JPH0633223A - Film coating product and its production - Google Patents

Abstract

PURPOSE:To provide a film coating product having a film excellent in hardness and toughness on its surface, and to provide its production method. CONSTITUTION:In the film coating product, an the surface of a base body 2, a nitrogen compd. film 6 composed of nitrogen and group IVA elements and group IIIB elements of the periodical table is formed and a mixture layer 4 consisting of the films 6 and 2 is formed on the interface between the relevant intermediate layer 6 and the base body 2. The coated product is obtd. by the vapor deposition of a material containing group IVA elements, vapor deposition of a material containing group IIIB elements, and the, irradiation of ions containing nitrogen ions on the base body 2 in a vacuum chamber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film adherend used for a cutting tool, a tool such as an excavating bit, a sliding part, and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, a film having a high hardness is formed (deposited) on the surface of a base material such as a tool base material in order to improve wear resistance, slidability, chemical stability and the like. Things have been done.

Typical materials constituting such a film include Ti, Zr and Hf which are elements of Group 4A of the periodic table of elements.
The nitrides TiN, ZrN, and HfN are listed. These have excellent hardness, are subjected to film synthesis by means such as ion plating, and are widely applied to various wear resistance fields.

Further, B, which is a 3B group element of the periodic table,
BN, AlN, and especially BN, which are Al nitrides, are also materials which are attracting attention in the field of wear resistance.

Depending on the crystal structure, the boron nitride (BN) has a cubic zinc blende type (c-BN), a structure similar to hexagonal graphite (h-BN), or a hexagonal system. Wurtzite type (w-BN).

Among them, c-BN has high hardness second only to diamond and is excellent in thermal and chemical stability, so that it is applied to a field requiring wear resistance such as a cutting tool. In addition, it is also used as a material for a heat sink by taking advantage of its characteristics of electrical insulation and high thermal conductivity. Although w-BN is inferior in hardness to c-BN,
Since it has hardness and thermal conductivity superior to those of other nitrides, it is expected to be applied to the same field as c-BN.

These c-BN and w-BN can be usually synthesized at high temperature and high pressure, and it has been difficult to synthesize the membrane at low temperature. However, in recent years, a method of synthesizing a c-BN film even at a low temperature by a non-thermal equilibrium process by exciting a vapor deposition atom by collision of the vapor deposition atom with an ion by using both vacuum vapor deposition and ion irradiation has been actively tried. .

[0008]

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention
Although N and w-BN have high hardness, they are brittle due to lack of toughness. When a substrate coated with a film made of c-BN or w-BN is used as a tool or a sliding part, for example, cracks are generated in the film. It enters and cannot play the role of protecting the substrate.

Further, although TiN is relatively excellent in toughness, it is inferior in hardness to c-BN and w-BN, so that its wear resistance is c-BN, w under severe abrasive wear conditions. -Inferior to BN.

As described above, it is the fact that a film which has been conventionally used in the wear resistance field and has excellent hardness and toughness has not yet been found.

Therefore, the main object of the present invention is to provide a film adherend in which a film excellent in both hardness and toughness is formed on the surface of a substrate and a method for producing the same.

[0012]

In order to achieve the above object, the film adherend of the present invention forms a film of a nitrogen compound consisting of a group 4A element, a group 3B element and nitrogen of the periodic table on the surface of a substrate. In addition, a mixed layer composed of both constituent elements is formed at the interface between the film and the substrate.

Further, according to the manufacturing method of the present invention, vapor deposition of a substance containing a group 4A element of the periodic table of elements and vapor deposition of a substance containing a group 3B element of the periodic table of elements are performed on a substrate in a vacuum chamber.
By irradiation with ions including nitrogen ions,
A film of a nitrogen compound including a group 4A element, a group 3B element and nitrogen is formed on the surface of the substrate.

[0014]

The nitride of the group 3B element generally has high hardness. On the other hand, the 4A group element is generally chemically active, and a film containing the same becomes better compatible with the substrate, less likely to generate internal stress, and excellent in toughness. Moreover, such a nitride of the 4A group element has a high hardness, though not so much as a nitride of the 3B group element.

Therefore, the above-mentioned film adherend is constituted by 4
A film of a nitrogen compound including a group A element, a group 3B element and nitrogen has excellent hardness and toughness. Moreover, since the mixed layer as described above formed at the interface between the film and the substrate acts like a wedge, the adhesion of the film to the substrate is also excellent.

Further, according to the above-mentioned manufacturing method, the vapor deposition atoms are excited near the surface of the substrate by the collision of the irradiation ions and the vapor deposition atoms.
A film of a nitrogen compound including a group element and nitrogen can be formed at a low temperature without heating the substrate to a high temperature.
Moreover, the collision between the irradiation ions and the vapor deposition atoms pushes the vapor deposition atoms onto the surface of the substrate, so that the above-mentioned mixed layer is formed at the interface between the film and the substrate at a low temperature together with the formation of the film. Therefore, the adhesion of the film to the substrate can be improved even when the film is formed at a low temperature.

[0017]

1 is a schematic sectional view showing an example of a film adherend according to the present invention. This film adherent forms a film 6 of a nitrogen compound consisting of 4A group elements, 3B group elements and nitrogen of the periodic table on the surface of the substrate 2, and at the interface between the film 6 and the substrate 2, both 6 Mixed layer 4 composed of 2 constituent elements
Is formed.

The type of the substrate 2 is not limited to a particular type, and may be, for example, high speed tool steel, cemented carbide, other metals, ceramics, resins, or other types. Further, the shape is not limited to a particular one.

Titanium (T
i), zirconium (Zr), and hafnium (Hf) belong, and, for example, boron (B) and aluminum (Al) belong to the 3B group element.

The nitride of the 3B group element generally has high hardness. On the other hand, the 4A group element is generally chemically active, and a film containing the same becomes better compatible with the substrate, less likely to generate internal stress, and excellent in toughness.
Moreover, such a nitride of the 4A group element has a high hardness, though not so much as a nitride of the 3B group element.

Therefore, the above-mentioned film adherend is constituted by 4
The film 6 of the nitrogen compound including the group A element, the group 3B element and nitrogen has excellent hardness and toughness. As a result, the film adherent is a nitride of a Group 4A element or 3
It has better wear resistance, slidability and chemical stability than the film-deposited ones containing only Group B element nitrides. Moreover, since the above-mentioned mixed layer 4 formed at the interface between the film 6 and the substrate 2 acts like a wedge, the adhesion of the film 6 to the substrate 2 is also excellent. .

Next, an example of a method for manufacturing the above film adherend will be described with reference to FIG.

A holder 12 for holding the substrate 2 as described above is provided in a vacuum container 10 which is evacuated by a vacuum evacuation device (not shown). To this end, in this example, two evaporation sources 14, 16 and An ion source 22 is arranged. In addition, a film thickness monitor 26 and an ion current monitor 28 are arranged near the holder 12 in this example.

On the other hand, the evaporation source 14 evaporates a substance 18 containing a group 4A element (for example, a simple substance of Ti, Zr or Hf, or their nitrides or oxides) and deposits it on the surface of the substrate 2. You can The other evaporation source 16 is 3B
A substance 20 containing a group element (for example, a simple substance of B or Al, or a nitride or oxide thereof) is evaporated and the substance is used as a base material
Can be deposited on the surface of. These evaporation sources 1
The methods of 4 and 16 are, for example, electron beam heating of evaporation material,
The heating method is high-frequency heating or resistance heating, but is not limited to a specific method.

Further, the vapor deposition of the substance containing the group 4A element and the vapor deposition of the substance containing the group 3B element as described above may be performed by the sputter vapor deposition in which a target is sputtered in addition to the above-mentioned vacuum vapor deposition. .

In either of the vacuum vapor deposition and the sputter vapor deposition, a mixture containing both the 4A group element and the 3B group element may be heated or sputtered from one evaporation source. In that case, however, it is often difficult to adjust the composition ratio of the film deposited on the substrate 2 because the vapor pressures of the substances composed of both elements are different. In that case, the sputter deposition is adopted. Is preferred.

The ion source 22 may be of any type as long as it can accelerate and extract the ions 24 containing nitrogen ions. For example, a multi-pole magnetic field type so-called bucket type ion source is preferable in terms of large area and large current, but of course, other ion sources may be used.

In manufacturing the film adherend as shown in FIG. 1, first, the desired substrate 2 is attached to the holder 12 and then
The inside of the vacuum container 10 is evacuated to maintain a predetermined degree of vacuum. After that, the substance 18 containing the 4A group element and the substance 20 containing the 3B group element as described above are evaporated from the evaporation sources 14 and 16, respectively, and these are evaporated on the surface of the substrate 2. At this time, the film thickness monitor 26 can be used to measure and adjust the amounts of the substances 18 and 20 that reach the substrate 2. Further, in conjunction with the vapor deposition of the substances 18 and 20, that is, simultaneously with vapor deposition, alternately or after vapor deposition, the above-mentioned ions 24 are accelerated and extracted from the ion source 22 and irradiated toward the substrate 2. The irradiation amount of the ions 24 at this time can be measured and adjusted by the ion current monitor 28.

As a result, the film 6 (see FIG. 1) of the nitrogen compound composed of the 4A group element, 3B group element and nitrogen as described above can be formed on the surface of the substrate 2.

The energy of the ion 24 in the above case is
The material is not limited to a particular one, and may be determined according to, for example, the type of the substrate 2, particularly its heat resistance, film thickness of film formation and the like. For example, in the case of a substrate having a high heat resistance such as metal, the energy of the ions 24 is set to 2 KeV or more, and in the case of a resin having a low heat resistance such as a resin, the energy of the ions 24 is set to 2 KeV.
It should be less than.

Further, the ratio of the number of atoms of the 4A group element, the number of atoms of the 3B group element and the number of nitrogen element in the formed film 6 is not particularly limited, but, for example, the substrate 2 is made of resin. If only small energy can be used as the energy of the irradiated ions 24, and therefore the thickness of the mixed layer formed at the interface between the film 6 and the substrate 2 cannot be made large, the following may be performed. That is, the number of atoms of the Group 4A element is increased at the interface between the film 6 and the substrate 2, and the high chemical activity is utilized to increase the adhesion strength of the film 6, while the vicinity of the surface of the film 6 is increased. Then, in order to improve the chemical stability of the film 6, the nitride of the group 4A element and the nitride of the group 3B element may be stoichiometric (Stoichiometric).

According to the above-described manufacturing method, the vapor deposition atoms are excited by the collision between the irradiation ions 24 and the vapor deposition atoms in the vicinity of the surface of the substrate 2, so that the 4A group element and the 3B group are formed on the surface of the substrate 2. Nitrogen compound film 6 consisting of element and nitrogen
Can be formed at a low temperature such as room temperature without heating the substrate 2 to a high temperature as in the CVD method. Therefore, the type of the base 2 is not limited.

Moreover, the collision of the irradiation ions 24 with the vapor deposition atoms pushes the vapor deposition atoms into the surface of the substrate 2. Therefore, at the same time as the formation of the film 6, the vapor deposition atoms 6 are formed at the interface between the film 6 and the substrate 2. The mixed layer 4 (see FIG. 1) as described above composed of the two constituent elements can be easily formed at the same low temperature.

Further, since the vapor deposition atoms are excited by the collision between the irradiation ions 24 and the vapor deposition atoms as described above, this causes a high temperature / high pressure phase in the film 6 when boron is used as the group 3B element, for example. A cubic cubic zinc blende type boron nitride (c-BN) and a hexagonal wurtzite type boron nitride (w-BN) are formed even at low temperatures, and a film 6 having further excellent hardness and thermal conductivity is formed. Can be formed.

Next, more specific examples according to the present invention and comparative examples corresponding to conventional examples will be described.

(Example 1) As the substrate 2, high speed tool steel (SKH51) was used, which was placed in the holder 12 and then the inside of the vacuum vessel 10 was maintained at a vacuum degree of 1 x 10 ^-6 Torr or less. After that, two evaporation sources using electron beam 1
From Nos. 6 and 14, boron (purity 99.5%) and titanium (purity 99.99%) were heated and vaporized to be deposited on the substrate 2. At the same time, nitrogen gas (purity 99.999%) was introduced into the ion source 22 and ionized to extract nitrogen ions as ions 24, and the substrate was irradiated with acceleration energy of 10 KeV.

At this time, the ratio of boron atoms to nitrogen atoms contained in the formed film (B / N composition ratio) and the ratio of titanium atoms to nitrogen atoms contained in the formed film (Ti The amount of evaporation of each element and the amount of irradiation of nitrogen ions were adjusted so that each / N composition ratio) was 1.

In this way, B-Ti is formed on the surface of the substrate.
A film of a nitrogen compound made of a -N element was formed to a thickness of 1 μm.

Example 2 Using the same substrate as in Example 1,
After the inside of the vacuum vessel 10 was maintained at a vacuum degree of 1 × 10 ⁻⁶ Torr or less, aluminum (purity 99.999%) and titanium (purity 99.99%) were respectively supplied from two evaporation sources 16 and 14 using an electron beam. ) Was heated and vaporized to be vapor-deposited on the substrate. At the same time, nitrogen ions were extracted from the ion source 22 in the same manner as in Example 1, and the substrate was irradiated with acceleration energy of 10 KeV.

At this time, the ratio of aluminum atoms and nitrogen atoms contained in the formed film (Al / N composition ratio).
Then, the evaporation amount of each element and the irradiation amount of nitrogen ions were adjusted so that the ratio of the titanium atom and the nitrogen atom (Ti / N composition ratio) contained in the film similarly formed was 1.

In this way, Al-Ti is formed on the surface of the substrate.
A film of a nitrogen compound made of a -N element was formed to a thickness of 1 μm.

Example 3 Using the same substrate as in Example 1,
After the inside of the vacuum vessel 10 was maintained at a vacuum degree of 1 × 10 ⁻⁶ Torr or less, two evaporation sources 16 and 14 using an electron beam were used to obtain boron (purity 99.5%) and zirconium (purity 99.5), respectively. %) Was heated and vaporized to be vapor-deposited on the substrate. At the same time, nitrogen ions were extracted from the ion source 22 in the same manner as in Example 1, and the substrate was irradiated with acceleration energy of 10 KeV.

At this time, the ratio of boron atoms to nitrogen atoms contained in the formed film (B / N composition ratio) and the ratio of zirconium atoms to nitrogen atoms contained in the formed film (Zr / N composition ratio) is 1 respectively,
The evaporation amount of each element and the irradiation amount of nitrogen ions were adjusted.

In this way, B-Zr is formed on the surface of the substrate.
A film of a nitrogen compound made of a -N element was formed to a thickness of 1 μm.

Comparative Example 1 Using the same substrate as in Example 1, the inside of the vacuum chamber 10 was maintained at a vacuum degree of 1 × 10 ⁻⁶ Torr or less, and then two evaporation sources 16 using an electron beam were used.
From No. 14, boron (purity 99.5%) and titanium (purity 99.99%) were heated and vaporized to be vapor-deposited on the substrate. At the same time, nitrogen gas (purity 99.999%) was introduced into the vacuum container 10 to generate nitrogen plasma by high frequency discharge in the vacuum container 10 to nitride the vaporized atoms.

At this time, the ratio of boron atoms to nitrogen atoms contained in the formed film (B / N composition ratio) and the ratio of titanium atoms to nitrogen atoms contained in the formed film (Ti / The evaporation amount of each element and the irradiation amount of nitrogen plasma were adjusted so that each N composition ratio) was 1.

In this way, B-Ti is formed on the surface of the substrate.
A film of a nitrogen compound made of a -N element was formed to a thickness of 1 μm.

(Comparative Example 2) Using the same substrate as in Example 1,
After the inside of the vacuum container 10 was maintained at a vacuum degree of 1 × 10 ⁻⁶ Torr or less, boron (purity 99.5%) was heated and vaporized by an evaporation source 16 using an electron beam to be deposited on a substrate. . At the same time, nitrogen ions were extracted from the ion source 22 in the same manner as in Example 1, and the substrate was irradiated with acceleration energy of 10 KeV.

At this time, the evaporation amount of boron and the irradiation amount of nitrogen ions were adjusted so that the ratio of boron atoms to nitrogen atoms (B / N composition ratio) contained in the formed film was 1. .

In this way, a film of a nitrogen compound consisting of the BN element was formed to a thickness of 1 μm on the surface of the substrate.

(Comparative Example 3) Using the same substrate as in Example 1,
After the inside of the vacuum vessel 10 is maintained at a vacuum degree of 1 × 10 ⁻⁶ Torr or less, titanium (purity 99.99%) is heated and vaporized by an evaporation source 14 using an electron beam to vapor-deposit it on the substrate. It was At the same time, from the ion source 22 to Example 1
Nitrogen ions were extracted in the same manner as above, and the substrate was irradiated with acceleration energy of 10 KeV.

At this time, the evaporation amount of titanium and the irradiation amount of nitrogen ions were adjusted so that the ratio of titanium atoms and nitrogen atoms (Ti / N composition ratio) contained in the formed film was 1. .

In this way, Ti-N is formed on the surface of the substrate.
A film of a nitrogen compound containing an element was formed to a thickness of 1 μm.

(Evaluation) The above Examples 1 to 3 and Comparative Example 1
The hardness of the film was measured by the Vickers hardness under a load of 10 g for the film adherend in which the film of the nitrogen compound was formed on the substrate in the above-described manners. Further, the adhesion strength of the film was measured by a scratch tester with an AE (acoustic emission) sensor. The results are shown in Table 1.

[0055]

[Table 1]

All of Examples 1 to 3 had excellent hardness and adhesion, but Comparative Example 1 was inferior in hardness and adhesion. The hardness and adhesion of Comparative Example 1 were inferior because the ion irradiation was not used during the film formation, so that the BN bond in the film was not hard c-BN or w-BN as in Example 1. This is probably because it has a structure (h-BN) similar to that of soft hexagonal graphite and that a mixed layer was not formed at the interface between the film and the substrate.

In Comparative Examples 2 and 3, Examples 1 and 3 are used.
Although it had the same hardness and adhesion as the above, when comparing the generation state of the cracks of the indentation at the time of measuring the Vickers hardness, in Examples 1 to 3, cracks were formed at the tip of the indentation. No generation was observed, whereas in Comparative Example 2, cracks were clearly observed at the tip of the indentation. Further, in Comparative Example 3, cracks were also generated at the tips of the indentations, although the cracks were slightly generated.
It was found that the toughness of each of the films was inferior to that of the example.

[0058]

As described above, since the film constituting the film adherend of the present invention is a film of a nitrogen compound consisting of a 4A group element, a 3B group element and nitrogen, it is excellent in both hardness and toughness. Therefore, the film adherend of the present invention has good wear resistance, slidability and chemical stability. Moreover, since the mixed layer is formed at the interface between such a film and the substrate, the adhesion of the film to the substrate becomes excellent.

According to the manufacturing method of the present invention, the vapor deposition atoms are excited near the surface of the substrate by the collision between the irradiation ions and the vapor deposition atoms, so that the 4A group element, the 3B group element and A film of nitrogen compound consisting of nitrogen,
It can be formed at low temperatures without heating the substrate to high temperatures. Moreover, since the vapor deposition atoms are pushed into the surface of the substrate due to the collision between the irradiation ions and the vapor deposition atoms, at the same time as the formation of the film, at the interface between the film and the substrate, the constituent elements of both of the above are formed. The mixed layer can likewise easily be formed at low temperatures. As a result, the film having excellent adhesion can be formed regardless of the type of the substrate.

Further, since the vapor deposition atoms are excited by the collision between the irradiation ions and the vapor deposition atoms as described above, when the boron is used as the Group 3B element, for example, cubic cubic sphalerite is contained in the film. Type boron nitride (c-BN)
A hexagonal wurtzite type boron nitride (w-BN) is formed, and a film having more excellent hardness and thermal conductivity can be formed.

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing an example of a film adherend according to the present invention.

FIG. 2 is a schematic sectional view showing an example of an apparatus for carrying out the manufacturing method according to the present invention.

[Explanation of symbols]

 2 Substrate 4 Mixed Layer 6 Nitrogen Compound Film 10 Vacuum Container 14, 16 Evaporation Source 18 4 Substance Containing Group A Element 20 3 Substance Containing Group B Element 22 Ion Source 24 Ion Containing Nitrogen Ion

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akinori Ebe 47 Umezu Takaunecho, Ukyo-ku, Kyoto City, Kyoto Prefecture Nissin Electric Co., Ltd.

Claims (2)

[Claims] 1. A film of a nitrogen compound consisting of a Group 4A element, a Group 3B element and nitrogen of the periodic table of elements is formed on the surface of a substrate, and a mixed layer consisting of both constituent elements is formed at the interface between the film and the substrate. A film adherend formed by forming. 2. A substrate in a vacuum chamber, the vapor deposition of a substance containing a group 4A element of the periodic table of elements, the vapor deposition of a substance containing a group 3B element of the periodic table of elements, and the irradiation of ions containing nitrogen ions. Is performed to form a film of a nitrogen compound consisting of a Group 4A element, a Group 3B element and nitrogen on the surface of the substrate by the method described above.