KR100845042B1 - High melting point metal based alloy material exhibiting high strength and high re-crystallization temperature and method for production thereof - Google Patents

Abstract

Solid solution dispersed and dispersed in the mother phase by the multi-stage nitriding treatment of an alloy processing material comprising one of Mo, W, and Cr as a mother phase and at least one of Ti, Zr, Hf, V, Nb, and Ta as a solid metal. A workpiece obtained by carbonizing a workpiece comprising nitride particles of metal using a carbon source in which oxygen coexists, comprising carbon that is intergranular segregated by the carbonization treatment and oxide particles converted from the nitride particles. High melting point metal alloy material with high strength and solid crystal temperature.

Solid solution metals, nitride particles, nitriding, carbonization, grain boundary segregation, carbon, oxide particles

Description

High melting point metal-based alloy material with high strength and solid crystal temperature and its manufacturing method

The present invention provides a high melting point metal alloy material having a high strength and solid crystal temperature of an oxide particle dispersion strengthening type having a high temperature heat resistant material, in particular, one type of high melting point metal, Mo, W, or Cr, and a manufacturing method thereof. It is about.

At present, TZM alloy (the maximum operating temperature of 1400 ° C.) of PLANGE (PANSEE AG.) In which Ti, Zr, and C are added to Mo is almost exclusively used as a high melting point metal-based heat-resistant alloy, but the alloy is difficult to process.

Mo alloy, which is a representative example of a high melting point metal alloy material, has a problem that it shows low temperature embrittlement or low strength at high temperature as a result of recrystallization once it is heated above its recrystallization temperature (1000 to 1300 ° C). to be. In order to solve this problem, the present inventors have developed a multi-stage internal nitriding method in which a Ni-nitred Mo-Ti alloy is first nitrided below a recrystallization upper limit temperature, and then the temperature is gradually increased to perform nitriding. It developed (patent document 1). The Mo alloy material obtained by this method has a recrystallization temperature of 1600 ° C due to the pinning effect of the precipitated TiN particles (Patent Document 1).

Furthermore, the inventors of the present invention have performed a multi-step internal nitriding treatment on an alloy processing material having Mo as a matrix, and employing at least one of Ti, Zr, Hf, V, Nb, and Ta, followed by external nitriding treatment. The method was developed (patent document 2). By this method, a high corrosion resistance, high strength, high toughness Mo alloy processing material was obtained. Furthermore, the present inventors reported a study on the carbonization treatment method of depositing a trace amount of carbon as a method of strengthening the grain boundary of Mo-based material and then diffusing the grain boundary by vacuum heating (Non-Patent Document 1). In addition, the present invention

A study on the control of material structure and toughening method by carbonization of TZM alloy using thin CO gas was reported (Non-Patent Document 2). Moreover, the present inventors reported the study regarding the material structure in the case of CO gas heat treatment of the recrystallized Mo-Ti type alloy (nonpatent literature 3).

Patent Document 1: Japanese Patent Application Laid-Open No. 2001-073060

Patent Document 2: Japanese Patent Application Laid-Open No. 2003-293116

Non-Patent Document 1: Tetsushi Hoshika et al. Powder and Powder Metallurgy 49 (2002) 32-36

[Non-Patent Document 2] Nomura Naoki, et al. 'Summary of the Powder Powder Metallurgy Association's 14th Fall Conference Lecture Summary' (2002) 201

Non-Patent Document 3: Nomura Naoki et al. 「Summary of the Powder Powder Metallurgy Association's 15th Fall Conference Lecture Summary」 (2003) 31

(Initiation of invention)

(Problem that invention tries to solve)

According to the multi-stage internal nitriding method developed by the present inventors, it is possible to obtain a recrystallization temperature of 1600 ° C in a Mo-Ti alloy, but the TiN particles from the surface of the alloy are insufficient because the TiN particles have insufficient stability at high temperature and high vacuum. As a result of the slow decomposition and denitrification reaction of N, the problem remains that recrystallization occurs and becomes brittle in long term use.

(Means to solve problems)

The present inventors have long studied the structure control and toughening by nitriding and carbonizing Mo-based materials, and in the multi-stage internalization step by raising the temperature stepwise in the nitriding treatment below the upper limit of recrystallization By carbonizing the nitrided alloy material again, even when used in high temperature and high vacuum at least 1600 ° C, it is stable without recrystallization over a long period of time and at room temperature and high temperature (e.g., It succeeded in developing the high-melting-point metal alloy material with excellent strength at 1500 ° C).

That is, the present invention (1) multi-stage nitriding treatment of an alloy processing material in which at least one of Mo, W and Cr is used as a mother phase and at least one of Ti, Zr, Hf, V, Nb, and Ta is a solid solution metal. The workpiece which contains nitride particles of solid solution metal dispersed and dispersed in the mother phase by means of carbonization using a carbon source in which oxygen coexists, which is subjected to grain boundary segregation by the carbonization treatment. It is a high melting point metal-based alloy material of high strength and recrystallization temperature, characterized by containing carbon and oxide particles converted from the nitride particles.

The present invention is (2) a high melting point metal-based alloy material having a high strength and a recrystallization temperature according to (1), wherein the surface portion of the alloying material is maintained in the processing structure, and the inside thereof is a recrystallized structure.

The present invention is the high melting point metal alloy material of the above (1) or (2), wherein (3) Mo is the mother phase, Ti is the solid solution metal, and the recrystallization temperature is 1600 ° C or higher.

Furthermore, the present invention provides (4) an alloy processing material which is based on one of Mo, W and Cr, and at least one of Ti, Zr, Hf, V, Nb, and Ta is a solid solution metal. (1) or (2), characterized in that carbonized particles using oxygen source co-exist in the alloying material after dispersing the nitride particles of the solid solution metal in the mother phase by multi-stage internal nitriding at It is a manufacturing method of a high melting metal alloy material.

In addition, the present invention (5) the first stage nitriding treatment is carried out at a temperature below the recrystallization upper limit temperature of the alloying material and the recrystallization lower limit temperature-(minus) 200 ℃ or more to disperse and form the nitride particles of the solid solution metal (4) The above-mentioned (4) characterized in that the nitriding treatment is performed at a temperature equal to or higher than the lower recrystallization lower limit temperature of the alloying material obtained in the first stage nitriding treatment to grow and stabilize nitride particles dispersed and formed by the first stage nitriding treatment. It is a manufacturing method of a melting point metal type alloy material.

(6) The high-melting-point metal alloy material of (4) or (5) above, wherein the carbonization treatment is performed using an inert gas containing 0.1 to 5 vol% of CO. It is a manufacturing method of.

The present inventors carbonize the high-melting-point metal working material in which the nitride particles are dispersed and contained in the mother phase using a carbon source in which oxygen coexists, so that grain boundary strengthening due to grain boundary segregation of carbon does not occur. It has been found that nitride particles are converted into oxide particles by diffusion of oxygen, and dispersion precipitation phenomenon (internal oxidation) of oxide particles of solid solution metal occurs.

The reason why oxide particles are formed by carbonization using a carbon source in which oxygen coexists is not clear, but when the heat treatment temperature is low, a very thin Mo ₂ C film is formed on the surface of the workpiece and oxygen As a result of the diffusion being prevented, only carbon can be diffused at the interface between the Mo ₂ C film and the workpiece, and internal carbonization occurs.However, when the heat treatment is performed at a high temperature, the Mo ₂ C film is hardly formed on the surface of the workpiece. This may be because the diffusion of oxygen occurs. For example, when the same heat treatment is performed with argon gas containing 2 vol% of CH ₄ gas, a very thick MoC ₂ film is produced regardless of the heat treatment temperature, and the material becomes soft. The coexistence of oxygen suppresses the formation of the MoC ₂ film (the carbonization reaction of Mo itself), and it can be considered that grain boundary diffusion of carbon and particle diffusion of oxygen occur simultaneously.

The oxide particles produced in this way have the same shape as the nitride particles and have a pinning effect that hinders the movement of grain boundaries. However, the oxide particles dispersed and deposited in the high melting point metal are thermodynamically stable compared to the nitride particles. Recrystallization embrittlement seen in the case of nitride particles is improved because it remains stable without decomposing for a long time even at high temperature and high vacuum, and the recrystallization temperature is also increased, thereby increasing the resistance to high temperature deformation.

The alloy material obtained by the multistage nitriding and carbonization treatment has a structure in which a processed rolling structure is maintained at least on the surface, and oxide particles of solid solution metal are dispersed and deposited from the surface to the inner layer. In this way, the strength is increased by grain boundary segregation of carbon, and the recrystallization temperature is improved by precipitation hardening of oxide particles. For example, Mo-Ti alloys exhibit strength characteristics two to three times that of conventional commercial Mo alloys in a wide range from room temperature to 1600 ° C., even under high temperature and high vacuum at 1700 ° C. where multi-stage internal nitride recrystallizes. It has excellent heat resistance that does not recrystallize at all.

(Effects of the Invention)

The present invention provides a high melting point metal-based heat-resistant alloy material exhibiting excellent heat resistance that is stable over a long period of time under high temperature and high vacuum and does not recrystallize. The rolled structure held on the surface of the alloying material has an effect of inhibiting the propagation of cracks, thereby being excellent in impact resistance. Moreover, the manufacturing method of the present invention is a method of processing an alloy material in an arbitrary shape, followed by heat treatment using a nitriding atmosphere, and then heat treatment using a carbon source in which oxygen coexists, and is easy to process a complicated shape product which has been processed in advance. Can respond.

(The best mode for carrying out the invention)

In the high melting point metal alloy material of the present invention, as the solid solution metal, Ti, Zr, Hf, V, Nb, and Ta are preferable. All of these metals form nitrides that are more stable than Group 6A elements such as Mo and W, and are therefore required for structure control by first multi-stage internal nitriding. In addition, since these oxides are all more stable than nitride, conversion reaction from nitride particles to oxide particles occurs by CO gas heat treatment after multistage nitriding treatment. The content of the solid solution metal is about 0.1 to 5.0 wt%, more preferably about 0.3 to 2.0 wt%. If it is less than 0.1 wt%, there are too few precipitated particles to suppress recrystallization. When it exceeds 5.0 wt%, the material after the nitriding-CO gas heat treatment becomes weak, making it difficult to use practically.

The high melting point metal-based alloying material containing these solid solution metals is processed into a desired shape and then subjected to multistage internal nitriding treatment. This multi-stage internal nitride material and its manufacturing method itself are known means as shown in Patent Document 1 (Patent No. 2001-073060).

In other words, the multi-stage internal nitride material is an alloy processing material which contains and disperses fine nitride formed by internal nitriding in a nitride atmosphere of a metal element employed in an alloy processing material having one of Mo, W and Cr as a matrix. At least the surface side has a structure in which nitride precipitated particles have grown while maintaining a processing structure such as rolling.

In addition, the method of manufacturing the alloy processing material is subjected to the first stage nitriding treatment at a temperature not lower than the upper limit of recrystallization of the alloy and the lower limit of recrystallization temperature-(minus) of 200 ° C or higher to disperse the nitride particles of the solid metal element. The second stage nitriding treatment is carried out at a temperature higher than the lower limit temperature of recrystallization of the alloying material obtained in the first stage nitriding treatment to stabilize the grains of nitride particles dispersed and formed by the first stage nitriding treatment.

The recrystallization temperature of the alloy processing material mainly has a predetermined width of the upper and lower recrystallization values depending on the manufacturing conditions of the alloy material such as workability. For example, in the Mo-1.0wt% Ti alloy processing material, it is 950 to 1020 ° C. It is enough. The temperature at which recrystallization occurs is lower as the workability increases.

The first stage nitriding treatment is below the recrystallization upper limit temperature because the material is recrystallized and weakened when the nitriding treatment is performed at a higher temperature. The recrystallization lower limit temperature is lower than the temperature of 200 ° C or higher. This is because the speed is so slow that internal nitriding to practically sufficient depth is difficult.

It is preferable that the number of stages of the multi-stage nitriding treatment is at least two stages, but the nitride particles dispersed and formed by the nitriding treatment of the previous stage by heating to a temperature higher than the recrystallization lower limit temperature of the alloying material obtained in the previous stage of nitriding treatment as the nitriding treatment after the third stage. It is also possible to carry out a method of stabilizing by growing again.

For example, when 1st stage nitriding is performed at 900 degreeC, in the obtained internal nitriding layer, the gradient (a lot of surface parts and few inside) generate | occur | produce in the distribution density of the precipitated TiN particle from the surface toward the inside. As a result, the recrystallization temperature in the nitrogen atmosphere of the internal nitride layer obtained in the first stage nitriding is the highest in the vicinity of the surface (for example, 1400 ° C. (recrystallization upper limit temperature)), and the end of the internal nitride layer has the lowest (for example, For example, it becomes 950 degreeC (recrystallization lower limit temperature).

Although the thickness of the internal nitride layer obtained in the first stage nitriding defines the theoretical maximum thickness which can finally leave the processed structure such as rolling, the lower temperature of recrystallization of the second stage of nitriding in order to leave the processed structure such as rolling as much as possible It is necessary to increase the precipitation density of the TiN particles at the end of the internal nitride layer obtained in the first stage nitriding and increase the size of the TiN particles immediately above. As a result, the lower recrystallization limit temperature (recrystallization temperature near the end of the inner nitride layer) after the second stage nitriding increases. Of course, when the second stage nitriding is performed at a temperature higher than the first stage nitriding temperature and below the lower recrystallization limit temperature, it is possible to leave the thickest structure such as rolling, but the number of processes of nitriding is increased and the time is also increased. Too long It can be said that the same result is obtained even when the nitriding treatment after the third stage is performed.

The shape of the nitride particles depends on the nitriding temperature. For example, in the three-step nitriding process of 900 ° C. to 1200 ° C. to 1600 ° C., the particles after the first stage of nitriding are disc-shaped particles having a diameter of about 1 to 2 nm. The amount of precipitation decreases toward the inside. Near the outermost surface, almost all alloying elements are precipitated as nitrides. After the second stage nitriding, grain growth is carried out at about several tens of nm, and the distribution density gradient (tilt) of the precipitated TiN particles in the processed structure such as rolling becomes smooth. After the third stage of nitriding, the TiN particles grow into rod-shaped particles having a length of 50 to 150 nm and almost all Ti is present as nitrides in the processing structure such as rolling remaining on the surface of the material.

In this manner, carbonization is performed on the high melting point metal alloy material in which the recrystallization temperature is increased by multi-stage internal nitriding using a carbon source in which oxygen coexists. As a result of this carbonization treatment, the rolled structure of the material surface part is maintained, and the inside has a two-layer structure characteristic of the recrystallized structure. This carbonization treatment does not affect the microstructure of the mother phase at all, and it is possible to convert only nitride particles precipitated by multi-stage internal nitriding into oxide particles.

The amount of carbon in the grain boundary segregation is about 30 to 150 ppm (wt%). If it is less than this, the effect of grain boundary strengthening cannot be expected. The nitride in the processing structure such as rolling remaining in the multistage nitriding is completely changed into oxide particles. At this time, the size and shape change. For example, rod-shaped TiN particles (aspect ratio: 4 to 7) having a length of 50 to 150 nm are changed to oxide particles having a length of 30 to 60 nm (aspect ratio: 2 to 3). And the smaller the size, the larger the number of particles.

As a carbon source in which oxygen coexists, a lean CO gas can be used, for example. It is preferable to make this lean CO gas into the inert gas containing 0.1-5 volume% of CO. If the CO concentration is higher than 5% by volume, carbonization of the high melting point metal occurs remarkably, which is not preferable. The lean CO gas is easy to control the carbon potential, and by adjusting the carbon concentration, it is possible to suppress the formation of a hard and weak carbide layer on the surface of the alloy material.

The carbonization treatment can also be carried out by a method in which oxygen is coexisted with a carbon source such as solid carbon and hydrocarbons around the high melting point metal alloy material, without being limited to lean CO gas. For example, when the heat treatment is performed while the carbon powder is placed in the vicinity of the workpiece without vacuum contact with the carbon source, but the vacuum powder is adsorbed by a rotary pump or the like, the same reaction occurs as when using a lean CO gas. . Under very poor vacuum conditions, a small amount of oxygen in the atmosphere reacts with carbon, resulting in the generation of CO gas, which is involved in the reaction. The same reaction occurs even when the processing material is mixed in the mixed powder of the carbon powder and the alumina powder and reacted in a low vacuum state. However, when a solid carbon source is used, a carbide layer of lean CO gas is more preferable because a carbide layer of hard and weak high melting point metal is easily formed on the surface of the workpiece when the heating temperature is low.

BRIEF DESCRIPTION OF THE DRAWINGS It is a drawing substitute photograph which shows the optical microscope structure of the test piece after processing in Example 1. FIG.

FIG. 2 is a drawing substitute photograph showing a TEM structure of a test piece after treatment in Example 1. FIG.

It is a graph which shows the result of the three point bending test of the test piece after a process in Example 1. FIG.

FIG. 4 is a drawing substitute photograph showing an optical microscope structure after heating the test piece after treatment in Example 1 at high temperature.

5 is a graph showing the results of a high temperature three-point bending test at 1500 ° C. of a test piece, a multistage nitride material, and a multistage nitrided carbonized material before treatment.

(Example 1)

As the test piece, two Mo-1.0 wt% Ti alloy rolled materials (thickness 1.0 mm x width 2.5 mm x length 25 mm) were used. The minimum recrystallization temperature of this alloy rolled material was 900 degreeC, and the upper limit temperature was 1020 degreeC. Here, multi-step internal nitriding treatment was performed at 900 ° C. for 64 hours, the second step at 1200 ° C. for 25 hours, and the third step at 1500 ° C. for 25 hours. The lower and upper recrystallization temperatures were 950 ° C and 1400 ° C after the first step, 1250 ° C and 1600 ° C after the second step, and 1600 ° C and 1800 ° C (in the nitrogen atmosphere) after the third step. Nitriding was performed in a 1 atm N ₂ gas stream. One of two test pieces was made into the comparative example as it was. The other test piece was carbonized at 1500 degreeC for 16 hours using lean CO gas atmosphere. The concentration of CO gas was Ar / CO = 49/1 (CO concentration 2% by volume).

In FIG. 1, the optical microscope structure of the test piece after a process is shown. It can be seen that the rolling structure is maintained on the surface of both the multistage nitride material and the multistage nitride + carbonized material. 2 shows the TEM structure of the test piece after the treatment. It can be seen that the rod-shaped TiN particles of the multistage nitride material are converted to elliptical Ti oxide in the multistage + carbonized material. 3, the result of a three point bending test is shown similarly. It can be seen that the mechanical properties do not change even after treatment with CO gas. DBTT (ductility-brittle transition temperature) does not change.

In FIG. 4, the optical microscope structure after vacuum-processing on the conditions of 1600 degreeC and 1 hour for the 1st step, and 1700 degreeC and 1 hour for the recrystallization temperature of a test piece is shown. In the multistage nitriding material of the comparative example, the bottom of the rolled structure was found to be white, and recrystallization occurred, whereas in the multistage nitriding + carbonization material of the example, the recrystallization did not occur even when heated at 1700 ° C. In FIG. 5, the high temperature 3-point bending test result at 1500 degreeC of a test piece, a multistage nitride material, and a multistage nitriding + carbonization material before a process is shown. It can be seen that the strength of the multistage material and the multistage + carbonized material is significantly improved compared to the untreated test piece.

The high-melting-point metal alloy material of the present invention is used in heat-resistant structural materials and the like, which have heat resistance exceeding current TZM alloys and correspond to ultra-high temperature environments. Specifically, for example, bolts and nuts for ultra high temperature members, heaters for ultra high temperature furnaces, filaments, reflecting plates, boats for firing semiconductor parts, etc. Heat sinks, hot dies and dies, aerospace gas injection nozzles, molten metal quench solidification dies and injection molding dies.

Claims (6)

For multi-stage nitriding treatment of alloy processing materials containing, as a base, one of Mo, W, and Cr, and containing at least one of Ti, Zr, Hf, V, Nb, and Ta as 0.1 to 5.0 wt% as a solid solution metal. The carbonized material is processed to a workpiece including nitride particles of solid solution metal dispersed and dispersed in the mother phase by using a carbon source in which oxygen coexists, and 30 to 150 ppm (wt%) of carbon having the grain boundary segregation by the carbonization treatment. A material for heat-resistant construction comprising a high melting point metal-based alloy having a high strength and a recrystallization temperature, comprising oxide particles converted from nitride particles. The heat-resistant structural material according to claim 1, wherein the surface portion of the alloy material is a processed structure, and the inside is a recrystallized structure. The heat-resistant structural material according to claim 1, wherein Mo is used as a mother phase, Ti is a solid solution metal, and a recrystallization temperature is 1600 ° C or higher. An alloy processing material containing 0.1 to 5.0 wt% of Mo, W, Cr as a mother phase and containing at least one of Ti, Zr, Hf, V, Nb, and Ta as a solid solution metal in a multistage interior of a nitride atmosphere. The nitriding treatment is performed by dispersing and containing the nitride particles of the solid solution metal in the mother phase, and then performing carbonization treatment using a carbon source in which oxygen coexists in the alloying material, wherein the high melting point metal alloy of claim 1 is used. Method of manufacturing the material. The method of claim 4, wherein the first stage nitriding treatment is performed at a temperature below the recrystallization upper limit temperature of the alloying material and at a recrystallization lower limit temperature-(minus) of 200 deg. C or higher to disperse and form nitride particles of the solid solution metal. Is carried out at a temperature above the lower limit of recrystallization of the alloying material obtained in the first stage nitriding treatment to stabilize and grow nitride particles dispersed and formed by the first stage nitriding treatment. Manufacturing Method The method for producing a heat-resistant structural material according to claim 4, wherein the carbonization treatment is performed using an inert gas containing 0.1 to 5% by volume of CO.

Images