JP2019077930A - Hard phase dispersed nickel group intermetallic compound composite sintered material, manufacturing method therefor, and corrosion resistant abrasion resistant component using the material - Google Patents

Abstract

To provide a corrosion resistant abrasion resistant material suitable for use in a corrosion resistant abrasion resistant component such as a cylindrical sleeve for pump shaft or the like, a corrosion resistant abrasion resistant mold, a corrosion resistant abrasion resistant tool or the like, and a manufacturing method therefor.SOLUTION: A hard phase dispersed nickel group intermetallic compound composite sintered material containing a first phase of 35 vol.% to 80 vol.% and a second phase of 20 vol.% to 65 vol.% is obtained by mixing a hard powder (the first phase) consisting of solid solution body of Ti, Mo and/or carbide, nitride or carbonitride of W, and a material (the second phase) containing 75 at.% to 85 at.% of nickel (Ni), 8 at.% to 13 at.% of silicon (Si) and 3 at.% to 13 at.% of titanium (Ti) and becoming a binding material of the hard powder to manufacture a mixed powder or an alloy powder, and heating and sintering the mixed powder or the alloy powder with adding pressure.SELECTED DRAWING: None

Description

  The present invention relates to a hard phase-dispersed nickel-based intermetallic compound composite sintered material, a method for producing the same, and a corrosion-resistant wear-resistant part using the material.

As materials for corrosion resistant sliding parts such as cylindrical sleeves for pump shaft, corrosion resistant wear molds and corrosion resistant wear tools etc., WC-Ni cemented carbide with high hardness and excellent corrosion resistance and wear resistance It is used.
However, the use environment including seawater and the corrosion resistance in an acidic aqueous solution are not sufficient, and the application range is limited to a very narrow range.

Here, Ni ₃ (Si, Ti) -based intermetallic compounds have been developed as materials excellent in corrosion resistance (patent documents 1 and 2 and non-patent documents 1 to 4), and hydrochloric acid of Ni ₃ (Si, Ti) alloy The corrosion resistance against sulfuric acid, nitric acid, etc. is shown in comparison with stainless steel and Ni, but Ni ₃ (Si, Ti) alone has hardness as a substitute for the corrosion resistant wear resistant member to which a cemented carbide material is applied. And the wear resistance was not sufficient.

Moreover, in order to solve the problems of corrosion resistance and wear resistance, Patent Document 3 combines Ni ₃ (Si, Ti) with a Ti-based hard material (carbide, nitride, carbonitride, oxide and boride). Materials have been proposed. A Ti-based hard material and a Ni ₃ (Si, Ti) phase ratio are widely described as a material excellent in high temperature properties, containing 10 to 90 vol%, preferably 10 to 60 vol% of TiC.
However, compared to hard materials such as TiC, the Ni ₃ (Si, Ti) phase is easily corroded, and when used near room temperature, if the Ni ₃ (Si, Ti) phase ratio is high, the hardness of the material itself And wear and tear due to wear, which are not sufficient materials in terms of corrosion resistance and wear resistance.

Public disclosure 3-274242 JP-A-5-320794 JP 2014-169471

Sanat Wagle et al., Corrosion Science 53 (2011), 2514-2517 Gadang Priyotomo et al., Applied Surface Science 257 (2011), 8268-8274 Sanat Wagle et al., Corrosion Science 55 (2012), 140-144 Gadang Priyotomo et al., Corrosion Science 60 (2012), 10-17

As mentioned above, WC-Ni-based materials having high hardness and excellent corrosion resistance and wear resistance as materials for corrosion resistant wear and sliding parts such as cylindrical sleeves for pump shafts, corrosion resistant wear molds and corrosion resistant wear tools and the like Carbide materials are used.
Although this WC-Ni-based cemented carbide material is superior in corrosion resistance to WC-Co-based cemented carbide material, it has corrosion resistance in an environment including seawater, for example, a brackish water area near the river mouth, and an acid solution Corrosive wear has been a problem in the processing of workpieces.

  Therefore, the present invention relates to a corrosion-resistant and wear-resistant material suitable for use in corrosion-resistant wear-sliding parts such as cylindrical sleeves for pump shafts, corrosion-resistant wear-resistant molds and corrosion-resistant wear-resistant tools, etc. Intended to be provided.

The hard phase-dispersed nickel-based intermetallic compound composite sintered material according to aspect 1 of the present invention is a hard phase wherein the first phase is a solid solution of Ti, Mo and / or a carbide, nitride or carbonitride of W. The second phase comprises 75 at% to 85 at% nickel (Ni), 8 at% to 13 at% silicon (Si), and 3 at% to 13 at% titanium (Ti), the second phase comprising consists mainly _Ni 3 crystal structure is a L1 ₂ type (Si, Ti) intermetallic compound, in the hard phase dispersed nickel-based intermetallic compound composite sintered material, the first phase is 35vol% ~80vol%, the It is characterized by containing 20 vol%-65 vol% of two phases.

A second aspect of the present invention is the hard phase-dispersed nickel-based intermetallic compound composite sintered material according to the first aspect, wherein the second phase further contains boron (B), and the Ni ₃ (Si, Ti) intermetallic compound It is characterized by containing 10 mass ppm-1000 mass ppm with respect to the mass of a phase.

Aspect 3 of the present invention is a method for producing a hard phase-dispersed nickel-based intermetallic compound composite sintered material according to aspect 1, comprising a solid solution of Ti, Mo and / or a carbide, nitride or carbonitride of W. And 75 at% to 85 at% of nickel (Ni), 8 at% to 13 at% of silicon (Si), and 3 at% to 13 at% of titanium (Ti). And a sintering step of heating and sintering the mixed powder or alloy powder produced in the mixing step while applying pressure to the mixed powder or alloy powder. I assume.
A fourth aspect of the present invention is the method for producing a hard phase-dispersed nickel-based intermetallic compound composite sintered material according to the third aspect, wherein boron (B) is further added to the mass of the material to be the bonding material in the mixing step. And 10 mass ppm to 1000 mass ppm.

The sliding component according to aspect 5 of the present invention is characterized by being composed of the hard phase-dispersed nickel-based intermetallic compound composite sintered material according to aspect 1 or aspect 2.
A mold according to aspect 6 of the present invention is characterized by being composed of the hard phase-dispersed nickel-based intermetallic compound composite sintered material according to aspect 1 or aspect 2.
The tool according to aspect 7 of the present invention is characterized by being composed of the hard phase-dispersed nickel-based intermetallic compound composite sintered material according to aspect 1 or aspect 2.

  It is possible to provide a material that is superior in corrosion resistance and wear resistance to conventional WC-Ni-based cemented carbide materials, as well as sliding parts, dies, tools or other members using the same.

_{WC-Ni 3 (Si, Ti} ) of the present invention is a diagram showing the relationship between volume percentage and hardness of the intermetallic compounds in the material Ni ₃ (Si, Ti). _{WC-Ni 3 (Si, Ti} ) of the present invention is a diagram showing the relationship between the fracture toughness value due to Ni ₃ in material (Si, Ti) volume percent and IF method (Indentation Fracture method). It is a figure which shows the result of the corrosion rate (g / m < ² > / day) of each material obtained by the corrosion test. Of the present invention is a diagram showing the relationship between volume percentage and hardness of the (Ti, Mo) (C, N) -Ni 3 (Si, Ti) Ni 3 (Si, Ti) in the material. (Ti, Mo) (C, N) of the present invention is a diagram showing the relationship between the fracture toughness value due to volume percentages and IF method _{-Ni 3 (Si, Ti) Ni} 3 in the material (Si, Ti). It is a figure which shows the result of the corrosion rate (g / m < ² > / day) of each material obtained by the corrosion test.

  Hereinafter, embodiments of the present invention will be described in detail.

First, some terms, measurement methods, and the like used in the present specification will be described.
The “solid solution and / or W of Ti, Mo” represents “solid solution of Ti, Mo, W”, “solid solution of Ti, Mo” or “W”.
With regard to the “hard phase”, the HV hardness as the composite material of the hard phase-dispersed nickel-based intermetallic compound composite sintering material of the present invention is a slide such as a seal ring which is required to have wear resistance although it depends In the case of a moving product, it may be a hard phase having a hardness of at least 800 kgf / mm ² or more.
“The second phase is mainly composed of Ni ₃ (Si, Ti) intermetallic compound whose crystal structure is L 1 ₂ type” means 75 at% to 85 at% nickel (Ni) and 8 at% to 13 at% silicon Of the second phase comprising (Si) and 3 at% to 13 at% titanium (Ti), the majority (at least 50% or more by volume, preferably 80% or more by volume) has a crystal structure Although it is composed of a Ni ₃ (Si, Ti) intermetallic compound of L ₁₂ type, some compounds such as Ni ₁₆ Ti ₆ Si ₇ may be formed in some cases other than this.
The volume percentage of the second phase or Ni ₃ (Si, Ti) intermetallic compound is averaged by image analysis or the like in cross-sectional structure observation (optical microscope observation, scanning electron microscope observation, EPMA) with a field of view of 100 μm × 100 μm or more. It calculates | requires from the relational expression of area percentage = volume percentage.
Ni ₃ (Si, Ti) intermetallic compound so long as it has an L1 ₂ type crystal structure, the amount of Ni in the atomic ratio, the ratio of the total amount of Si and Ti 3: stoichiometric composition of 1 As well as in some cases, it may have a composition out of the stoichiometric composition.
"Ni-based (nickel-based)" means that the amount of Ni is the largest among the respective elements contained, preferably containing 50% or more of Ni in atomic ratio (at%), more preferably Contains 60% or more of Ni in atomic ratio (at%).
Hereinafter, embodiments of the present invention will be described in detail.
One of the features of the method for producing a composite sintered material according to the present invention is to use a sintering method in which sintering is performed under pressure, and a sintering powder having a predetermined composition is produced before sintering. Do.
The sintering powder contains a material that forms a first phase that is a hard phase, and a material that forms a second phase that has an intermetallic compound as a main phase.
With respect to the material forming the second phase, for example, elemental powders such as Ni powder, Si powder, Ti powder, and as necessary, B powder may be used as raw material powders, or they may be molten metals having a predetermined composition (molten alloy The alloy powder may be obtained by atomizing or the like. Furthermore, it may be a mixed powder obtained by mixing an elemental powder and an alloy powder.
Further, for the hard phase to be the first phase, for example, WC powder or (Ti, Mo) (C, N) powder or the like which is less than 10 μm commercially available may be used as a raw material powder.
The raw material powder may be mixed using any method used in this technical field such as mortar and pestle when obtaining mixed powder, but preferably powder dispersion with high pulverizing effect such as ball mill, attritor, bead mill and uniform Mix using methods that allow mixing.
In addition, it can wet-mix using alcohol as a mixed solvent.

The composition of the powder for sintering is substantially the same as the composition combining the first phase and the second phase after heat treatment, which will be described later, or after that, if necessary, as appropriate.
That is, defining the composition of the sintering powder here is defining the composition of the main phase of the sintered body.
Therefore, the composition of the powder for sintering (main phase) contains 35 vol% to 80 vol% of a hard phase consisting of a solid solution of Ti, Mo and / or a carbide, nitride or carbonitride of W as a first phase, 75 at% and ～85At% of nickel (Ni), and 8at% ~13at% of silicon (Si), Ni ₃ formed with 3at% ~13at% of titanium (Ti), or further a boron (B) as the binding material It contains 20 vol% to 65 vol% of a second phase comprising 10 mass ppm to 1000 mass ppm based on the mass of the (Si, Ti) intermetallic compound phase.
The remainder consists of unavoidable impurities.
Boron (B) powder is effective to suppress intergranular cracking particularly in polycrystals in order to improve hardness, strength, toughness, oxidation resistance and corrosion resistance, so it is added as necessary, but Ni ₃ If the amount is less than 10 mass ppm with respect to the mass of the (Si, Ti) intermetallic compound phase, hardness, strength, toughness, oxidation resistance, corrosion resistance, inhibition of intergranular cracking can not be improved, and if more than 1000 mass ppm, toughness or calcined Since the binding property is reduced, 10 mass ppm or more and 1000 mass ppm or less are appropriate with respect to the mass of the Ni ₃ (Si, Ti) intermetallic compound phase.

Sintering is carried out, for example, by general powder metallurgy in which a powder for sintering is put into a die and pressure is applied by a punch to obtain a compact (green compact) and then heated to a predetermined sintering temperature You may carry out by the sintering method.
In the manufacturing method according to the present invention, it is possible to easily obtain a sintered body having a shape of a final product or a shape close to the shape (near net shape) by using a sintering method based on powder metallurgy. That is, the sintered body can be manufactured with high dimensional accuracy.

It is preferable to sinter while applying pressure to the sintering powder (pressure sintering). This is because the bulk density of the obtained sintered body can be increased, and the density (true density) of the molten material can be made closer.
In the case of applying pressure to the powder for sintering, when sintering is performed after obtaining the formed body, pressure is applied to the powder for sintering in the formed body by applying pressure to the formed body. Including being done.

A hot press can be mentioned as a preferable example of the method (pressure-sintering method) to sinter while giving pressure to such a powder for sintering.
In addition, as an example other than hot pressing, there is a method of performing hot isostatic pressing (HIP treatment) or gas pressure sintering after vacuum sintering.

The pressure sintering by the hot pressing method may be performed as follows.
For example, a lower punch is inserted from below into a vertically extending through hole provided in a die made of graphite, and the above-mentioned sintering powder or powder containing the above-mentioned sintering powder inside the through hole and above the lower punch Place.
Thereafter, the upper punch is inserted from above the through hole, and stress is applied to the upper and lower punches so that a predetermined pressure is applied to the sintering powder.
Then, in a state where a predetermined pressure is applied to the sintering powder, the sintering powder is heated and sintered, for example, by heating a die.
Also, instead of placing the sintering powder or the powder containing the sintering powder inside the through hole of the die and above the lower punch, using the powder containing the sintering powder or the powder for sintering The formed body may be arranged.

The sintering conditions such as sintering temperature, temperature rising rate, sintering time, stress for pressing the sintering powder (or molded body) when using the hot press method, sintering conditions such as sintering atmosphere, are the composition of the sintering powder to be used According to the characteristics of the sintered body to be obtained, it may be appropriately adjusted.
Preferred conditions are exemplified below.

The sintering temperature is preferably 750 ° C to 1150 ° C. If it is less than 750 ° C., sintering may not be sufficient and a dense sintered body may not be obtained, and if it is higher than 1150 ° C., grain growth may occur to lower hardness and abrasion resistance may be insufficient. It is from. _Ni 3 (Si, Ti) in this temperature range a long if L1 ₂ crystal structure phase can be obtained. More preferably, the sintering temperature is 950 ° C to 1150 ° C. This is because the Ni ₃ (Si, Ti) intermetallic compound can be formed more reliably, a denser sintered body can be obtained, and higher hardness can be obtained at high temperature.

The temperature raising rate at the time of raising the temperature to this sintering temperature is preferably 10 ° C./min or less. If the temperature rise rate is too fast, the temperature distribution may become uneven, which may cause internal and external differences in the characteristics of the sintered body.
Moreover, as for the time hold | maintained at the above-mentioned preferable sintering temperature, 60 minutes-360 minutes are preferable. If the holding time is shorter than 60 minutes, densification may be insufficient. If the holding time is too long, the crystal grains may be coarsened to deteriorate (or degrade) the characteristics such as hardness.

The stress applied to the sintering powder (or compact) is preferably 10 MPa to 60 MPa. If the stress is lower than 10 MPa, densification may be insufficient, and if it is too high, the carbon mold may be broken.
Sintering is preferably in vacuum or in a reduced pressure atmosphere of an inert gas such as Ar (argon), N ₂ (nitrogen) and He (helium). In an atmosphere containing oxygen, the powder may be oxidized to inhibit densification.

The hard phase-dispersed nickel-based intermetallic compound composite sintered material (sintered body) produced in this manner is not a part of the second phase of the sintered body except Ni ₃ (Si, Ti) depending on the sintering conditions. Or the formation of Ni ₃ (Si, Ti) may be insufficient. Heat treatment may be performed to form Ni ₃ (Si, Ti) from at least a part of such a portion.
It is preferable to carry out heat treatment at a temperature of 1100 ° C. or less, preferably 1050 ° C. or less, which is higher than the sintering temperature and at which no liquid phase occurs.
Even if such heat treatment is performed, the heat treatment temperature is selected to be lower than the melting temperature at the time of producing the molten material (cast material), so Ni ₃ (Si, Ti) metal at a lower temperature Inter-compounds can be formed, and the effects of the present invention can be obtained.

The suitable heat treatment conditions are illustrated below.
The preferred heat treatment temperature is 900 ° C to 1050 ° C. Is less than _{900 ℃, Ni 3 (Si,} Ti) Ni 3 formed is insufficient in (Si, Ti) intermetallic compound other than is formed. When the temperature is higher than 1050 ° C., formation of Ni ₃ (Si, Ti) is ensured, but the liquid phase is released to cause grain growth, the hardness is lowered, and the problem of wear resistance is caused.
It is preferable to hold | maintain this heat processing temperature for 0.5 hour-72 hours. Is less than 0.5 _{hours, Ni 3 (Si, Ti)} Ni 3 formed is insufficient in (Si, Ti) intermetallic compound other than is formed. If it exceeds 72 hours, formation of Ni ₃ (Si, Ti) becomes certain, but grain growth occurs, the hardness decreases, and a problem occurs in the wear resistance.
The heat treatment is preferably performed in vacuum or in an inert gas atmosphere such as Ar. This is because the sintered body is oxidized in an atmosphere containing oxygen.

Thus, a sintered body having a second phase containing a Ni ₃ (Si, Ti) intermetallic compound can be obtained.

Example 1
Commercially available Ni powder with an average particle diameter of 2.5 μm, Si powder with a particle diameter of 75 μm to 150 μm, Ti powder with a particle diameter of 45 μm or less, B powder with a particle diameter of 38 μm or less, WC powder with an average particle diameter of 1.5 μm Each mixture was blended at a predetermined ratio so as to obtain the composition shown, and mixed in an organic solvent for 72 hours with a ball mill mixer, and the obtained mixed powder was press-molded at 100 kgf / cm ² . Hot press sintering was performed at 1150 ° C. under a pressure of 30 MPa in vacuum. Then, the sample of Example 1-1, Example 1-2, Example 1-3, Example 1-4, and the comparative example 1 was produced by hold | maintaining in vacuum at 1050 degreeC for 48 hours. In addition, about B powder, it showed with the ratio (defined as outmass%) with respect to the total mass (100 mass%) of elements other than B.
Next, X-ray diffraction (CuKα) was performed on the obtained samples of Example 1-1, Example 1-2, Example 1-3, and Example 1-4. The results of X-ray diffraction, only the crystal peak of the hard phase WC, L1 ₂ type nickel-base intermetallic compound _Ni 3 (Si, Ti) was confirmed. The hard phase-dispersed nickel-based intermetallic compound composite sintered material of the present invention for the samples of Example 1-1, Example 1-2, Example 1-3, and Example 1-4 according to this result and SEM and optical microscope observation Was confirmed to be formed.
Also, the atomic ratio composition in Ni ₃ (Si, Ti) in the materials shown in Table 1 is shown in Table 2. It should be noted here that Ni ₃ (Si, Ti) has a certain composition width and forms an intermetallic compound within that range, so it is not fixed to the atomic ratios in Table 2 .

_{WC-Ni 3 (Si, Ti} ) of the present invention obtained in FIG. 1 embodiment of the material 1-1, Example 1-2, Example 1-3, occupied in Example 1-4 _Ni 3 (Si, The relationship between the volume percentage of Ti) and hardness is shown. About the data of Example 1-1 and Example 1-2, since hardness was substantially the same, it overlapped and displayed. Double circles (◎) in FIG. 1 are data of WC-20 vol% Ni composition (WC particle diameter: 1.5 μm) of Comparative Example 1, and WC-20 vol% Ni _{3 of} Example 1-1 of the present invention. _{(Si, Ti), WC-} 20vol% Ni 3 of example 1-2 (Si, Ti) -0.005 outmass % B , this a binding material of Comparative example 1 of the composition of the same volume WC-20 vol% It can be confirmed from FIG. 1 that the hardness is higher than Ni. The wear-resistant applications such as seal rings, depending on the opposite material, Ni ₃ since at least HV hardness is needed 800 (kgf / mm ²⁾ or more, by extrapolation in the graph of FIG. 1 ( It was found that the content of Si, Ti) is suitably 65 vol% or less.

_{WC-Ni 3 (Si, Ti} ) of the present invention obtained in the embodiment in FIG materials 1-1, Example 1-2, Example 1-3, occupied in Example 1-4 _Ni 3 (Si, The relationship between the volume percentage of Ti) and the fracture toughness value by IF method (Indentation Fracture method) is shown. About the data of Example 1-1 and Example 1-2, since hardness was substantially the same, it overlapped and displayed. Double circles (◎) in FIG. 2 are data of WC-20 vol% Ni composition (WC particle diameter: 1.5 μm) of Comparative Example 1. As the use of wear resistant members, the fracture toughness value needs to be 8 MPa · m ^1/2 or more, so in the graph of FIG. 2, about 20 vol% or more of Ni ₃ (Si, Ti) is required by the outer insertion method. I understand.

Next, WC-20 vol% Ni of Example 1-1, Example 1-2, Example 1-3, Example 1-4, and Comparative Example 1 of the WC-Ni ₃ (Si, Ti) material of the present invention The material was subjected to a corrosion test by the following method.
As a corrosion test method, a ferric chloride corrosion test method of JIS G 0578: 2000 stainless steel was applied. The test vessel was a glass beaker, and the test solution was prepared with hydrochloric acid and distilled water defined in JIS K 8180. 900 ml of N / 20 hydrochloric acid solution, iron chloride (III) chloride prescribed in JIS K 8142. The solution was dissolved and adjusted to a hydrochloric acid 6% ferric chloride solution.
The amount of the test solution was prepared to be 20 ml or more per 1 cm ² of the surface area of the test piece, and the test piece mass was measured to the order of 1 mg before and after the test. The test temperature was 35 ± 1 ° C. as a standard. After conducting a continuous 24 hour immersion test, after the test, the test piece is washed and dried, and the mass is weighed to determine the weight loss, and the corrosion rate is divided by the surface area.

The result of the corrosion rate (g / m < ² > / day) of each material obtained by the above-mentioned corrosion test is shown in FIG. Example 1-1, Example 1-2, Example 1-3, and Example 1-4 of the WC-Ni ₃ (Si, Ti) alloy of the present invention (however, Example 1-1 and Example) It was confirmed that the corrosion rate is slower and the corrosion resistance is excellent compared to WC-20 vol% Ni of Comparative Example 1 in any order substantially the same as 1-2).

From the above results, the WC-Ni ₃ (Si, Ti) material of the present invention has a content of Ni ₃ (Si, Ti) of 20 vol% for the use of sliding parts, dies and tools excellent in corrosion resistance and wear resistance. It turned out that 65 vol% or less is suitable. That is, a first phase consisting of a hard phase containing tungsten carbide (WC), 78 at% to 85 at% nickel (Ni), 8 at% to 13 at% silicon (Si), and 3 at% to 13 at% titanium (Ti) and a second phase containing, the second phase consists primarily _Ni 3 (Si, Ti) intermetallic compound crystal structure is L1 ₂ type, the first phase 35vol% ~80vol%, second The hard phase dispersed nickel base intermetallic compound composite sintered material consisting of 20vol% to 65vol% of the phase is used as a corrosion resistant wear sliding part such as a cylindrical sleeve for a pump shaft, a corrosion resistant wear die or a corrosion resistant wear resistant tool It could be confirmed that it is a suitable material.

Example 2
Commercially available Ni powder having an average particle diameter of 2.5 μm, Si powder having a particle diameter of 75 μm to 150 μm or less, Ti powder having a particle diameter of 45 μm or less, B powder having a particle diameter of 38 μm or less, Ti: Mo = 0 having an average particle diameter of 0.8 μm (Ti, Mo) (C, N) powder which is a carbonitride of a solid solution of Ti and Mo having a ratio of 8: 0.2, C: N = 0.6: 0.4 to 0.5: 0.5 Were mixed at a predetermined ratio to obtain the composition shown in Table 3, mixed in an organic solvent for 72 hours in a ball mill mixer, and press-formed at 100 kgf / cm ^{2 of} the obtained mixed powder. Hot press sintering was performed at 1150 ° C. in an inert gas atmosphere such as nitrogen or argon under vacuum or reduced pressure at a pressure of 30 MPa. Then, the sample of Example 2-1, Example 2-2, Example 2-3, Example 2-4, and the comparative example 1 was produced by hold | maintaining under vacuum at 1050 degreeC for 48 hours. In addition, about B powder, it showed with the ratio (defined as outmass%) with respect to the total mass (100 mass%) of elements other than B.
Next, X-ray diffraction (CuKα) was performed on the obtained samples of Example 2-1, Example 2-2, Example 2-3, and Example 2-4. The results of X-ray diffraction, only the crystal peak of the hard phase (Ti, Mo) (C, N) and L1 ₂ type nickel-base intermetallic compound _Ni 3 (Si, Ti) was confirmed. The hard phase-dispersed nickel-based intermetallic compound composite sintered material of the present invention is a sample of Example 2-1, Example 2-2, Example 2-3, and Example 2-4 according to this, SEM, and optical microscope observation. It could be confirmed that it was formed.

Of the present invention obtained in FIG. 4 (Ti, Mo) (C , N) -Ni 3 (Si, Ti) Example of materials 2-1, Example 2-2, Example 2-3, Example 2 _Ni 3 (Si, Ti) occupied to -4 shows the relationship between the volume percentage and hardness. About the data of Example 2-1 and Example 2-2, since hardness was substantially the same, it overlapped and displayed. Double circles (◎) in FIG. 4 are data of WC-20 vol% Ni composition (WC particle size: 1.5 μm) of Comparative Example 1, and (Ti, Mo) (Example 2-1 of the present invention) _{C, N) -20vol% Ni 3} (Si, Ti), (Ti example 2-2, Mo) (C, N ) -20vol% Ni 3 (Si, Ti) -0.005 outmass% B is It can be confirmed from FIG. 4 that this and the bonding material have higher hardness than WC-20 vol% Ni of Comparative Example 1 having the same volume composition. Since HV hardness is required to be 800 (kgf / mm ² ) or more for wear resistance applications such as seal rings, the intermetallic compound Ni ₃ (Si, Ti) can be obtained by extrapolating to the graph in FIG. It has been found that the content is about 65 vol% or less.

Figure 5 obtained of the present invention _{(Ti, Mo) (C,} N) -Ni 3 (Si, Ti) Example of materials 2-1, Example 2-2, Example 2-3, Example 2 _Ni 3 (Si, Ti) occupied to -4 shows the relationship between the volume percentage and IF method (Indentation fracture method) fracture toughness value by (fracture toughness). About the data of Example 2-1 and Example 2-2, since the fracture toughness value was substantially the same, it overlapped and displayed. Double circles (◎) in FIG. 5 are data of WC-20 vol% Ni composition (WC particle diameter: 1.5 μm) of Comparative Example 1. As the use of the wear resistant member, since the fracture toughness value needs to be 8 MPa · m ^1/2 or more, the extrapolation method in the graph of FIG. 5 requires about 20 vol% or more of Ni ₃ (Si, Ti) I understand.

Next, the present invention _{(Ti, Mo) (C,} N) -Ni 3 (Si, Ti) Example of materials 2-1, Example 2-2, Example 2-3, Example 2-4 and In order to compare the use environment including seawater and the corrosion resistance in an acidic aqueous solution, the WC-20 vol% Ni material of Comparative Example 1 was subjected to a corrosion test in the same manner as in Example 1.
The result of the corrosion rate (g / m < ² > / day) of each material obtained by the said corrosion test is shown in FIG. Example 2-1, Example 2-2, Example 2-3, and Example 2-4 of the (Ti, Mo) (C, N) -Ni ₃ (Si, Ti) Alloy of the Present Invention In each of Example 2-1 and Example 2-2, it was confirmed that the corrosion rate is slower and the corrosion resistance is excellent as compared to WC-20 vol% Ni of Comparative Example 1 in all cases.

From the above results, the (Ti, Mo) (C, N) -Ni ₃ (Si, Ti) material of the present invention is Ni ₃ (Ni, ₃ ) with respect to applications of sliding parts, molds and tools excellent in corrosion resistance and wear resistance. It was found that the content of Si, Ti) is preferably 20 vol% or more and 65 vol% or less. That is, a hard phase (first phase) containing (Ti, Mo) (C, N), 78 at% to 85 at% nickel (Ni), 8 at% to 13 at% silicon (Si), 3 at% to 13 at% and a second phase containing a titanium (Ti), the second phase is predominantly crystalline structure L1 ₂ type _Ni 3 (Si, Ti) made of an intermetallic compound, the first phase 35vol% ~80vol It was confirmed that the hard phase-dispersed nickel-based intermetallic compound composite sintered material comprising 20% by volume and 20% by volume of the second phase is a material suitable for anticorrosion and wear parts.
_{Similarly, W (C x, N 1} -x) (0 ≦ x ≦ 1) -Ni 3 (Si, Ti), (Ti x, Mo 1-x) C (0 ≦ x ≦ 1) -Ni 3 ( Si, Ti), (Ti _x , Mo _1-x ) N (0 ≦ x ≦ 1) -Ni ₃ (Si, Ti), (Ti _x , Mo _Y , W _Z ) (C _α , N _1-α ) (0 ≦ α ≦ 1, x + y + z = 1, x, y, z ≠ 0) -Ni ₃ (Si, Ti) materials, etc. Other hard phase-dispersed nickel-based intermetallic compound composite sintered materials of the present invention The same results were obtained for the above, and it was confirmed that the material was suitable for the corrosion and wear resistance parts.

  The hard phase-dispersed nickel-based intermetallic compound composite sintered material of the present invention has corrosion resistance and wear resistance, and corrosion-resistant wear-sliding parts such as a cylindrical sleeve for a pump shaft, a corrosion-resistant wear die and a corrosion-resistant It can be used for applications requiring various corrosion resistance and wear resistance such as wear tools.

Claims (7)

A first phase which is a hard phase consisting of a solid solution of Ti, Mo and / or a carbide, nitride or carbonitride of W;
A second phase comprising 75 at% to 85 at% nickel (Ni), 8 at% to 13 at% silicon (Si), and 3 at% to 13 at% titanium (Ti); consists mainly _Ni 3 crystal structure is a L1 ₂ type (Si, Ti) intermetallic compound,
Hard phase-dispersed nickel-based intermetallic compound composite sintered material characterized in that the first phase contains 35 vol% to 80 vol% and the second phase contains 20 vol% to 65 vol%. The hard phase dispersion according to claim 1, wherein the second phase further contains boron (B) in an amount of 10 mass ppm to 1000 mass ppm based on the mass of the Ni ₃ (Si, Ti) intermetallic compound phase. Nickel-based intermetallic compound composite sintered material. Hard powder consisting of solid solution of Ti, Mo and / or carbide, nitride or carbonitride of W, 75 at% to 85 at% of nickel (Ni), 8 at% to 13 at% of silicon (Si), 3 at% to 13 at Mixing step with a material that contains 20% titanium (Ti) and becomes a bonding material of the hard powder to produce a mixed powder or an alloy powder,
The hard phase-dispersed nickel-based intermetallic compound composite according to claim 1, comprising a sintering step of heating and sintering the mixed powder or alloy powder produced in the mixing step in a state where pressure is applied thereto. Method of manufacturing sintered material   4. The hard phase-dispersed nickel-based intermetallic compound according to claim 3, wherein boron (B) is further added in an amount of 10 mass ppm to 1000 mass ppm with respect to the mass of the material serving as the bonding material in the mixing step. Method of manufacturing composite sintered material   A sliding component comprising the hard phase-dispersed nickel-based intermetallic compound composite sintered material according to claim 1 or 2.   A mold comprising the hard phase-dispersed nickel-based intermetallic compound composite sintered material according to claim 1 or 2.   A tool comprising the hard phase-dispersed nickel-based intermetallic compound composite sintered material according to claim 1 or 2.