JPS59162270A - Surface coating method - Google Patents

Abstract

PURPOSE:To form a surface coating film of Al2O3 at a high growth rate on a base body by bringing a base material of a sintered hard alloy, etc. heated to a high temp. into contact with reactive gas contg. an adequate amt. of additive such as TiCl4, etc. and consisting of H2, AlCl3, an oxidizing agent, etc. CONSTITUTION:The surface coating of Al2O3 at a high rate of growing the film at which industrial production is permitted is made possible by adding 0.5- 30vol% >=1 kind among TiCl4, ZrCl4 and HfCl4 to the reactive gas consisting of H2, AlCl3, an oxidizing agent and/or hydrolyzing agent in a surface coating method by which a base material consisting of a sintered hard alloy, cermet or ceramics heated to 500-1,500 deg.C is brought into contact with the above-mentioned reactive gas and Al2O3 is coated on the surface of said substrate. If the amt. of the TiCl4, etc. to be added is <=0.5%, the growing rate of the film depends on the concn. of the TiCl4, etc. and therefore such amt. is undesirable. If >=30%, the hardness of the Al2O3 coated film decreases considerably and therefore such amt. is undesirable.

Description

[Detailed description of the invention] B. Technical field The present invention relates to improvements in methods for coating surfaces of cemented carbide.

BACKGROUND TECHNOLOGY So-called superstructures are made by bonding one or more carbides and/or carbonitrides selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten with an iron group metal. Surface-coated cemented carbide chips (hereinafter referred to as coating chips), which are made of hard metal and coated with a hard thin film by chemical vapor deposition, have both the toughness of the base material and the wear resistance of the surface. It is widely used as a cutting tool material. Titanium carbide, carbonitride, titanium nitride, hafnium nitride, aluminum oxide, etc. are used as the hard coating. In recent years, in order to improve efficiency, cutting speeds of 5 degrees have been increasing, and in order to respond to this trend as cutting tool materials, we have improved hardness at high temperatures, mechanical stability, ++'IJtOxidizing properties, etc.Kasutrei has become a heavy ring, and from that point on, oxides, especially aluminum oxide, have come to be used mainly for hard film formation.Production The method involves heating a cemented carbide substrate to 5D D''C to 1500'C and treating it with hydrogen, aluminum trichloride, an oxidizing agent and/or a hydrolyzing agent, usually from the group consisting of water, carbon dioxide, -carbon oxide. Then, a reaction gas consisting of a flaming gas (1) is brought into contact with the surface of the substrate + rt to coat aluminum using the so-called chemical vapor deposition method (
I'm offering this. A known method for coating the surface of aluminum oxide is a chemical vapor deposition method in which a reactive gas consisting of hydrogen, aluminum trichloride, an oxidizing agent, and a hydrolyzing agent is coated on the surface of the surface. Q is very slow at 01 μm/hr ~ 0.31 b m/hr, so it is not widely used as a coating chip (
The thickness of the aluminum oxide provided is 1
, Q p, rn -5,0 μm is covered by 1
It is necessary to hold it for a long time of 1° from 011 to 71. Heating the substrate at such high temperatures for long periods of time is undesirable as it can cause serious deterioration.As a solution to this problem, surface coating with aluminum oxide by the known chemical vapor deposition method is proposed. The reaction gas of the 11% chemical vaporization method, which is a method of
A knob method has been disclosed which significantly increases the growth rate of aluminum oxide films. Example 10 of this Japanese Patent Application Laid-open No. 111''154-10614 Aluminum oxide coating conditions described here (Koshitosugi commercially available Tic
Coating chip (product name AC720) model number SNMN
4ro 2.1000 IM+ -1 stainless steel u1
50mm x 500mm reaction vessel (charged +%%
, (Coating with hyaluminum laminate was performed. The aluminum oxide coating conditions were as follows: (2 to 90 volumes i; j 2% 1, to ICl 3 to 2 volumes: I): %, C02 6 volumes; , 1%, Ticl is 04 50 Torr, reaction/ll+'1 degree osc'c, reaction time is 111'';1''
The lie that was told is that the reaction gas
In the IKI Al"te 1.), 12 μm aluminum oxide was removed from Mf, M, and the reaction gas was discharged into the exhaust section (Fig. 1, section B) (here, aluminum oxide was 06 μm thick). 4" (Mozu, Wang Ao r2
Only 600 throws charged from part A to part 0 in Fig. 7 Waychinov (ko, -4-kisuushi 5 open 11f
No. 454-IO314-(The disclosed method is difficult to produce industrially.

C.9 Disclosure of the Invention 1-1 of the present invention is among the above; providing a method for surface ablation of aluminum oxide, which has a significantly high film growth rate and is a major enabler of industrial production; There is G. The inventor is q,
lJ open/close 4-1031. The composition of the surface aluminum oxide layer of the aluminum oxide coated chip prepared by the disclosed method was analyzed using spectroscopy. Nu I:-
Assuming that titanium exists in the form of titanium dioxide, as much as 1% of 63-fold neat was detected (
λ・↑In Figure 1B, the shape of titanium dioxide is:
・E,: Only ili:% or less was detected. This indicates that the growth rate of oak wood in aluminum oxide, which is also disclosed in Japanese Patent No. 54-10314, is the same as the amount of titanium tetrachloride added to the reaction gas. /), 4#, 7, O, F3p, m /
A high rate of growth of the hyaluminum acid film was obtained (on the contrary, only a small amount of tetrachloride was consumed in the exhaust section of the reactant gas, which has a low concentration). It is considered that a growth rate of only 0.2 μm and 7 hours was obtained.

4'f 1986-10314-υ- discloses that the amount of titanium tetrahydride added to the reaction should be 006-05% by volume under favorable pressure and 0.2% by volume or less. However, the amount of titanium oxide added (the growth rate of aluminum oxide) is disclosed only up to approximately 0.12 volume percent of titanium tetrachloride. I conducted an experiment to see what would happen if the addition of titanium (I:) was increased.The results of the experiment are shown in Figure 2 (not shown).As a result, the cooling power of titanium tetrachloride
i, FB knee or 7-koshika (the amount of titanium tetrachloride added (this depends on the film formation and zeta conformity, 0,5
I discovered the surprising fact that it remains almost constant above the capacity %. Therefore, if the reaction gas (titanium tetrachloride is at least 05'rφ11) [% or more, preferably 1% by volume or more] is added, the concentration of titanium tetrachloride ( Since the growth rate of this film does not depend on the location Q of the reaction vessel, I thought that it would be possible to obtain a constant film formation Ju, 11j I=. Therefore, when we actually conducted an experiment using the equipment shown in Figure 1 with the addition of 1.5% titanium tetrachloride, the effect was as expected. The detailed reason why the film growth rate is almost the same when the amount added to the reaction gas is less than 5% by volume is unknown, but when the amount of titanium added to the reaction gas is less than 5% by volume, titanium It is thought that titanium oxide will precipitate out if the titanium oxide is dissolved in solid solution.

Note that this effect is not limited to titanium tetrachloride Q, but also to titanium tetrachloride.
Vconium, hafraum tetrachloride (also recognized, '1.
It was found that when zirconium tetrachloride was added to No. 1, the cutting ability was significantly improved when a mixture of aluminum oxide and zirconium oxide was added. Also 1・, 6
It goes without saying that the effect G remains the same even if the salt substance to be added is a halide other than an oxide. In addition, the addition of titanium tetrachloride is less than 0.5% by volume, but it depends on the growth rate of the film or the concentration of titanium tetrachloride (it is not preferable to exceed 30% by volume because it depends on this). Significant decrease in hardness l; JJ grinding performance - unfavorable.

As mentioned above, Examples (Explanation 3, Example 1 Commercially available Tic coach ink - Chia)
Name A C720) Model number SNMN432.1000 was coated with aluminum oxide using a trowel. Note that the conditions for coating aluminum oxide were as shown in 1. below.

Reaction gas composition H290 volume 11)% AlCl32 yt CO2' (5// TiCl4t5 yt Co Q, 5 // Reaction gas flow rate 2 m, 7 seconds Reaction gas pressure 50 To r r 111□lV, 950"C Reaction time 6 The result is a throw away tube of 10 DOs (where the thickness of the aluminum oxide coating is 10-D2
It was μm. Figure 1 A, B, C section ζ Coated throw 7
The weight knobs were designated as itA, B, and C, respectively, and commercially available aluminum oxide 17Li'n and TTIC61 were used for comparison.
The material coated with L was designated as D, and a hardness cutting test was conducted under the above conditions.

Cutting agent F C25 1; IJ cutting conditions V-150m/' molecule 20.4 Q
mn1.7 r d = 2 mm After cutting for 10 minutes, the flank wear of A, B, C, and D was Q, i 3 mm to 0.22 mm, and all of the G trowels still had cutting +JJ performance.

Example 2 Commercially available Tic coating Kutinoff (trade name AC720)
Model number SNMN 432 G trowel] Under these conditions (acid (
Then, aluminum coating was applied. Note that the conditions were the same as in Example 1 except for the composition of the gas.

Table-1 Throw 7 way knobs from E to ■ (ζi of iron example 1)
J cutting edge +'l- (Flank wear of 0 and 5' cut for 5 minutes with a trowel is Q1't5 +', :n+, F is Q13m)
m, G was Q21mm, H was CI22+i+iil (on the other hand, King was 0.58mm. Also, J could only be cut in 4 minutes and 15 seconds.

ISO, MIO root cemented carbide, type No. SN, VIN
After coating 432G CoTie with a thickness of 6 μm '01 +Q, it was coated with aluminum oxide l under the following conditions.

Reaction gas composition H288 Kasa1. :%AlCl3
3 Volume: 119% CO26 Answer: 11:% ZrCl45% by volume Reaction gas flow rate 15 m/sec Reaction gas pressure 2 Q Torr Reaction temperature 950°C Reaction time 3 hours As a result, 1.0 μm of aluminum oxide was coated 3, 1 with the cutting nest of Example 1 using this Narrow Away Knob.
After cutting for 0 minutes, flank wear was Q''16 mm.

Example 4 Same experiment as Example 6, but with ZrC and L instead! YHfCL
was added as an addition. The result was a coating of 09 μm of acid (hyalium monium).

1 is an aluminum chloride generator, 2 is an electric furnace, 6 is a reactor, 4 is an electric furnace, 5 is a cold trap, 6 is a vacuum extraction device, 11 is a charging section for metal AI, and 61 is a profiteering device. Indicates joining.

Figure 2 shows the effect of adding titanium tetrachloride on the film growth rate of 7;:1, where A is the opposite of 1. Temperature 1oo.

℃, B 950 ℃, Cii 900''C not shown.

Agent: Patent Attorney - Tetsuji Nidai, 1. .

7.1) Child 7 7p figure Figure Chrysanthemum ■: [p4 (capacity%)

Claims (1)

[Claims] 500 to 1500°C (heated base material made of cemented carbide, cermet, or ceramics) is heated to a reaction gas of hydrogen, aluminum trichloride, an oxidizing agent, and/or a hydrolyzing agent (
In the surface coating method of coating the profiteer surface Q aluminum dioxide by contacting it, 05
~60% by volume of titanium tetrachloride, zirconium tetrahide,
Four-warm heating system