JP2008024993A - Method of diffusing or implanting element to metallic member by driving hard particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of diffusing or implanting an element into a metallic member by which a problem that a conventional modification method of a metallic member by element implantation is carried out only in a limited specific purpose and lacks versatility such as homogeneous alloying is solved. <P>SOLUTION: A hard particle comprising an element to be diffused or implanted which is harder than a metallic member to be treated is driven into the metallic member at a high speed to diffuse or implant the element to be diffused or implanted from the contact interface between the driven hard particle and the metallic member. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a method for diffusing and injecting an element into a metal member by hard particle implantation, which is applied to diffuse and inject the element into a metal member and improve the performance of the member. Specifically, hard particles containing a large amount of the element to be diffused / injected are accelerated at supersonic speed to collide with the surface of the metal member at room temperature, and hard particles containing beneficial alloy elements are driven into the metal member surface in a wedge shape. A hard particle layer, or a layer of hard particles with a hard particle that is uniformly formed without being multi-layered, although it is somewhat accompanied by plastic deformation of the particles when implanted. And a method for easily and effectively diffusing and implanting elements.

It is known that metallic materials are greatly affected by the addition of a trace amount of elements and are strongly affected. For example, in structural steel, elements such as O, H, S, and Pb act as harmful elements, and the inclusion of these elements significantly impairs the toughness and ductility of the steel. On the other hand, elements such as B, C, N, Ce, La, Zr, and Hf are evaluated as acting as beneficial trace elements, and are blended and used as important alloy elements in various alloy designs. .

These elements are known to be strongly affected by the properties of the metal even if they are added in trace amounts on the ppm level. It is known that the amount of beneficial elements can be controlled appropriately, so that metals added with active ingredients can be significantly improved in toughness, corrosion resistance, high-temperature strength, etc., compared to the metals before addition. . For this reason, in general metal materials including iron-based metals, components are adjusted by adding various elements to improve performance. It is a well-known fact that various types of steels and various alloys with special properties and applications have been developed.

Various types of steels and various alloys specializing in applications and properties with the addition of such beneficial elements are manufactured by melting and uniformly melting a metal mixture having a designed component composition. However, manufacturing by such a melting method requires special adjustment of the material as a separate charge, which requires extra energy and is costly. Also, from the viewpoint of building a recycling-based society in recent years, an alloy containing many kinds of alloy elements has a low utility value as a general-purpose material because it contains a special component, and therefore reuse is limited. Therefore, an alloy containing a special component cannot be said to be preferable. For this reason, a structure is designed using an existing metal material that can be obtained, and after the design, the necessary components, such as elemental components such as B and C, are diffused / injected, and then revised afterwards. It can be thought of as quality. What is implemented as such a partial modification method is a surface modification method in which a hard compound is generated in the surface layer by so-called surface treatment, and the member itself is modified by element diffusion / injection. Is not implemented.

As a surface modification method by surface treatment, a general method is a surface modification method by surface reaction or element diffusion / injection, and a gas containing an additive element such as B in a specific sealed heating furnace. Known are gas diffusion heating methods by heating in an atmosphere, powder methods by heating by burying in powder containing additive elements, and salt bath methods for immersing and heating in molten salt. Yes. The surface reaction and element diffusion / injection method by contacting the surface of these materials with the target element-containing material is performed by heating the metal member to be processed to a high temperature of 650 to 1050 ° C.

Therefore, the additive element by this method reacts in the contacting surface layer portion, and is diffused and injected only in the extreme surface layer portion. This method diffuses the target element deeply in the material, and furthermore, it is difficult to adjust and control the atomic ratio of the alloy composition to a very small amount, and is unsuitable for modification of the member.
It was difficult. A typical application of this technique is a boride treatment in which boron is injected into the surface, but it is limited to a modification operation that hardens the surface exclusively. That is, although it is suitable for surface hardening treatment, it is not suitable for other purposes, modification of materials and members, for example, property improvement such as toughness and high temperature strength. Therefore, it has not reached the point where it is possible to locally inject beneficial elements and to enable material design and alloy design with intended physical properties. This method is not suitable for in-situ “in-situ injection” except in a specific heating furnace.

Recently, the thermal spraying method has come to be used as a surface modification method. Using a combustion gas, laser, and high frequency induction plasma as a heat source, the film forming material is melted to form a film material on the material surface, and beneficial elements are diffused and injected from the film into the metal material surface through the contact interface. However, the metal material film containing beneficial elements obtained by this method is likely to be altered due to oxidation reaction, etc., and there are many pores due to entrainment of bubbles, and the adhesion to the base material is low. It is extremely bad, and further, the base material is remarkably altered and deteriorated. for that reason,
The state of the contact interface is not a suitable technique for diffusion / injection from the film into the metal member, but it can be diffused / injected deep into the material to modify the member itself and increase the amount of elements. It is not suitable for the purpose of controlling the accuracy and designing the intended material and alloying. And this method is also
Not suitable for “in-situ injection” on site.

In addition, recent patent literature includes various high-temperature heat-resistant products such as molybdenum steel, chromium-molybdenum steel, chromium-molybdenum-vanadium steel, molybdenum-vanadium steel, chromium-molybdenum-tungsten steel, etc. In order to improve the creep strength and fatigue strength of a boiler tube made of metal or a welded heat affected zone in a related plant, boron compound powder such as B ₄ C is applied to the corresponding part, or iron boride Fe ₂
A reforming method comprising a step of plasma spraying a wire made of B to form a coating containing B element and then diffusing and infiltrating the B element by heating is described (see, for example, Patent Document 1) ) In addition, about this coating method and a thermal spraying method, in FIG. 1, (c), (d)
The embodiment is shown in FIG.

However, also in the film formation method in the modification method according to the proposal described in this patent document,
The film forming method is merely the coating method or the thermal spraying method shown in FIGS. 1 (c) and 1 (d). Therefore, these are basically out of the range of conventional methods. And to spread,
A high-temperature heating step is essential, and the formed film itself cannot be expected to function as a base protective layer. That is, according to the coating method, there is a possibility that the film may fall off. In addition, the thermal spraying method by high-temperature melting such as plasma spraying of the wire has the disadvantage that the adhesion between the coating and the base material is poor, and the base material itself may be deteriorated. Such an undesired phenomenon is caused, the problem is inherent in the film itself, and it is difficult to form a film in a good state.

The inventors have already accelerated the soft particles containing beneficial elements to supersonic speed as a method capable of diffusing and injecting beneficial elements deeply into materials and members, and colliding and plasticizing material surfaces. By deforming, the adhesion is good, the surface film is formed without altering the material itself,
A method for diffusing and injecting beneficial elements of the surface film into the material has been invented and a patent application has been filed (Patent Document 2). The method according to the invention of the earlier patent application can be said to be a technical aspect belonging to the cold spray method, and can be easily carried out even at room temperature, and can be easily applied to large members and on-site work. However, it is necessary to use plastically deformable particles,
There are some unique restrictions such as the fact that the amount of beneficial elements added to the particles is generally limited to a small amount, and that it is necessary to form a uniform and thick film (100 μm or more). Some problems remained in that advanced adjustments were required.
JP 2004-91832 A Japanese Patent Application No. 2006-133469 (Shinya, Kyono, “Metal film forming method applied to high-precision diffusion and implantation of beneficial elements”)

As described above, the conventional reforming method by element implantation is limited to a specific component element and is limited to a specific purpose. Therefore, it cannot be said that the technique is suitable as a basic reforming operation that can be used for various material designs. The invention previously filed by the inventors of the present invention is intended to provide a film forming method that makes this possible, but is limited to easy plastic particles and thick film forming conditions for forming a thick film. However, it is not necessarily general. Therefore, we provide a simple and easy method that does not require the plastic deformation of the particles, and that only hard particles that contain a large amount of beneficial elements and do not need to form a thick film are placed on the surface of the material or member at room temperature. It is something to try. This makes it possible to diffuse elements that are beneficial to the required location by a controlled effective amount without heating to a very high temperature, especially in various plants and facilities operating at high temperatures. The purpose of this invention is to provide a simple and easy method for diffusing and injecting beneficial elements in order to immediately modify metal members such as pipes for various purposes on site.

For this reason, as a result of earnest research, the present inventors have accelerated hard particles capable of containing a large amount of beneficial elements to supersonic speed and collided with metal members at room temperature, and hard particles containing beneficial elements on the metal member surface. Particles are driven into a wedge shape, and the particles are uniformly injected into the surface of the metal member.
The beneficial element is diffused and injected using the hard particles as the diffusion source, which consists of diffusing elements that diffuse through the interface between the implanted particles and the metal member. Has been found to be diffused, alloyed and modified.
This invention is made | formed based on this knowledge, The structure is the following (1)-(12
).

(1) A step of driving hard particles, which are harder than the metal member to be processed and containing elements to be diffused / injected, into the metal member at a high speed, and then a contact interface between the hard particles thus implanted and the metal member And a step of diffusing the element to be diffused / injected into the metal member. A method of diffusing / injecting the element into the metal member by hard particle implantation.
(2) The step of driving the hard particles into the metal member at a high speed is performed under a wide temperature range including normal temperature. Element diffusion and implantation methods.
(3) The step of driving the hard particles into the metal member at a high speed or the step of diffusing the element to be diffused / injected into the metal member is performed at the site where the metal member is installed.
(1) or (1) or (1) characterized in that the operation is performed without or without interruption
2) A method for diffusing and injecting elements into a metal member by hard particle implantation.
(4) The elements to be diffused / implanted are C, N, B, Ce, La, Zr, Hf, Ti
, One or more elements selected from the group consisting of Nb and Mo,
(1) The diffusion / injection method of an element into a metal member by hard particle implantation according to any one of (3).
(5) The hard particles are hard particles obtained by pulverization, (1)
Or diffusion of elements into the metal member by hard particle implantation described in any one of (4)
Injection method.
(6) To the metal member by hard particle implantation according to any one of (1) to (5), wherein the hard particles are hard particles having a diameter of 1 to 100 μm. Element diffusion and implantation methods.
(7) The hard particles are composed of hard particles selected from Fe ₂ B, FeB, or iron boride capable of forming a eutectic or hypereutectic alloy with Fe, (1) to ( 6) The method for diffusing and injecting an element into a metal member by hard particle implantation according to any one of 6).
(8) The hard particles are composed of hard particles selected from Ni ₃ B or nickel boride capable of forming a eutectic or hypereutectic alloy with Ni, (1) to (6) The element diffusion / injection method to the metal member by hard particle implantation according to any one of the above.
(9) The metal member into which the element is injected is a metal member selected from any one of carbon steel, low alloy steel, and austenitic steel, (1) to (8) Any one
A method for diffusing and injecting elements into a metal member by hard particle implantation as described in the section.
(10) The step of diffusing the element to be diffused / implanted into the metal member is performed by heating the metal member in a state where the hard particles are implanted by the previous step. A method for diffusing and injecting elements into a metal member by hard particle implantation described in 1).
(11) When the metal material is carbon steel or low alloy steel, the heating is in a temperature range of 500 to 750 ° C., and when the metal material is austenitic stainless steel, 650 to 900 ° C.
The method for diffusing and injecting elements into a metal member by hard particle implantation according to (9), characterized in that the method is carried out in a temperature range of
(12) When the metal member is a metal member used at a temperature of 1/3 or more of the melting point temperature Tm (absolute temperature) at the site of use, the diffusion step after the hard particle implantation is not particularly heated. It is characterized by diffusing by exposing to the temperature used as it is (1
The diffusion / injection method of elements into a metal member by hard particle implantation as described in (11) to (11).

FIG. 1 illustrates the present invention in comparison with the conventional coating method or thermal spraying method, and further to the invention relating to the soft particles described in the prior application of the present inventors. Is clearly understood. FIG. 1 (a) shows an embodiment according to the diffusion source hard particle implantation layer forming method of the present invention, and FIG. 1 (b) is an earlier application by the present inventors, which is a beneficial element of the present application. The method is an embodiment by a method of forming an alloy film including, and an embodiment by a method of forming a film by plastic deformation of soft particles (patent pending as Japanese Patent Application No. 2006-133469). Further, FIG. 1 (c) shows an embodiment according to a conventional method in which particles containing beneficial elements are applied (for example, JP-A-2004
No. -91832) and (d) in FIG. 1 shows a mode in which particles and wires containing beneficial elements are sprayed to form a film.

In carrying out the present invention, it is desirable that the metal member to be treated in advance is cleaned and a fresh metal ground is secured. Further, when the compound and the alloy particles are collided, the compound and the alloy particles are jetted at a normal temperature, but the metal member may be at a normal temperature, or may be in high temperature actual use as long as it is operating at a high temperature.

The hard particles injected at supersonic speed deform the metal member at the moment of collision and are driven into the metal member. At this time, the hard particles are flying with the least air resistance, that is, the sharpest surface facing the tip. Therefore, the hard particles are driven into the metal member in a wedge shape. After hard particle implantation, diffusion and heating processes are added, thereby adjusting the diffusion and injection of beneficial elements,
Control. The heating temperature condition of the diffusion / heating process is 500 to 750 in the case of carbon steel and low alloy steel.
In the case of ℃, austenitic stainless steel, it is preferable to carry out using a temperature of 650 to 900 ℃ as a guide.

The diffusion source hard particle implantation layer forming method applied to the diffusion / injection of the element according to the present invention comprises a compound or alloy fine particle containing a beneficial element to be diffused / injected and having a hardness higher than that of the metal member to be implanted. It is used at normal temperature, accelerated to supersonic speed, collides with the metal member to be processed, and hard particles are driven into the surface of an arbitrary region in a wedge shape or more uniformly, so that the metal member The surface does not have any problems associated with conventional surface treatments such as the influence of temperature and the deterioration due to oxidation and chemical changes.

The outermost layer of the metal member is hardened, and causes work hardening, but is beneficial because it has the same effect as the shot peening effect for improving the mechanical properties of the metal member surface, and is particularly harmful. Absent. The hard particles are deeply wedged with an acute angle surface as a tip, or form a wave-like layer when accompanied by plastic deformation, but since they are all stable, they are not detached in the subsequent heat treatment process or the like. Since a clean diffusion source is implanted on the surface and is in close contact with the metal member, it is possible to easily diffuse and inject beneficial elements through the contact interface.

In the present invention, the use of hard particles is a requirement, so that these particles hardly or hardly undergo plastic deformation. Therefore, the state of the metal member after being driven by the collision of the hard particles with the metal member is naturally restricted when the hard particles colliding thereafter are occupied when the hard particles are occupied by the first hard particles. In other words, hard particles collide with the particles that were initially injected, but in this case, the particles that collide later are regulated by the first particles, and the hard particles overlap each other, resulting in a multilayer state. It is never formed. That is, one hard particle is formed autonomously. Therefore,
There is no case where a thick film over multiple layers is formed unlike the conventional method including the invention of the prior application. Rather, multilayering is difficult. However, since it is possible to contain a large amount of beneficial elements in the hard particles, there is no particular problem even if it is not a thick film.

The material of the hard particles used can select a stable material such as a stable compound or a heat-resistant alloy, so the diffusion source forming surface into which the hard particles are implanted is thermally, chemically, It is also mechanically stable. Accordingly, it may be possible to independently perform the diffusion / injection step by the subsequent diffusion / heating step at any time and in any place. Typically, after the hard particle implantation layer forming step is performed, there is no problem even if it is left without performing the diffusion step by heating, and the heating step may include an embodiment in which the heating step is not performed until necessary. Typically, diffusion source hard particle implantation may be performed at the factory, transported to the field, operated, and diffused and injected at the operating temperature, which may include this aspect.

The diffusion source hard particle implantation layer obtained by the method of the present invention is generally clean, has good adhesion, and is optimal for diffusing and injecting trace elements. Moreover, it can be formed on site. This technology can be applied immediately to various devices and plants at the installation site, and is a highly effective technology with a wide range of applications. That is, the diffusion source hard particle implantation method of the present invention is excellent in applicability and economy because it is low in cost, simple in equipment, and easy on-site work. If this method can inject beneficial elements such as B that greatly extend the lifetime only to the target site, it will improve the economics and reliability of the new plants, and will greatly increase the lifetime of aged plants. Can be extended.

Hereinafter, the present invention will be specifically described based on the drawings and examples. However, these are disclosed only as an aid for easily understanding the present invention, and the present invention is not limited thereto.

Example 1;
The diffusion source hard particles for diffusing / implanting the B element were ferroboron in which 19% by weight of B was added to the Fe base and having a eutectic structure of α-Fe and Fe ₂ B. An Fe-B alloy bath was prepared, solidified and then mechanically pulverized, and the powder was classified using a 53 μm mesh. Since the material was hard and brittle, it could be easily mechanically pulverized to obtain fine particles. The average particle size is 17 ±
4 μm. The reason for setting the Fe-based material is that the main material of the metal member into which the diffusion source hard particles are implanted is Fe-based, and that ferroboron is easily available. This is because it is extremely stable in handling, and this was used as a base material for diffusion source hard particles. FIG. 2 is a photograph of the Fe-containing eutectic alloy powder containing B observed with a scanning electron microscope. Its shape is polygonal, slightly elongated, has an acute angle surface, and is suitable for driving in a wedge shape. Although there were variations in size, the powder was rich in monodispersity.

Next, the Fe—B eutectic alloy powder is supersonic flow from the nozzle with N ₂ gas, and the SU—
S304 was made to collide with the steel sample surface and driven into the sample surface. The sample size is 20mmφ ×
A hard particle implantation layer was formed on the surface of 10 pieces each at 3 mmt. The optimum conditions, which are key points such as the gas pressure to be set, were examined in advance using a dummy sample. as a result,
The driving conditions obtained were as shown in Table 1. Although the velocity at the time of particle implantation is not measured, in the experiment using particles of the same size under the same pressure conditions as this experiment,
Report of a particle velocity of 640 m / s (Kazuhiko Tsuji; Thermal spray technology, vol. 26, No. 2, p. 3
2, 2000), the particle velocity is considered to have reached supersonic speed.

The alloy powder was made to collide with the surface of SUS304 steel under the conditions shown in Table 1.
FIG. 3 shows an Fe—B eutectic alloy implantation layer formed on the surface of SUS304 steel. The sample shown in FIG. 3 is subjected to heat treatment at 750 ° C. for 10 hours after implantation. Hard particles were driven into the surface of the steel plate and formed in close contact with the steel plate. From this figure, it was determined that B could easily diffuse through the contact interface. Due to the heat treatment, hard particles of Fe ₂
The B component of B diffused into the SUS304 steel and the hard particles began to shrink partially. Moreover, there were no reaction products and the surface was chemically clean. Since a Fe—B eutectic alloy was used as the hard particles, the hard particles were partly plastically deformed, and the implanted hard particles were partly deformed in a wedge shape, forming a 5-30 μm wavy layer. In addition, as the inner side of the implantation layer was implanted to a depth of 100 μm, a processed layer in which a slip band was formed was observed.

Example 2;
In this embodiment, a diffusion / heat treatment process is added to the diffusion source hard particle implantation process in the first embodiment. That is, after implantation, a sample of SUS304 steel was heated in an Ar atmosphere to perform diffusion / injection treatment of the B element into the sample. Table 2 shows the conditions for diffusion and injection by heating.

Quantitative measurement of the injection amount of the B injection by the diffusion source hard particle implantation and the subsequent diffusion / injection treatment was performed. For the quantitative measurement of B, laser ICP mass spectrometry (LA-ICP-MS) was used, and the diffusion / injection amount of trace B in the depth direction was quantitatively determined by high-precision local analysis. ICP
The mass spectrometer is a Perkin Elmer Elan6000 (quadrupole) type, and the high frequency output is 40.68 MHz and 1 kW. For laser ablation, an Nd-YAG fixed laser was used. The laser spot size is 100 μm.

FIG. 4 shows the relationship between the measurement position from the laser-ablated surface and the ion intensity of B measured by an ion mass spectrometer. In the figure, the data of the heating material of the SUS304 steel material that has not been implanted with Fe-B eutectic alloy particles is also shown for comparison.

As a result, in the comparative sample in which the Fe—B eutectic alloy is not implanted, the B ion intensity is naturally not changed by the heat treatment or in the depth direction, and remains at a low level. On the other hand, the Fe-B eutectic alloy particles are implanted and the heat-treated sample has a very high B ion intensity in the surface layer portion, and rapidly decreases with the distance in the depth direction from the surface. After a rapid drop, equilibrium is reached and the value becomes almost constant. This constant ionic strength is
The higher the heating temperature and the longer the heating time, the higher the value. This constant value is considered to correspond to the solid solution amount of B that brings about the effect of beneficial elements.

FIG. 5 is a calibration curve showing the relationship between B ion intensity and B content. From FIG. 5, Fe
It was found that by implanting -B eutectic alloy particles, several ppm to 200 ppm of B element can be diffused and implanted at a depth of several mm. Since the element B sufficiently exhibits its beneficial effect even when several ppm is added, it has been confirmed that the diffusion source hard particle implantation layer forming method of the present invention is extremely effective for austenitic stainless steel. It was.

FIG. 6 is a patent application of the B diffusion / injection result of SUS304 stainless steel in FIG. 5 (a metal film forming method applied to high system diffusion / injection of beneficial elements, Japanese Patent Application No. 2006-133).
469). The heat treatment conditions for diffusion / implantation are the same, and the B distribution in the depth direction is similar, and is substantially the same especially inside the depth of 200 μm or more. The method of the present invention is a simple method for implanting only one hard particle, but the same effect as the method of forming a thick film was obtained. This is mainly because the diffusion source is hard particles that do not require plastic deformation,
This is because a large amount of B is contained. Therefore, if limited to B injection, it can be said that the present invention is simpler and more effective in injecting B. The conventional coating method and thermal spraying method could not be compared because quantitative measurement of diffusion and injection of beneficial trace elements was not performed and there was no analysis data.

As described above, according to the present invention, the polygonal hard particles that are the diffusion source of beneficial elements are uniformly or wedged into the metal member, and the beneficial components contained therein are divided between the hard particles and the metal member. It is to diffuse and inject through the interface to modify the metal member. The hard particles can be easily and deeply driven by a normal cold spray method simply by flowing at high speed at room temperature. The wedge-shaped hard particles are exclusively used as a diffusion source for diffusing and injecting beneficial elements, but because of their good adhesion to the base metal, they function as a diffusion source stably for a long period of time. . This hard particle implantation process is the same as shot peening performed to improve normal mechanical properties, and the residual strain of the surface layer caused by hard particle implantation improves mechanical properties such as improving crack formation resistance. Has an effect.
In the examples, the B element that can be expected to have a material modification effect was selected as the index useful element, and the reason is as described above. The present invention is not limited to the B element as long as it is a beneficial element that can be modified. Moreover, although the iron-type metal material was used as an object metal member, it is not limited to this. That is, it should be understood that the combination of the material of the metal member and the beneficial element may include various combinations that can be alloyed.

The present invention presents a method that can be easily modified afterwards without interrupting the operation of an already designed / manufactured metal member or at the installation site. It can be said that it is a highly practical proposal and can be used greatly as a repair and life extension measure in various plants in the future.

Comparison of beneficial element injection method of the present invention with conventional methods. In the figure, (a) is a diffusion source hard particle implantation layer forming method of the present invention, (b) is a method of forming an alloy film containing beneficial elements for which the inventors have applied, (c) is a conventional coating method, (D) shows the conventional thermal spraying method. ΑFe and Fe 2 _B of observation drawings by scanning electron microscope of the eutectic alloy particles comprising the active element (B) used in Examples. The observation drawing by the scanning electron microscope of the implantation particle | grains to the sample surface layer obtained by making the alloy particle | grains shown in FIG. 2 collide with the SUS304 steel surface. The figure which showed the diffusion condition of the useful element (B) by heating temperature and time after particle | grain implantation on the surface of SUS304 steel by the ionic strength corresponded to the depth from the surface, and B amount. In the figure, (a) shows the case of heating at 750 ° C., and (b) shows the case of heating at 850 ° C. The figure which shows the calibration curve of B content by the ionic strength of the standard sample of B amount. The B diffusion / injection effects of the diffusion source hard particle implantation layer forming method and the alloy film forming method of the present invention are compared and shown.

Claims (12)

Hard particles that are harder than the metal member to be treated and that contain the elements to be diffused / injected into the metal member at a high speed, and then diffused from the contact interface between the hard particles and the metal member. A method for diffusing and injecting an element into a metal member by implanting hard particles, the method comprising: diffusing an element to be injected into the metal member. The diffusion of elements into the metal member by hard particle implantation according to claim 1, wherein the step of driving the hard particles into the metal member at a high speed is performed under a wide temperature range including normal temperature. -Injection method. The step of driving the hard particles into the metal member at a high speed and the step of diffusing the element to be diffused / injected into the metal member interrupt the use work at the use site where the metal member is installed, The method of diffusing and injecting an element into a metal member by hard particle implantation according to claim 1, wherein the method is performed without interruption. The elements to be diffused / implanted are C, N, B, Ce, La, Zr, Hf, Ti, N
The element diffusion into the metal member by hard particle implantation according to any one of claims 1 to 3, wherein the element is one or more elements selected from the group consisting of b and Mo.
Injection method. The element diffusion / injection method to a metal member by hard particle implantation according to any one of claims 1 to 4, wherein the hard particles are hard particles obtained by pulverization. The element diffusion to the metal member by the hard particle implantation according to any one of claims 1 to 5, wherein the hard particles are hard particles having a diameter of 1 to 100 µm. Injection method. Said hard particles, Fe 2 _B, FeB or characterized by comprising the selected hard particles of Fe eutectic or hypereutectic iron boride which can form a eutectic alloy, any one of claims 1 to 6, 2. A method for diffusing and injecting elements into a metal member by hard particle implantation according to item 1. 7. The hard particle according to claim 1, wherein the hard particle comprises Ni ₃ B or a hard particle selected from nickel boride capable of forming a eutectic or hypereutectic alloy with Ni.
A method for diffusing and injecting elements into a metal member by hard particle implantation as described in the section. The metal member into which the element is injected is a metal member selected from any one of carbon steel, low alloy steel, and austenitic steel, according to any one of claims 1 to 8. The element diffusion / injection method to the metal member by hard particle implantation as described. The step of diffusing the element to be diffused / implanted into the metal member is performed by heating the metal member in a state where the hard particles are implanted by the previous step. The element diffusion / injection method to the metal member by hard particle implantation as described. When the metallic material is carbon steel or low alloy steel, the heating is performed in a temperature range of 500 to 750 ° C., and when the metallic material is austenitic stainless steel, the heating is performed in a temperature range of 650 to 900 ° C. The element diffusion / injection method to the metal member by hard particle implantation according to claim 9. When the metal member is a metal member that is used at a temperature of 1/3 or more of the melting point temperature Tm (absolute temperature) at the site of use, the diffusion step after the hard particle implantation is used without heating. 12. The method of diffusing and injecting an element into a metal member by hard particle implantation according to claim 1, wherein the element is diffused by being exposed to a certain temperature as it is.

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