JPH116056A - Target containing intermetallic compound, and manufacture of hard covered member using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the target containing the intermetallic compound which is small in secular change of the composition in forming the film, and capable of forming the covering of the (Ti, Al) compound of excellent quality by containing the intermetallic compound of Ti and Al by the prescribed quantity in a diffusion manner, and mainly constituting the balance of Ti and Al. SOLUTION: A target containing the intermetallic compound which consists of the sintered alloy obtained through sintering by the powder metallurgical method, containing >=30 atm.% of the intermetallic compound of Ti and Al with the balance Ti, Al and inevitable impurities, and is capable of forming a hard covering which is small in micro particles, hard in hardness, and uniform, is obtained. In the intermetallic compound, Ti:Al is preferably 50-55:50-45 atomic ratio, or Ti:Al is 48-75:52-25 in the whole target. The inevitable impurities of Si, Fe, B, etc., are preferably limited to <=1%. The covering excellent in the uniformity, peeling resistance, high hardness, and high toughness can be formed by achieving the arc ion plating using the target.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a nitride, carbonitride, nitride oxide, carbonate, carbonitride of titanium and aluminum on a substrate of a metal, alloy or ceramics sintered body by physical vapor deposition. The present invention relates to a target containing an intermetallic compound which is optimal as an evaporation source for coating a (Ti, Al) compound film composed of an oxide and a method of manufacturing a hard coating member using the target. Control of film uniformity, peeling resistance, high hardness,
Intermetallic compound-containing target capable of coating a (Ti, Al) compound film with excellent toughness and a cutting tool represented by a turning tool, milling tool, drill, end mill using this target Tools such as cutting blades, slitters, cutting blades and dies, punches and other mold tools and corrosion-resistant and wear-resistant members such as nozzles, tunnel drill bits, and civil engineering construction represented by construction tools. TECHNICAL FIELD The present invention relates to an intermetallic compound-containing target for producing an optimal hard-coated member as a tool for use, and a method for manufacturing a hard-coated member using the target.

[0002]

2. Description of the Related Art Metal, alloy and ceramic substrates are coated with a ceramic film having a thickness of 20 μm or less,
Many coating members have been proposed that attempt to achieve a long life by effectively extracting the characteristics of the substrate and the coating. The coating method of the coating member is roughly classified into a chemical vapor deposition method (CVD method), a physical vapor deposition method represented by a sputtering method and an ion plating method (PVD method). Among these, as one kind of the coating by the PVD method,
There is a cover member represented by a (Ti, Al) compound film proposed in the mid 1980's. The coating of the (Ti, Al) compound is generally applied by a sputtering method using a target containing a Ti element and an Al element as an evaporation source. Such Ti element and A
Representative examples of targets disclosed in Japanese Patent Application Laid-Open Nos. Sho 62-56565, Hei 6-210502, and Hei 6-210
511 and JP-A-7-197235. Further, as a representative example of a target in which an intermetallic compound is dispersed, see JP-A-8-100.
No. 255 publication.

[0003]

Among the prior arts disclosed with respect to a target containing a Ti element and an Al element, JP-A-62-56565 and JP-A-6-2565.
Japanese Patent Application No. 10502 and Japanese Patent Application Laid-Open No. 6-210511 disclose a target of a Ti-Al alloy (containing 20% of Al). The targets disclosed in these prior arts are alloys in which Ti: Al has a ratio of 4: 1. Therefore, it is difficult to produce a target in terms of alloy. Even if a target is produced, it is used as an evaporation source. When the film is used for coating, there is a problem that microparticles are liable to be generated in the film, the film tends to be non-uniform, low in hardness and easily peelable, and the life is short. Japanese Patent Application Laid-Open No. 7-197235 discloses that Al _X
Ti _1-X Specifically, an Al _0.7 Ti _0.3 target is disclosed. When the target disclosed in the publication is a mixture of an Al element and a Ti element, the same problem as described above is included except for the production of the target. Includes the same problems as those described above when producing a target and forming a film using the target.

On the other hand, Japanese Patent Application Laid-Open No. HEI 8-100255, which discloses a target containing an intermetallic compound, discloses one or more alloy components of Nb, V, Ti, Zr, Ni, Pt and W. Disclosed is a sputtering target material for forming a thin film of a thin film transistor in which an intermetallic compound of Al having an average particle diameter of 30 μm or less and an alloy component having a composition of 20 wt%, the remaining Al and unavoidable impurities is dispersed in a base material. ing. The target disclosed in the publication is an alloy composed of two or more metal elements containing Al as a main component, and is excellent when a thin film for a thin film transistor is formed, whereas a compound containing a nonmetallic element is used. When a thin film is formed, there is a problem that microparticles are easily generated in the film as in the above-described prior art, and the film tends to be non-uniform, low in hardness and easily peelable, and has a short life.

The present invention has solved the above-mentioned problems in the conventional target and the film forming method using the target. Specifically, the present invention is directed to a method in which an intermetallic compound of titanium and aluminum is reduced to 30 atoms. % As a target uniformly dispersed and contained, and using this target (T
When a coating of an (i, Al) compound is applied, it is difficult for the composition of the target to change with time during the film formation, it is possible to suppress microparticles on the coating surface, it is possible to increase the hardness of the coating, Easy adjustment, uniformity of coating material and thickness,
As a result, it is an object of the present invention to provide a target capable of forming a long-life coating member and a method of manufacturing a hard coating member using the target.

[0006]

The present inventors have proposed (Ti,
A conventional target used for producing a film of an Al) compound is a Ti-Al alloy, particularly an alloy having a low Al content. The film produced using this target generates microparticles. It has been studied for many years because of the problems of easy coating, uneven coating, and low hardness coating. The film produced using the target containing the inter-compound at 30 atomic% or more has been found to be able to solve the above-mentioned problems, and has completed the present invention.

[0007] The target of the present invention is characterized in that the intermetallic compound of titanium and aluminum is at least 30 atomic%, and the balance consists of titanium element, aluminum element and unavoidable impurities.

Specifically, the intermetallic compound in the target of the present invention has a Ti: Al atomic ratio of 1: 1 (TiAl intermetallic compound), which is said to be, for example, an intermetallic compound of titanium and aluminum. 3: 1 (Ti ₃ A
1 intermetallic compound) and 1: 3 (TiA ₃ intermetallic compound). Among these intermetallic compounds, it is possible to produce a stable target to be made of a TiAl intermetallic compound in which the atomic ratio of Ti: Al is close to 1: 1. It is preferable because the generation is suppressed and the characteristics of the coating are excellent.
It is preferable to contain a large amount of an intermetallic compound having an atomic ratio of i: Al of 50 to 55:50 to 45. It is preferable that the intermetallic compound is uniformly dispersed in the target.

The composition of the target of the present invention is such that, in addition to the above-mentioned intermetallic compound, Ti metal and Al metal, T
In the case where Ti and / or Al are mixed in the i-Al alloy or the Ti-Al alloy, specifically, for example, in the case of the first configuration made of TiAl intermetallic compound + Ti metal and / or Al metal, TiAl metal Compound +
In the case of the second configuration made of (Ti-Al) alloy, TiAl
Intermetallic compound + (Ti-Al) alloy + Ti metal and / or
Alternatively, the case of the third configuration made of Al metal can be cited. What is important in the composition of this target is
The content of the intermetallic compound contained in the target, the ratio of the Ti element and the Al element present in the target, and the ratio of the Ti element and the Al element in the above-mentioned intermetallic compound. Among them, the atomic ratio of the Ti element and the Al element present in the target is Ti: Al = 48 to 75:52.
It is preferable that the ratio is from 25 to 25 since the characteristics of the film can be improved.

The target of the present invention can be manufactured by a sintering method, a melting casting method, or the like in a powder metallurgy method conventionally known as an alloy manufacturing method.
Of these, sintering, in particular, reaction sintering or high-temperature sintering is preferable because it is easy to manufacture a dense and uniform target satisfying the above-mentioned conditions.

This target has unavoidable impurities contained in a starting material for producing the target and impurities which are mixed when producing the target. As these impurities, for example, C (carbon), Si, Mn,
V, Fe, Ni, N (nitrogen), Cr, O (oxygen), B
(Boron). Of these, Si,
It is preferable that at least one of Fe and B is limited to 1 atomic% or less based on the entire target.

Using the target of the present invention, one of a nitride, a carbonitride, a nitride oxide, a carbonate and a carbonitride of titanium and aluminum by various physical vapor deposition methods (PVD methods). A hard film consisting of a single layer or two or more layers can be coated on a base material of a metal material, a sintered alloy, or a ceramic.

[0013] Among the physical vapor deposition methods, the method for producing a hard coated member according to the present invention comprises a first step of bombarding the surface of a substrate, and introducing a film forming material evaporated from a target to the surface of the substrate. And forming a coating of a single layer or a multilayer of two or more of nitrides, carbonitrides, nitrides, carbonates and carbonitrides of titanium and aluminum. Wherein the target used in the second step is an intermetallic compound-containing target containing at least 30 atomic% of an intermetallic compound of titanium and aluminum. is there.

The substrate used in the method for producing a hard-coated member of the present invention is not particularly limited in terms of material, and is a material capable of withstanding a heating temperature when coating the film, for example, a metal member. , Sintered alloys or sintered ceramics have no problem. Specifically, for example, stainless steel, heat-resistant alloy, high-speed steel, die steel, Ti alloy,
Metal members typified by Al alloys, cemented carbides, cermets, sintered alloys typified by powdered high-speed steel, Al ₂ O ₃ based sintered bodies, Si ₃ N ₄ based sintered bodies, sialon based sintered bodies , ZrO ₂
Ceramic sintered bodies typified by system-based sintered bodies can be given. Among these, when used as a cutting tool or a wear-resistant tool, a substrate of a cemented carbide, a nitrogen-containing TiC-based cermet, or a ceramic sintered body is preferable.

After cleaning and drying the surface of the substrate, the substrate is placed in a reaction vessel for a physical vapor deposition device capable of adjusting the vacuum and gas atmosphere, and a conventional bombarding process can be performed. . In particular, the bombardment treatment is 773 in the following pressure 10 ^-3 Torr vacuum
It is preferable to increase the temperature to 1273 K and apply a negative bias current to the base material so that the effect of the target can be more easily obtained.

After the bombardment treatment, a nitride, carbonitride, nitride oxide, carbonate, or carbonitride of titanium and aluminum is deposited on the surface of the substrate placed in the reaction vessel using the above-mentioned target as an evaporation source. This is a method including a second step of coating a film composed of one kind of single layer or two or more kinds of multilayers. In particular, the conditions in the reaction vessel in the second step are as follows:
At a temperature of 773 to 1273 K, the flow rate of the nitrogen gas and / or the nitrogen source gas for supplying the nitrogen was set to 300 S
It is preferable to carry out the process by applying a negative bias current to the base material at a CCM or higher. The nitrogen source gas at this time may be any gas that reacts or decomposes into nitrogen gas, and specifically includes, for example, ammonia, amine-based materials, and cyan-based materials. Further, when the flow rate of the nitrogen source gas during the second step is specifically exemplified for use in an arc ion plating apparatus, it is more preferable to adjust the flow rate of the nitrogen source gas per ampere (A) of the arc current. , Whose value is preferably 2-4 SCCM / A.

The physical vapor deposition method in the method for producing a hard coated member of the present invention can be used as an ion plating method, a sputtering method, or a laser vapor deposition method, but the ion plating method is particularly preferable. Of these methods, the arc ion plating method is preferable because the crystal plane of the coating can be easily oriented and the characteristics of the coating can be further improved.

[0018]

According to the target of the present invention, the intermetallic compound uniformly contained in the target acts to suppress the temporal change of the composition during film formation, and the action to suppress the generation of microparticles as foreign matter. And facilitates orientation of the crystal plane of the coating. In addition, the method of manufacturing a hard coated member of the present invention facilitates the display of the characteristics of the target, suppresses microparticles in the coating, and facilitates the orientation of the crystal plane of the coating. The coating of the (Ti, Al) compound in the resulting hard coating member increases the coating hardness, acts to improve the fracture toughness and wear resistance of the entire coating, and remains near the interface between the base material and the coating. In particular, in the case of a substrate made of a cemented carbide, it acts to increase the residual compressive stress in the coating and enhance the adhesion to the substrate.

[0019]

[Experimental Test 1] After melting and casting at 1473-1573K in an argon atmosphere using a commercially available sponge titanium and granular aluminum as raw materials in a casting furnace,
The target of the product 1 of the present invention was produced by polishing and molding. Also, after using a commercially available Ti powder having an average particle diameter of 5 μm and an Al powder having an average particle diameter of 2 μm, a lump of TiAl intermetallic compound is produced, and the lump is pulverized and then re-used in a conventional powder metallurgy. After the mixing, molding, and sintering (the sintering temperature at this time was 1373 K), the target of the product 2 of the present invention was produced.

As a comparison, a target of a comparative product 1 was prepared in the same manner as the product 2 of the present invention, except that the step of preparing a lump of the TiAl intermetallic compound was omitted and sintering was directly performed at 1173K. In addition, a target made of a clad material of a commercially available Ti plate and an Al plate was used as Comparative Product 2.

The hardness (Vickers hardness under a load of 0.05 kgf) of the inventive products 1 and 2 and the comparative products 1 and 2 thus produced and the intermetallic compounds contained in the target were determined and are shown in Table 1. Was. The intermetallic compound is calculated from the intensity ratio of diffraction lines obtained by X-ray diffraction and the lattice constant.

The products of the present invention 1, 2 and the comparative products 1, 2
Get S as an evaporation source, and a commercially available shape S
Cemented carbide of NGA120408 (JIS standard B4053
Base material) and the surface of the base material with an organic solvent
After cleaning, the chamber of the arc discharge plasma PVD device
It was set up inside. Initial conditions in this chamber are
Degree: 600 ° C, Pressure: 1 × 10^-FourTorr vacuum,
Hold for 60 minutes. Then pressure: 1 × 10^-3 Torr
Vacuum, arc current: 60 A, substrate bias: -6
00V and a bombard treatment with a holding time of 10 minutes
gave. Then, pressure: 20 × 10^-3Torr, nitrogen flow
Amount: 380 SCCM, arc current: 100 A, base material
Ass (V): -40 (hold for 15 minutes) to -100 (1 minute)
Hold) to -200 (1 minute hold) to -300 (1 minute
Hold) to -40 (hold for 4 minutes).
Using a target evaporation source, apply a coating of about 4 μm on the surface of the substrate.
Coated to thickness. The hardness of the coated cemented carbide film thus obtained
Check the scratch strength and microparticles
Table 1 shows the results.

The hardness, scratch strength and microparticles of the film were measured using a Vickers hardness tester, a film peeling tester corresponding to a scratch abrasion tester and a scanning electron microscope. Hardness is 0.05kgf load,
For the scratch strength, the critical peeling load until the film was peeled was determined as the peeling resistance of the film, and the number of microparticles per visual field in a scanning electron microscope with a magnification of 800 times was calculated and converted per unit area. The microparticles at this time were those having a size of 1 μm or more, which can be confirmed at 800 times.

[0024]

[Table 1]

[0025]

[Test 2] The targets of Inventions 3 to 11 and Comparatives 3 and 4 were prepared in substantially the same manner as the target of Product 2 of the present invention in Experiment 1, and the content of the intermetallic compound in the target was adjusted. Obtained. The composition components of each of the targets of the present invention products 3 to 11 and comparative products 3 and 4 thus obtained were measured with a fluorescent X-ray analyzer and an X-ray diffractometer, and the results are shown in Table 2.

Using each of the targets of the present invention products 3 to 11 and comparative products 3 and 4 shown in Table 2, a coated cemented carbide having a coating on the substrate surface was obtained in substantially the same manner as in the test 1. Was. The hardness, scratch strength, and microparticles of the coating of the coated cemented carbide thus obtained were measured in the same manner as in the test 1, and the results are shown in Table 3.

Next, products 3 to 11 of the present invention and comparative products 3,
The following turning test was performed on the coated cemented carbide obtained using No. 4 and the cutting time up to the life at that time was determined and also shown in Table 3. The turning test conditions were as follows: Work material: S48C (HB2
05-223), cutting speed 150m / min, feed:
0.3 mm / rev, depth of cut: 1.5 mm, chip shape: SNGA120408, performed by dry cutting test,
The peeling, chipping or average flank wear width of the coating is 0.
The life was defined as 1 mm, and the cutting time until the life was calculated.

[0028]

[Table 2]

[0029]

[Table 3]

[0030]

The target of the present invention is (Ti, Al)
Compared to conventional targets that have been used for coating compound films, the effect of suppressing the temporal change of the composition during film formation is high, and the effect of suppressing microparticles generated in the film is high. It has an excellent effect that the coated film has high hardness, high toughness and wear resistance. Further, the method for producing a hard coated member of the present invention is such that the orientation of the crystal plane of the coating is easy,
The effect of the target described above is synergistic with the uniformity of the thickness of the coating film and the variation of the coating material being small, and when the obtained hard coated member is used as a cutting tool, a wide area from a low speed cutting area to a high speed cutting area. And a long life is expected especially as a rotary cutting tool as a cutting tool for milling, an end mill and a drill as compared with the conventional manufacturing method.

Claims (11)

[Claims] 1. A target containing an intermetallic compound, characterized in that the intermetallic compound of titanium and aluminum is at least 30 atomic% and the balance consists of titanium element, aluminum element and unavoidable impurities. 2. The target containing an intermetallic compound according to claim 1, wherein the intermetallic compound has an atomic ratio of Ti element to Al element of 50 to 55:50 to 45. 3. The target has an atomic ratio of Ti element to Al element contained in the entire target of 48 to 7;
The intermetallic compound-containing target according to claim 1 or 2, wherein the ratio is 5:52 to 25. 4. The unavoidable impurity according to claim 1, wherein at least one of Si, Fe, and B is limited to 1 atomic% or less based on the entire intermetallic compound target. Or the intermetallic compound-containing target according to 3. 5. The method according to claim 1, wherein the target is a sintered alloy sintered by a powder metallurgy method.
5. The target containing an intermetallic compound according to 2, 3, or 4. 6. A first step of bombarding a surface of a base material, and introducing a film-forming material evaporated from a target to the surface of the base material to form a nitride, carbonitride, and oxynitride of titanium and aluminum. To form a coating consisting of one single layer or two or more layers of materials, carbonates and carbonitrides
In the method of forming a film by physical vapor deposition including a step,
The method for producing a hard coated member, wherein the target used in the second step is an intermetallic compound-containing target containing 30 atomic% or more of an intermetallic compound of titanium and aluminum. 7. The bombardment treatment is performed at 10 ⁻³ Torr.
In a vacuum having the following pressure, a temperature of 773 to 1273K,
6. The method according to claim 5, wherein the substrate is treated by applying a negative bias current to the substrate. 8. The method according to claim 5, wherein the intermetallic compound has an atomic ratio of Ti element to Al element of 50 to 55:50 to 45. 9. The target according to claim 1, wherein an atomic ratio of Ti element to Al element with respect to the whole target is 48 to 75:
The method for producing a hard-coated member according to claim 5, wherein the number is 52 to 25. 10. The method according to claim 10, wherein the second step is performed under reduced pressure.
The method according to claim 5, wherein the temperature is 273K, the flow rate of the nitrogen gas and / or the nitrogen source gas for supplying nitrogen is 300 SCCM or more, and the step is performed by applying a negative bias current to the substrate. 9. The method for producing a hard coated member according to item 8. 11. The method according to claim 5, wherein the physical vapor deposition method is an arc ion plating method.