JPS60234961A - Hard material parts for tool having very hard coating layers - Google Patents

Abstract

PURPOSE:To obtain hard material parts for a tool having very hard coating layers by forming a cubic BN-base coating layer having a specified atomic weight ratio of B/(N+O) and contg. Ti and/or Al in a specified ratio to B atomic weight on the surface of a hard substrate. CONSTITUTION:The very hard coating layer is formed on the surface of each hard material substrate for a tool. The layer has 0.5-10mum average thickness and consists of cubic BN-base fine grains of <=1mum average grain size having 0.95-1.2 atomic weight ratio of B/(N+O) and contg. Ti and/or Al in 1/500-1/20 ratio to B atomic weight.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a hard material component for tools such as cutting tools and wear-resistant tools having an extremely hard coating layer with excellent wear resistance. The ultra-hard coating layer is characterized in that it is mainly composed of cubic boron nitride (hereinafter referred to as cBN).

[Conventional technology and its problems]

Various conventional tool materials (i.e. cemented carbide, cermets), c
BN-based ceramics or silicon nitride (hereinafter referred to as S I 3
Base ceramics (denoted as N4) have excellent wear resistance and toughness, and have been used as cutting tools and wear-resistant tools used under harsh conditions. Various coatings have been tried and put into practical use to increase wear resistance. As the coating material, carbides and nitrides of Ti and Hf, A
J oxide is widely used because it can be chemically vapor deposited, but in recent years diamond coating and cBN combing have also been tested. In particular, cHN-coated tool materials are expected to be used for cutting /dlr1 and cast iron, but since cBN crystals are stable at high pressure, coating by physical vapor deposition at normal pressure or in i4: If the physical d?cBN extracted machine produces? The range of the i conditions is narrow, and the cBN production rate is low, that is, the produced tetragonal layer contains phases other than cBN and foreign substances. Therefore, the current situation is that there is no material with sufficient wear resistance.

[Purpose of the invention]

The purpose of this invention is to increase the cBN a) content in the coating layer as much as possible, and as a result, to provide a coating material for tools that has a coating layer with improved hardness and has extremely improved wear resistance as a whole. It's about getting. .

[Knowledge]

As a result of extensive investigation, the present inventors obtained the following knowledge.

a) In order to increase the content of cHN in the SA layer, it is important to select not only physical conditions but also chemical conditions, that is, composition; b) In addition to boron and nitrogen components, A small amount of one or both of Ti or Al components is deposited on the coating layer, and Ti or AA is added to the coating layer.
By including one or both of the following, the proportion of cBN in the resulting coating layer increases and the hardness of the coating layer increases significantly. When provided on the surface of the tool, the wear resistance of the material for the tool is extremely excellent.

[Matters essential to the structure of the invention and embodiments]

This invention was invented as a result of further research based on the above findings. 1) A hard material for tools is used as a base material, and boron/
The atomic ratio of (nitrogen + oxygen) is in the range of 0,695 to 1.2, and one or both of titanium and aluminum is contained in a ratio of 11,500 to 1/20 to the number of boron atoms. 1. A hard material part for a tool having an ultra-hard coating layer, characterized in that the main body is provided with a coating layer having an average layer thickness of 0.5 to 10 μm and composed of fine particles with an average particle size of 1 μm or less.

2) The ultra-hard coating according to claim 1, wherein the hard material forming the crystal phase is an ultra-hard alloy made of a bonding metal and one or more of carbides and nitrides of group 4a, 5a and 6a metals. Hard material parts for tools with layers.

3) The hard material serving as the base material is a super hard alloy made of a bonded metal with one or more of the carbides and nitrides of group 4a, 5a and 6a metals, and the inner layer is made of carbides and nitrides of Ti and Hf, A coating having one layer or multiple layers of one compound or a mixture of two or more of the group consisting of carbonitrides, carbonitrides, carbonates, and nitrides and oxides of A-1. Claim 1 which is a super hard alloy
A hard material part for a tool having an ultra-hard coating layer as described in 1.

4) The hard material serving as the base material is CBN as a dispersed phase:
3o to 93 capacitance and Ti carbides, nitrides, oxides and borides as binding phases, Al nitride.

Claim 1, which is a cBN-based ceramic consisting of a one-phase or multi-phase N9-7 volume ratio of one compound or two or more solid solutions from the group consisting of borides, oxides, and Sr3N4. A hard material part for a tool having an ultra-hard coating layer as described.

5. The hard material used as the base material is Ti carbide, nitride,
and carbonitrides, nitrides and oxides of Al, oxides of Y, oxides of Si, and oxides of Zr. A hard material part for a tool having an ultra-hard coating layer according to claim 1, which is made of 3N4 ceramics.

6) Hard materials serving as base materials include Ti carbides, nitrides, and carbonitrides, AJ nitrides and oxides, Y oxides, S
One or more of the oxide of i and the oxide of Zr is 5 to 20% by weight, and the remainder is 813N4.
i One or two compounds from the group consisting of carbides, nitrides, carbonitrides, carbonitrides, and carbonates of Ti and Hf, and nitrides and oxides of AI, as an inner layer on the surface of the 3N4-based ceramics. A hard material part for a tool having an ultra-hard coating layer according to claim 1, which is a coated ceramic having one layer or multiple layers of the above mixture.

[Components of the invention]

The configuration of the present invention will be described below, focusing on the coating layer.

1) Atomic ratio of boron/(nitrogen+oxygen) This value is preferably in the range of 0.95 to 1.2. cBN is a chemical entity, and theoretically the boron/nitrogen atomic ratio (hereinafter referred to as the B/N ratio) is 1/1, and large cBN single crystals are very close to this value, but in general, physical steaming is When a coating layer made of boron nitride is produced using the method, the H/N ratio can be arbitrarily set within a wide range, and the oxygen component is replaced with a nitrogen component. As the number of wrinkles in the oxygen component increases, the number of B-N bonds decreases, and the number of H-0 bonds increases accordingly.
The ratio of +0) and R) become smaller. That is, 13/(
If the ratio of N+0) is less than 0.95, the number of 13-0 bonds increases or the nitrogen component becomes excessive, resulting in a decrease in the production rate of cBN and a decrease in the hardness of the resulting coating layer.

On the other hand, when the ratio of H/(N+0) is greater than 1.2, the boron component becomes excessive, so the cBN production rate decreases and the hardness of the coating layer decreases. Therefore, the ratio of B/(N+0) was determined to be 0.95 to 1.2.

1) Content of titanium or aluminum If one or both of titanium or aluminum are deposited simultaneously and included in the coating layer, the coating will have a higher cB in the layer
The N production rate increases and the hardness increases significantly.

When the amount of titanium or aluminum is less than 11,500 relative to the number of boron atoms, there is no significant effect on improving the cBN production rate. On the other hand, if it exceeds 1/20, the entire formed coating layer will soften, so the range should be reduced to 1/20.
It is set as 1500 to 1/20.

III) Content of cBN Boron nitride has two transformations: cBN and hexagonal boron nitride (hereinafter referred to as HBN).
(i.e., total nitride 1l (the ratio of cBN to Al is over 500% by weight).

+V) Particle diameter cB of particles forming a coating layer such as CBN
It is preferable that the particles forming the coating layer such as N be composed of cotton balls with an average particle size of 1 μm or less. be.

■) 4~ on average.

c) The ISN-based layer XI may have an average layer thickness of 0.5 to 10 μm. (), 5 μm droplets have a small effect on wear resistance 1ii1, and J This is because the reaping performance is close to the limit and the coated parts are more likely to chip.

(A Ming Imperial matter 1) The coating i- of the present invention is formed by, for example, a sputtering method.

For example, when forming a coating layer by sputtering, it is possible to change the B/(N + g) ratio of the coating layer by changing the degree of purity and the N2/Ar ratio in the atmospheric gas. By changing the ratio of the distance between the N target and the base material and the distance between the Ti or Al target and the base material, the (Ti + AA
) / B ratio can be changed, and the average layer thickness of the coating layer can be changed by changing one of the following: vacuum degree, distance between target and substrate, and deposition time. In order to form a coating layer having the ratio of H/(N+0), the ratio of (T+A/)/B and the average layer thickness described in the claims of this application, a sputtering method can be used. In the case of vacuum degree 10-10 degree H9-
N2/Ar ratio 1/20 to 5/1. Distance between HBN target and base material: 10~70cm, Ti or A vine
Distance between get and base material 1i1it15~l 00 xme
The deposition time is preferably 1.0 to 20 hours. Further, in order to make the average particle size of the particles constituting the coating layer 1 μm or less, sputtering is preferably performed at a base material heating temperature of 150 to 1000° C. and a bias pressure of 50 to 500 V.

〔Example〕

Hereinafter, the structure and effects of the present invention will be described in detail using Examples as well as Comparative Examples.

Example 1 and Comparative Examples A powder formulation consisting of 94% by weight of WC powder with an average particle size of 1 μm and 6% by weight of Co powder with the same 1.2 μm was mixed in alcohol for 72 hours in a ball mill, taken out and dried. ,l
The molded body was press-molded at a pressure of t/cm'' and sintered in hydrogen at 1400''C for 1 hour. By applying pressure in this way, a super hard alloy made of WC and CO is manufactured according to ISO standard 5.
A cutting tip conforming to NGN432 was manufactured.

This cutting chip was used for profit and loaded into a high frequency sputtering device targeting HBN. A second titanium target was installed inside this device, allowing titanium to be deposited simultaneously with boron nitride. Furthermore, a mechanism was provided to rotate the chip once, so that a vapor-deposited coating layer with a uniform thickness could be obtained on the chip surface.

At a substrate heating temperature of 4()0°C, a bias voltage of 150 V between the substrate and the HBN target, and a N2/Ar ratio of 1/4, HBN was sputtered under a vacuum of 10 gml. At the same time, The titanium target was applied with a voltage of -1 oonv to cause titanium sputtering, and the distance between the titanium target and the base material was set at 20 to 90 mm.
The amount of titanium contained in the vapor deposited coating layer on the chip surface can be varied by changing the titanium deposition rate between 11 and 11 (fixed at 30 cages without changing the distance between the HBN target and the substrate). changed. The deposition time was 6 hours in both cases. In this way, the present invention products &1 to 6 and comparative product A
1-5 were manufactured.

Also, when performing the above sputtering, by fixing the distance between the titanium target and the base material at 50 dragons, changing the vacuum degree of the atmosphere, and changing the N2/Ar ratio,
Inventive products A7-9 and comparative products /I66-7 were manufactured by changing the ratio of B/(N+o) of the vapor-deposited coating layer on the chip surface.

B/
(N+O) ratio, Ti/B ratio, CBN/(cBN+H
The weight ratio of BN), the average particle diameter of the particles constituting the coating layer, the average layer thickness, and the Vickers hardness were measured, and the results are shown in Table 1. (The conventional product is only a base material without a coating layer.) The weight ratio of cHN/(cBN+HBN) was calculated by X-ray diffraction analysis.

The average particle size of the particles constituting the coating layer was determined directly from a scanning electron beam image of the fracture surface.

Furthermore, the average layer thickness was measured from a scanning electron beam image of the fracture surface or a polished cross section.

Next, a cutting test was conducted under the following conditions using the above-mentioned products of the present invention, comparative products, and conventional products, and the results are also shown in Table 81.

Cutting test> Rigid material: FC30 (Prinel hardness: 250) Cutting speed:
250m/min feed: 0. 20m evening/rev.

Depth of cut: 3 Dragon cutting oil: Emulsion type As shown in Table 1, as the amount of Ti in the coating layer increases, the cBN production rate of the coating layer increases, the Vickers hardness also increases, and Ti/B (atomic number It is maximum when ratio) = 0.01, but if it increases beyond the scope of this invention,
Hardness decreases significantly.

Also, the ratio of Ti / B is assumed to be constant, and B / (N +
0), this value increases from 0.97 to 110
If the hardness is outside the range, the hardness decreases. In addition, with only the base material (conventional product) that does not have a layer to be laminated according to the present invention, the tool life is 0.
It can also be seen that the tool life of the inventive product is 11 to 20 minutes, whereas the comparative product/I61, which has a coating layer containing cBN but not Ti, has a tool life of 7 minutes. .

Example 2 and Comparative Examples Using the same equipment as in Example 1, cBN-based coating layers were coated on the surfaces of the various substrates shown in Table 2 by high-frequency sputtering.

The conditions for forming the laminated layer at this time were almost the same as in Example 1, but by fixing the distance between the Ti target and the base material at 50 mm and changing the deposition time between 0.5 and 30 hours. Inventive products A1-10 and comparative products I61-2 were manufactured by changing the average layer thickness of the resulting coating layer.

For each of the above-mentioned products of the present invention and comparative products, the ratio of B / (N + 0), Ti / B ratio, cBN
The weight ratio of /(cBN+HBN), the average particle diameter of particles constituting the coating layer, and the average layer thickness were measured, and the results are shown in Table 2.

Furthermore, using the products of the present invention, comparative products, and conventional products A1 to A5, a cutting test was conducted under the same conditions as in Example 1, and the tool life was measured. The results are also shown in Table 2.

From Table 2, it can be seen that the coating i- of the present invention has the effect of extremely improving the abrasion resistance even when coated on various base materials, and the average layer thickness of the coating layer is as follows. It can also be seen that outside the scope of the invention, the effect of improving wear resistance by the coating layer is significantly reduced.

Example 3 By placing an HBH target and an AJ target in a high-frequency sputtering device and sputtering them alternately, various boron nitride TA layers with different AJ contents were formed into 8! It was coated on the surface of 3N4 ceramics.

The base material 513N4-based ceramic has the following composition: 80 Si3N4-10 Tt N 5 A11
A material containing N 5 Y2O3 (the above, weight %) was used.

Base material heating temperature: 650°C, N2/Ar ratio: 11
The true nitrogen degree was 5°, the degree of nitrogen was 0.8×10-3 HI, and the bias vehicle pressure of the base material was 200V. The deposition rate was about 0.5 μm/hour, and a boron nitride coating layer with an average layer thickness of 5 μm was deposited on the substrate over a deposition time of 10 hours.

The ratio of B/(N+0) of the obtained coating layer was 1.02, and the average particle size of the particles constituting the coating layer was 0.07 μm. The weight ratio of cHN/(cBN+HHN) obtained from the peak value of Xa diffraction differs depending on the AA/B ratio, but the A711/B ratio reaches its maximum near o and oi, showing a value of 0.95. Ta.

Also, this A/! A cutting tip having a coating layer with a /H ratio of 0.01 exhibited a tool life of 150 minutes under the cutting conditions of Example 1. For comparison, the tool life of the base material without the boron nitride coating layer was 40 minutes.

Claims (1)

[Claims] l) A hard material for tools is used as a base material, and boron/
The atomic ratio of (nitrogen + oxygen) is in the range of 0.95 to 1.2, and one or both of titanium or aluminum is contained in a ratio of 11500 to 1/20 to the number of boron atoms, Mainly cubic boron nitride, average grain size 1I
Average layer thickness composed of fine particles of ITrL or less: 0.5~
A hard material part for a tool having an ultra-hard coating layer, characterized in that the coating layer has a thickness of 10 μm. 2) The hard material to be exploited is a super hard alloy made of a bonded metal with 18 or more carbides and nitrides of group 4a, 5a and 6a metals. Hard material parts for tools with. 3) The hard material serving as the base material is a super hard alloy made of a bonding metal with 1ffi or more of carbides and nitrides of group 4a, 5a and 6a metals.
1 of the group consisting of carbides, nitrides, cash compounds, carbonitrides, and carbonates of A/, and further nitrides and oxides of A/
2. A hard material part for a tool having an ultra-hard coating layer according to claim 1, which is a punched ultra-hard alloy having one layer or multiple layers of the compound 1a or a mixture of two or more thereof. 4) The hard material serving as the base material is cubic boron nitride as a dispersed phase: 30 to 93 capacitance and carbides, nitrides, oxides and borides of Ti as a binder phase, nitrides and borides of A/ The claim is a cubic boron nitride-based ceramic consisting of l-phase or multi-phase near 0 to 7 volume ratio of one kind of compound or two or more kinds of solid solutions from the group consisting of A hard material part for a tool having an ultra-hard coating layer according to item 1. 52 The hard material serving as the base material is Tj carbide, nitride,
and carbonitrides, nitrides and oxides of A7, oxides of Y, oxides of Si, and oxides of Zr. A hard material part for a tool having an ultra-hard coating layer according to claim 1, which is a silicon-based ceramic. 6) The hard material serving as the base material is Ti carbide, nitride, and carbonitride, AI nitride and oxide, Y oxide,
One or two of the oxide of Sl and the oxide of Zr
Carbide, nitride, carbonitride of '1゛i and -1f as an inner layer on the surface of a silicon nitride-based ceramic consisting of 5 to 20i mass % and the remainder silicon nitride. It is a phylogenetic seciminox having one layer or multiple layers of one compound or a mixture of two or more of carbonate nitrides, carbonates, and nitrides and oxides of AI. Super hard 1- according to claim 1
Hard material parts for tools with no coating layer 3.