 9 is formed by repeatedly laminating the DLC layer 26 and the CN layer 28 alternately and forming the CN layer 28 as the uppermost layer, and the overall film thickness D is in the range of 0.01 to 3 μm. It is a thing. Also about this, as shown in FIG. 10, this invention product (No5-No11) and a comparative product (No1-No4) were prepared, and the durability test was done on the same processing conditions as the case of the said FIG. In the comparative product, the shaded columns are items that are out of the requirements of the present invention (Claim 1). The nanoindentation hardness of the DLC layer 26 is in the range of 40 to 50 GPa for both the product of the present invention and the comparative product.

  As is apparent from the test results of FIG. 10, in all of the products of the present invention, the flank wear width of the cutting edge 12 is smaller than 0.2 mm, which is an acceptance criterion. Compared to the hard coating 24 having the two-layer structure, in the case of a multilayer, even if the total film thickness D is 3 μm as in the sample No. 7, peeling is suppressed and good wear resistance is obtained. It is considered that the individual film thicknesses D1 and D2 are thin, and the progress of peeling and cracking is prevented by peeling of a part of the upper layer. However, if the entire film thickness D is increased to 4 μm as in the comparative product No1, wear is accelerated by peeling, and therefore the entire film thickness D needs to be 3 μm or less even in a multilayer film. In comparative product No. 2 having a film thickness D of 0.006 μm, the effect of improving the wear resistance by the hard coating 60 cannot be sufficiently obtained. Further, in the case of the comparative product No. 3 in which the nitrogen content of the CN layer 28 is 44 at%, the coating layer hardness (nanoindentation hardness) of the CN layer 28 becomes too high and becomes brittle, and wear is accelerated by chipping or peeling. On the other hand, in the comparative product No. 4 having a nitrogen content of 1 at%, the film hardness (nanoindentation hardness) is low and the wear is promoted.

  As described above, in the hard coatings 24 and 60 of the drill 10 of the present embodiment, the DLC layer 26 is provided on the surface of the tool base 22, and the CN layer 28 having a nitrogen content of 3 to 40 at% constitutes the outer surface. So that the overall film thickness D is in the range of 0.01 to 3 μm, and therefore the CN layer 28 of the uppermost layer has superior heat resistance, wear resistance, and Weld resistance is obtained. Moreover, since the DLC layer 26 is provided on the surface of the tool base 22, high adhesion strength is obtained, peeling and the like are suppressed, and excellent durability is obtained. This improves the welding resistance of processing in an environment where welding is likely to occur (such as in a vacuum) and enables processing of ferrous materials, resulting in excellent tool life, while non-ferrous such as aluminum alloys. Dry processing and semi-dry processing (mist processing) are possible for the system material.

  Further, both the DLC layer 26 and the CN layer 28 can be easily adjusted in hardness by changing the film forming conditions. In this embodiment, the nanoindentation hardness of the DLC layer 26 is 40 to 50 GPa. Since the nanoindentation hardness of the CN layer 28 is in the range of 15 to 55 GPa, excellent wear resistance is obtained, and the durability of the drill 10 is improved.

  Further, in this embodiment, the CN layer 28 includes both single bond and double bond CNs. Therefore, by changing the film formation conditions and changing their ratio, the CN layer 28 is hardened. Can be adjusted. That is, the single bond CN is harder than the double bond CN. Therefore, if the film forming conditions such as the bias voltage and the arc current are set so that the ratio of the single bond CN is increased, the CN layer 28 While the overall hardness can be increased, toughness can be improved by increasing the proportion of CN of double bonds.

  Further, in this embodiment, since the thickness of the DLC layer 26 and the CN layer 28 are both within the range of 0.005 to 1 μm, the presence of the DLC layer 26 improves the adhesion strength and is superior to the CN layer 28. Heat resistance, wear resistance, and welding resistance can be obtained.

  1 has a two-layer structure in which the CN layer 28 is directly provided on the DLC layer 26, and the entire film thickness D is in the range of 0.01 to 2 μm. Therefore, exfoliation and the like are suppressed and excellent durability is obtained, and the structure is simple and inexpensive.

  As mentioned above, although the Example of this invention was described in detail based on drawing, these are one embodiment to the last, and this invention is implemented in the aspect which added the various change and improvement based on the knowledge of those skilled in the art. be able to.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the drill provided with the hard film of this invention, (a) is a front view, (b) is an enlarged bottom view seen from the front end side, (c) is an expanded sectional view of the surface vicinity of a body. 1 is a schematic diagram for explaining the structure of CN (carbon nitride), in which (a) has a single bond and a double bond similarly to the CN layer of the hard coating in FIG. 1, (b) has a single bond, and (c ) Is for a double bond. It is an example of the Raman spectrum of CN which has a single bond and a double bond. It is a conceptual diagram explaining a pin-on-disk friction test apparatus when performing a frictional wear test using a test piece provided with a predetermined hard coating. It is a figure which shows an example of the result of having measured the friction coefficient of CN, DLC, and TiN using the apparatus of FIG. It is a figure which shows the wear trace (welding) of CN and DLC after performing a friction abrasion test using the apparatus of FIG. It is the schematic explaining the arc ion plating apparatus which can form suitably the hard film of FIG. It is a figure explaining the item of this invention used when performing a durability test, the specification of a comparative product, and the result of a durability test. It is a figure explaining the other Example of this invention, and is sectional drawing of the hard film corresponded to (c) of FIG. It is a figure explaining the item of this invention used when performing the durability test regarding the hard film of FIG. 9, and the comparison product, and the result of a durability test.

Explanation of symbols

  10: Drill (hard coating coated tool) 22: Tool base material (base material) 24, 60: Hard coating 26: DLC layer 28: CN layer (carbon nitride layer)

Claims (5)

A hard coating provided on the surface of a predetermined substrate,
A DLC layer provided on the surface of the substrate;
A carbon nitride layer composed of carbon nitride having a nitrogen content in the range of 3 to 40 at%, and a carbon nitride layer provided on the uppermost layer so as to constitute the outer surface;
And
The total film thickness is in the range of 0.01 to 3 μm,
The hard coating characterized in that the carbon nitride layer contains both single bond and double bond carbon nitride. The two-layer structure in which the carbon nitride layer is provided directly on the DLC layer is formed, and the total film thickness is in the range of 0.01 to 2 μm. Hard coating. The nanoindentation hardness of the DLC layer is in the range of 40 to 50 GPa, and the nanoindentation hardness of the carbon nitride layer is in the range of 15 to 55 GPa. Hard coating. The DLC layer and the thickness of the carbon nitride layer, a hard coating according to any one of claim 1 to 3, characterized in that both in the range of 0.005 to 1 [mu] m. A hard film coated tool in which a hard film is provided on the surface of a substrate,
The hard film-coated tool according to any one of claims 1 to 4 , wherein the hard film is the hard film according to any one of claims 1 to 4 .

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