JPS6156306B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention combines Zr into a sintered hard alloy mainly composed of Ti.
This invention relates to a sintered hard alloy whose cutting characteristics are significantly improved by containing Zr, Al, and oxygen, or Zr, Al, and oxygen. Conventionally, by adding Zr to cermet,
Alloys with improved wear resistance and thermal toughness are known, but cermets containing Zr and oxygen or Zr and Al
It is not known that the performance has been further improved by containing oxygen and oxygen. In the present invention, Zr can be replaced with Zr or Zr compounds such as
Titanium oxide, titanium carbonate, titanium carbonate nitride, and titanium oxynitride are mixed in the form of ZrC and ZrN.
Combining a species or two or more species and/or sintering with CO gas prevents deoxidation, or enriches oxygen to incorporate Zr and oxygen into the alloy, greatly improving cutting performance. It is an alloy made of aluminum. Furthermore, when Al is contained and Zr, Al, and oxygen are contained, the cutting performance is further improved. When Zr and oxygen are contained in the alloy, the plastic deformation resistance and thermal cracking resistance of the cutting edge during high-speed cutting decreases due to Zr.
This is an even more significant improvement than when used alone. The reason for this is not clear, but the bonding of oxygen in Zr occurs on the atomic order in the hard phase or binder phase of the alloy, adding properties similar to zirconium oxide to the cermet, improving plastic deformation resistance and thermal cracking resistance. It seems that this will be the case. In addition to oxygen in Zr, adding Al further improves cutting performance. As mentioned above, Zr
When Al and oxygen combine, properties similar to zirconium oxide are added, but when Al and oxygen combine, properties similar to aluminum oxide are added, and the properties of both zirconium oxide and aluminum oxide overlap, greatly improving cutting performance. considered to be a thing. a and/or a and/or a group metal and/or a compound with Al and a nonmetallic element;
For example, Ti ₃ AlC, Ti ₃ AlN, Ti ₂ AlC, Ti ₂ AlN,
The powders of V ₂ AlC, Ta ₂ AlC, and AlN (the above molecular formulas are averages, and of course there are variations in composition) are stable up to the point where they appear in the liquid phase, so no evaporation of Al occurs in the alloy. This is advantageous for stably dissolving Al in solid solution. Regarding the limitations of the alloy of the present invention, it is a hard alloy containing Zr and oxygen or Zr, Al and oxygen, and mainly consists of a and/or a and/or group a metal and a non-metallic component. Alloys combined with iron group metals, in which the metal component of the hard phase is Ti and the total amount of Zr in the alloy is 0.01 to 10% by mole.
The total amount of Al in the alloy is from 0.1 to 10% by weight. When Zr is 0.01% by weight or less, Zr has no effect, and when it is 10% by weight or more, sinterability deteriorates.
Also, when Al is less than 0.1% by weight, there is no effect of Al,
When it is 10% by weight or more, sinterability deteriorates. When Ti is less than 20 mol% of the metal component of the hard phase, the wear resistance as a cermet is lost. The total composition of the hard phase of the invention alloy in atomic ratio is (
a _A , a _B , a _C ) (C _u , N _v , O _w ) When expressed as _z , the range of A, B, C, u, v, w, and z is 0.15≦A≦0.98, 0.01≦B≦0.30 , 0.01≦C≦
0.50, 0.49≦u≦0.95, 0.04≦v≦0.49, 0.01≦w
≦0.20, 0.80≦z≦1.05. The ranges A, B, and C are suitable for maintaining cutting performance as a cermet, and Ti
It also contains the largest amount of group a metals. Next, regarding the nonmetallic components of the hard phase, the molar fractions of carbon, nitrogen, and oxygen in the nonmetallic components are u, v,
When expressed as w, if v is 0.04 or less, nitrogen will not have the effect of refining the alloy or stably containing oxygen, and if Zr and Al are added, v will be 0.49.
If it exceeds this, sinterability will deteriorate. Further, if w is 0.01 or less, there is no effect of oxygen inclusion, and if w is 0.20 or more, sinterability deteriorates. z is the stoichiometric parameter, which is the number of bonds in gram atoms of carbon and nitrogen and oxygen per gram atom of metal (Group A metal + Group A metal + Group A metal), varying between 0.80 and 1.05 . Below 0.80, a brittle phase exists, and 1.0
Above that, Free Carbon exists, but there are no performance problems up to 1.05. When the bonding metal is 100% by weight of the entire alloy,
The content is 3 to 25% by weight, but if it is less than 3%, the wettability will be poor, and if it is more than 25%, the abrasion resistance will deteriorate. In addition to iron group metals as bonding metals, Cu,
0.2~ of a metal that combines one or more types of Ag, Si, and B
Although the content is 2.5% by weight, the effect of the invention can be maintained even if a trace amount of 5% by weight or less is added by replacing the iron group metals Co, Ni, and Fe. In other words, adding Cu suppresses grain growth and improves thermal conductivity. It also has the function of making the surface and internal structure uniform. Adding Ag improves wettability and can also be expected to improve thermal conductivity. Si,B
Also contributes to improving sinterability. In addition, the metal bonding phase includes Ti, Zr, Al, Hf, V,
Naturally, hard phase forming elements such as Nb, Ta, Cr, Mo, W, C, N, and O are contained. As described above, the present invention uses oxides, carbonates, oxynitrides, and carbonate nitrides as raw materials and performs CO gas sintering as a sintering method to prevent deoxidation and/or
Alternatively, oxygen can be contained in the alloy by sintering a finished powder that is oxygen-enriched but does not contain oxygen with CO gas. Also CO
The gas pressure was set in the range of 0.01 to 300 Torr because
This is because below 0.01 Torr, oxygen is likely to be released as CO and CO ₂ gases, and above 300 Torr, carburization becomes intense and the carbon content fluctuates greatly. Applications of the alloy of the present invention are not limited to those described in the examples, but can also be applied not only to cutting tools but also to pen balls, wear-resistant tools, dies, wear-resistant parts (apex seals), ornaments, etc. Examples are shown below, but carbides, nitrides, carbonitrides such as TiC and TiN in the examples are replaced with TiC, TiC, and TiN for convenience.
Although it is displayed as TiN, it is actually TiCx or TiNx. Example 1 Commercially available TiC powder, TiN powder _, WC powder, Mo ₂ C powder and TiO _0.95 powder, as well as Ni powder, Co powder,
TaN powder, ZrN powder, and AlN powder were blended according to the composition shown in Table 1. This is TiC−Mo with a diameter of 10 mm.
- Add acetone using a Ni ball and an 18-8 stainless steel lined pot, and use a wet ball mill to
Mixed for an hour. To this mixed powder, 3% camphor was added and stamped at 2t/cm ² . When sintering this stamped body, in the temperature raising process,
The alloy is created under a vacuum of 10 ^-3 mmHg up to 1200°C, maintained at a CO gas partial pressure of 50 Torr from 1200°C to 1380°C, and then fired at 1380°C for 60 minutes under a vacuum of 10 ^-3 mmHg or less to create an alloy. did. The results of analysis of the obtained alloy are shown in Table 2. The mechanical properties of the obtained alloy are shown in Table 3, and the cutting performance is shown in Table 4. As is clear from Tables 3 and 4, Alloy A containing Zr and oxygen, Alloy B containing Zr, Al, and oxygen
There is almost no difference in transverse rupture strength and hardness between the alloys of the present invention and comparative alloy C, but as is clear from the cutting test results, alloys A and B of the present invention have superior wear resistance and plasticity resistance. It can be seen that the deformability and thermal fatigue toughness are far superior to Comparative Alloy C. It can be seen that the B alloy containing Zr, Al, and oxygen is particularly excellent.

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[Table] Example 2 a, a, group a carbides, nitrides, carbonitride powders and titanium carbonate, titanium oxynitride, titanium carbonate nitride, titanium oxide, Zr, Zr compounds, and group a and/or Group A and/or Group A metals and/or compounds with Al and non-metallic elements, Ni powder, Co powder, Cu powder, Ag powder, SiN powder, SiC powder, Si powder, BN powder, _TiB2 powder, etc. Alloys shown in Table 5 were prepared using various powders in the same manner as in Example 1. The mechanical properties of the obtained alloy are shown in Table 6, and the cutting performance is shown in Table 7.
Shown in the table. In addition, in Table 5, Zr is added to the hard phase.
Al is shown separated into a bonded phase all at once, but in reality it is
It is thought that Zr and Al are partially dissolved in both the binder phase and the hard phase. As can be seen from Tables 6 and 7, there is almost no difference in transverse rupture strength and hardness between the alloy of the present invention and the comparative alloy, but the cutting test results show that the alloys have excellent wear resistance, plastic deformation resistance, and thermal fatigue resistance. It can be seen that the alloy of the present invention is superior in toughness. Especially Zr, Al and oxygen

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[Table] Example 3 Using commercially available TiC powder, TiN powder, WC powder, Mo ₂ C powder, ZrC powder, Ni powder, Co powder, and TaN powder, the results shown in Table 8 were prepared in the same manner as in Example 1. An alloy was prepared as shown below. The mechanical properties of the obtained alloy are shown in Table 9, and the cutting performance is shown in Table 10. As can be seen from Table 8, this example does not use an oxide as a raw material, but since the same CO gas sintering method as in Example 1 is used, it can be seen that oxygen is contained in the alloy. Although there is no difference between the inventive alloy and the comparative alloy in terms of transverse rupture strength and hardness in Table 9, as is clear from the cutting test results in Table 10, the inventive alloy has wear resistance, plastic deformation resistance, It can be seen that the heat fatigue toughness is superior to the comparative alloys.

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Claims (1)

[Scope of Claims] 1. A hard alloy containing Zr and oxygen in an amount of 0.01 to 10% by weight when the total amount of Zr in the hard phase and bond metal is 100% by weight of the entire alloy, which comprises a, a, and An alloy in which a hard compound consisting of a group A metal and a non-metal component is combined mainly with an iron group metal, the metal component of the hard phase is mainly Ti, and the non-metal component of the hard phase contains carbon, nitrogen and oxygen, When the total composition of the hard phase is expressed as (a _A , a _B , a _C ) (C _u , N _v , O _w ) _z in atomic ratio, the range of A, B, C, u, v, w, z is as follows. 0.15≦A≦0.98 0.01≦B≦0.30 0.01≦C≦0.50 0.49≦u≦0.95 0.04≦v≦0.49 0.01≦w≦0.20 0.80≦z≦1.05 Iron group metals are alloys A sintered hard alloy characterized in that the content is 3 to 25% by weight when the total weight is 100%. 2 Ti is 20 mol% or more of the metal component of the hard phase and 95%
A sintered hard alloy according to claim 1, characterized by comprising the following: 3. A hard alloy containing 0.01 to 10% by weight of Zr and oxygen, where the total amount of Zr in the hard phase and bonding metal is 100% by weight of the entire alloy, and is composed of group a, group a, and group a metals and nonmetallic components. It is an alloy in which hard compounds consisting of Expressed as a ratio (a _A , a _B , a _C ) (C _u , N _v , O _w ) _z , the range of A, B, C, u, v, w, z is 0.15≦A≦0.98 0.01≦ B≦0.30 0.01≦C≦0.50 0.49≦u≦0.95 0.04≦v≦0.49 0.01≦w≦0.20 0.80≦z≦1.05, and furthermore, the iron group metal of the metal binding phase was 100% by weight of the entire alloy. A sintered hard alloy characterized in that the hard phase and the bonding metal contain Al in a total amount of 0.1 to 10% by weight when the total amount of the alloy is 100% by weight. 4. A hard alloy containing 0.01 to 10% by weight of Zr and oxygen when the total amount of Zr in the hard phase and bonding metal is 100% by weight of the entire alloy, and is composed of a, group a and group a metals and non-metallic components. It is an alloy in which hard compounds consisting of Expressed as a ratio (a _A , a _B , a _C ) (C _u , N _v , O _w ) _z , the range of A, B, C, u, v, w, z is 0.15≦A≦0.98 0.01≦ B≦0.30 0.01≦C≦0.50 0.49≦u≦0.95 0.04≦v≦0.49 0.01≦w≦0.20 0.80≦z≦1.05, and furthermore, the iron group metal of the metal binding phase was 100% by weight of the entire alloy. 3 to 25% by weight, and in addition to iron group metals, Cu, Ag,
0.2~ of a metal that combines one or more types of Si and B
A sintered hard alloy characterized in that it contains 2.5% by weight. 5 a, a, group a metal carbides, nitrides,
A mixture of one or more oxides, carbonates, carbonitrides, one or more Zr, ZrC, or ZrN, and iron group metal, and part or all of the heating, sintering, and cooling processes. The CO gas partial pressure is maintained at 0.01 to 300 Torr intermittently or continuously to prevent deoxidation, and the alloy is made of group a, group a, and a metals and nonmetallic components containing Zr and oxygen. It is an alloy in which hard compounds are combined mainly with iron group metals, the metal component of the hard phase is mainly Ti, the non-metallic components of the hard phase include carbon, nitrogen, and oxygen, and the total composition of the hard phase is expressed as an atomic ratio ( a _A , a _B , a _C ) (C _u , N _v , O _w ) _z , the range of A, B, C, u, v, w, z is 0.15≦A≦0.98 0.01≦B≦0.30 0.01≦C≦0.50 0.49≦u≦0.95 0.04≦v≦0.49 0.01≦w≦0.20 0.80≦z≦1.05, and furthermore, the iron group metal of the metal binding phase is 3 when the entire alloy is 100% by weight. - 25% by weight, and the total amount of Zr in the hard phase and the binding metal is 0.01 to 10% by weight, and the total amount of Zr in the binding metal is 0.01 to 3% by weight. 6 a, a, group a metal carbides, nitrides,
One or more of oxides, carbonates, and carbonitrides, and one or two powders of titanium oxynitride and titanium carbonitride.
One or two types of Zr or ZrC or ZrN
Deoxidation can be prevented by mixing ferrous metals with iron group metals and maintaining the CO gas partial pressure intermittently or continuously at 0.01 to 300 Torr during part or all of the heating, sintering, and cooling processes. , an alloy in which a hard compound consisting of a, a, and a group metals containing Zr and oxygen and non-metal components is combined mainly with iron group metals, and when the entire alloy is taken as 100% by weight, the hard phase and The total amount of Zr in the bond metal is 0.01 to 10% by weight, the metal component of the hard phase is mainly Ti, the non-metallic components of the hard phase include carbon, nitrogen, and oxygen, and the total composition of the hard phase is atomic. Expressed as a ratio (a _A , a _B , a _C ) (C _u , N _v , O _w ) _z , the range of A, B, C, u, v, w, z is 0.15≦A≦0.98 0.01≦ B≦0.30 0.01≦C≦0.50 0.49≦u≦0.95 0.04≦v≦0.49 0.01≦w≦0.20 0.80≦z≦1.05, and furthermore, the iron group metal of the metal binding phase was 100% by weight of the entire alloy. 3 to 25% by weight, and the Zr content in the bonding metal is 0.01 to 3% by weight.