WO2014185181A1

WO2014185181A1 - Powder for forming sprayed layer, thermite sprayed layer, thermite coating material, and method for producing thermite coating material

Info

Publication number: WO2014185181A1
Application number: PCT/JP2014/059430
Authority: WO
Inventors: 太一中道
Original assignee: 東洋鋼鈑株式会社
Priority date: 2013-05-17
Filing date: 2014-03-31
Publication date: 2014-11-20
Also published as: CN104797731A; CN104797731B; SG11201509282SA; JP2014224297A; JP6116998B2

Abstract

This powder for forming a sprayed layer and containing an Mo₂(Ni, Cr, V, Fe)B₂-type complex boride is characterized in that the composition is 5.5-6.5 wt% of B, 48.8-57.7 wt% of Mo, 1.8-2.5 wt% of Si, 6.0-10.0 wt% of Cr, 1.0-3.0 wt% of V, 6.0-10.0 wt% of Fe, and at least 17.0 wt% of Ni. By means of the present invention, it is possible to provide a powder that is for forming a sprayed layer and that is for forming a thermite sprayed layer that is magnetic, has superior corrosion resistance and wear resistance, and is such that fusion processing for increasing adhesion to the base material can be carried out at relatively low temperatures.

Description

Powder for forming sprayed layer, cermet sprayed layer, cermet coating material, and method for producing cermet coating material

The present invention relates to a thermal spray layer forming powder, a cermet thermal spray layer, a cermet coating material, and a method for producing the cermet coating material.

In order to improve the surface characteristics of a base material such as metal, a processing method is used in which a coating is formed by spraying an alloy powder or the like on the surface of the base material by a thermal spraying method. Such a thermal spraying method is widely applied to various members because it can be carried out relatively easily. Especially, it is industrially effective as an effective method for partially imparting corrosion resistance and wear resistance to the surface of a substrate. It is used in various fields.

In general, Ni-based self-fluxing alloys, Co-based stellite alloys, and the like are used as alloy powder materials for forming a film on a substrate by a thermal spraying method because of excellent adhesion to the substrate. It has been. In particular, in a Ni-based self-fluxing alloy, after a thermal spray layer is formed by thermal spraying, the thermal spray layer is heated and subjected to fusing treatment (melting treatment), whereby the thermal spray layer is melted and thermally diffused with the base material. It is known that the adhesion to the material is further improved. However, although Ni-based self-fluxing alloys and Co-based stellite alloys have excellent adhesion to the substrate, there is a problem that the corrosion resistance and wear resistance of the sprayed layer are insufficient.

On the other hand, for example, Patent Document 1 discloses a technique for improving corrosion resistance and wear resistance by using a cermet material containing a Mo ₂ NiB ₂ type double boride as a powder material used in a thermal spraying method. Has been.

JP 2009-68052 A

However, in the technique described in Patent Document 1, the Mo ₂ NiB ₂ type double boride serving as the cermet sprayed layer is excellent in corrosion resistance and wear resistance, but compared with the above-described Ni-based self-fluxing alloy, There was a possibility that adhesiveness with a substrate might fall. On the other hand, in order to improve the adhesion to the base material, a method of performing a fusing treatment on the cermet sprayed layer made of Mo ₂ NiB ₂ type double boride is also used. Is required to be a high temperature of 1200 ° C. or higher, which is the melting temperature of the cermet sprayed layer, so that excessive heat may cause deformation of the substrate and deterioration of properties.

Further, conventionally, when a cermet coating material having a cermet sprayed layer is used as a member for a resin molding machine or the like, if cracks and peeling of the cermet sprayed layer occur, the fragments of the cermet sprayed layer become resin. There was a problem that it was mixed in, causing contamination of the resin and failure of the resin molding machine. Therefore, it is necessary to remove the debris of the cermet sprayed layer mixed in the resin. For example, if the debris of the cermet sprayed layer mixed in the resin has magnetism, the debris can be removed using a magnet. It becomes possible to collect easily, thereby preventing contamination of the resin and failure of the resin molding machine. However, in the technique described in Patent Document 1, since the formed cermet sprayed layer is weak in magnetism, a recovery method using such a magnet cannot be applied, and fragments of the cermet sprayed layer are taken out from the resin. This is difficult, and has resulted in deterioration of the quality and yield of the resulting resin molding.

The present invention has been made in view of such a situation, and its purpose is to have a fusing treatment that has magnetism, is excellent in corrosion resistance and wear resistance, and further improves adhesion to the substrate. Provided is a powder for forming a sprayed layer for forming a cermet sprayed layer that can be carried out at a low temperature. Another object of the present invention is to provide a cermet sprayed layer and a cermet coating material obtained by using such a thermal spray layer forming powder, and a method for producing such a cermet coating material.

The present inventors contain Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride as a powder for forming a sprayed layer for forming a cermet sprayed layer, and have a specific composition range. The inventors have found that the above object can be achieved by using the prepared powder, and have completed the present invention.

That is, according to the present invention, a powder for forming a thermal spray layer containing Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride, and the composition is B: 5.5 to 6.5 wt%. , Mo: 48.8 to 57.7% by weight, Si: 1.8 to 2.5% by weight, Cr: 6.0 to 10.0% by weight, V: 1.0 to 3.0% by weight, Fe There is provided a powder for forming a thermal spray layer, characterized by being 6.0 to 10.0% by weight and Ni being 17.0% by weight or more.

According to the present invention, there is provided a cermet sprayed layer formed by spraying the above-mentioned powder for forming a sprayed layer, and a hard material containing the Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride. There is provided a cermet sprayed layer characterized in that the phase is contained in a proportion of 55.0 to 75.0% by weight and the balance is a binder phase mainly composed of a Ni-based alloy.

Moreover, according to this invention, the cermet coating | covering material by which the said cermet sprayed layer is formed on a base material is provided.
Alternatively, according to the present invention, a cermet comprising a diffusion layer formed by thermally diffusing the base material and the cermet sprayed layer by subjecting the cermet sprayed layer to a melting treatment by heating at 1000 to 1150 ° C. A dressing is provided.

In the present invention, in any of the above cermet covering materials, preferably, the base material is alloy steel, carbon steel, or stainless steel.

Further, according to the present invention, the thermal spray layer forming powder containing the Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride is sprayed on the base material, so that the cermet thermal spraying is performed on the base material. A method for producing a cermet covering material comprising a step of forming a layer, wherein the composition for sprayed layer formation is such that the composition is B: 5.5 to 6.5% by weight, Mo: 48.8 to 57.7% by weight , Si: 1.8 to 2.5 wt%, Cr: 6.0 to 10.0 wt%, V: 1.0 to 3.0 wt%, Fe: 6.0 to 10.0 wt%, Ni : 17.0% by weight or more of powder and containing a hard phase containing the Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride in a proportion of 55.0 to 75.0% by weight A method for producing a cermet coating material, characterized in that the remainder forms a cermet sprayed layer that is a binder phase mainly composed of a Ni-based alloy. There is provided.

In the method for producing a cermet coating material according to the present invention, preferably, after the cermet sprayed layer is formed on the substrate, the cermet sprayed layer is further subjected to a melting process of heating at 1000 to 1150 ° C.

According to the present invention, there is provided a cermet sprayed layer that has magnetism, is excellent in corrosion resistance and wear resistance, and can perform a fusing treatment for improving adhesion to a substrate at a relatively low temperature. A powder for forming a thermal spray layer for forming can be provided. In addition, the present invention can also provide a cermet sprayed layer and a cermet coating material formed by using such a thermal spray layer forming powder, and a method for producing such a cermet coating material.

FIG. 1 is a diagram showing the evaluation results of the abrasion resistance of the cermet sprayed layer in Examples and Comparative Examples. FIG. 2 is a view showing a test piece for measuring the adhesion of the cermet sprayed layer. FIG. 3 is a diagram showing the evaluation results of the adhesion of the cermet sprayed layer in Examples and Comparative Examples.

<Powder for thermal spray layer formation>
First, the thermal spray layer forming powder of the present invention will be described.
The thermal spray layer forming powder of the present invention is an alloy powder for forming a cermet thermal spray layer on a substrate by thermal spraying, and includes Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride, Composition: B: 5.5 to 6.5 wt%, Mo: 48.8 to 57.7 wt%, Si: 1.8 to 2.5 wt%, Cr: 6.0 to 10.0 wt%, V: 1.0 to 3.0% by weight, Fe: 6.0 to 10.0% by weight, Ni: 17.0% by weight or more.

In the present invention, the powder for thermal spray layer formation contains Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride, and the composition is in the above range. There is an effect. That is, first, when the powder for forming a thermal spray layer of the present invention is sprayed on a base material to form a cermet thermal spray layer, the obtained cermet thermal spray layer is made of Mo ₂ (Ni, Cr, high corrosion resistance and wear resistance). Due to the action of the V, Fe) B ₂ type double boride, it can be made excellent in corrosion resistance and wear resistance. In addition, the melting temperature of the obtained cermet sprayed layer can be lowered by the action of lowering the eutectic point due to Si, thereby spraying the powder for forming the sprayed layer of the present invention onto the substrate. In the case where the fusing treatment is performed on the formed cermet sprayed layer in order to improve the adhesion to the base material, the heating temperature during the fusing treatment can be lowered. Therefore, according to the present invention, when a fusing treatment is performed on the obtained cermet sprayed layer, the diffusion layer is formed by thermally diffusing the cermet sprayed layer with the base material while preventing deformation and deterioration of the base material due to heat. It is possible to effectively improve the adhesion between the base material and the cermet sprayed layer.

In addition, in the present invention, the cermet sprayed layer obtained by adding a specific amount of Fe to the Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride constituting the powder for forming the sprayed layer. Is provided with magnetism. In particular, according to the present invention, since the content of Fe in the double boride is in the above range, the magnetism imparted to the cermet sprayed layer can be made moderate. When the cermet coating material obtained by thermal spraying on the material is used as a member such as a resin molding machine, cracks and peeling occur in the cermet sprayed layer, and fragments of the cermet sprayed layer are mixed in the resin. Moreover, it becomes possible to collect | recover fragments easily using a magnet, and can thereby prevent the contamination of the resin manufactured with a resin molding machine, and the failure of a resin molding machine.

In the present invention, a cermet sprayed layer can be formed by spraying the above-mentioned powder for forming a sprayed layer of the present invention on a substrate, and the obtained cermet sprayed layer is usually Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride containing a hard phase that contributes to the hardness (wear resistance) of the cermet sprayed layer and a binder phase that forms a matrix for binding such a hard phase It will be formed.

Hereinafter, the action of each element described above contained in the thermal spray layer forming powder of the present invention will be described.

B (boron) is an element for forming a double boride that becomes a hard phase in the cermet sprayed layer when the cermet sprayed layer is formed. By setting the content ratio of B in the above range, when a cermet sprayed layer is formed, Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride is appropriately formed, and the obtained cermet sprayed layer Abrasion resistance and strength can be made excellent. When the content ratio of B is too low, the formation amount of the double boride is reduced, which may reduce the wear resistance of the obtained cermet sprayed layer. On the other hand, when the content ratio of B is too high, the formation amount of double boride increases, and in the obtained cermet sprayed layer, the contact ratio between the hard phases increases, and as a result, the mechanical strength decreases. Resulting in.

Similarly to B, Mo (molybdenum) is an element for forming a double boride that becomes a hard phase in the cermet sprayed layer when the cermet sprayed layer is formed. Moreover, when a part of Mo is used as a cermet sprayed layer, it has an effect of improving the corrosion resistance due to solid solution in the binder phase in the cermet sprayed layer. If the Mo content is too low, the wear resistance and corrosion resistance of the resulting cermet sprayed layer may be reduced. On the other hand, when the content ratio of Mo is too high, when a cermet sprayed layer is formed, a third phase is formed and the mechanical strength is lowered. In the present invention, when the cermet sprayed layer is used, a part of Mo in the Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride is W, Nb, Zr, Ti, Ta, It may be substituted with another element such as Hf.

Ni (nickel), like B and Mo, is an element for forming a double boride that becomes a hard phase in the cermet sprayed layer when the cermet sprayed layer is formed. Moreover, when it is set as a cermet sprayed layer, it is a main element which forms the Ni base alloy used as a binder phase in a cermet sprayed layer, and contributes to the outstanding corrosion resistance. In the present invention, a part of Ni in the double boride of the obtained cermet sprayed layer may be substituted with other elements such as Cr, V, and Fe as described later. In the case of the cermet sprayed layer, the Ni-based alloy constituting the binder phase is not particularly limited, but for example, at least one selected from Ni and Co, Cr, Mo, W, Fe, Mn, and V. An alloy with a seed metal may be mentioned.

When Cr (chromium) is used as a cermet sprayed layer, the cermet sprayed layer has a solid solution with Ni in the double boride that becomes the hard phase, and stabilizes the crystal structure of the double boride to a tetragonal crystal. Have Further, when the added Cr is used as a cermet sprayed layer, it is dissolved in the binder phase in the cermet sprayed layer, and the corrosion resistance, wear resistance, high temperature characteristics, and mechanical characteristics are greatly improved. When the Cr content is excessively large, borides such as Cr ₅ B ₃ are formed in the obtained cermet sprayed layer, and the mechanical strength is lowered.

Fe (iron) is an element for forming a double boride by substitutional solid solution with Ni in the double boride which becomes a hard phase in the cermet sprayed layer when the cermet sprayed layer is formed. Further, when a part of Fe is used as a cermet sprayed layer, in the cermet sprayed layer, it is also dissolved in the binder phase. In the present invention, by containing Fe, magnetism can be imparted to the obtained cermet sprayed layer. In particular, by providing the content ratio of Fe within the above range, the magnetism imparted to the cermet sprayed layer is moderate. Can be adjusted to things. If the content ratio of Fe is too low, the effect of imparting magnetism to the obtained cermet sprayed layer cannot be sufficiently obtained. On the other hand, if the content ratio of Fe is too high, the hardness of the obtained cermet sprayed layer decreases, resulting in As a result, the wear resistance is reduced.

When V (vanadium) is used as a cermet sprayed layer, the effect of stabilizing the crystal structure of the double boride in a tetragonal crystal by replacing it with Ni in the double boride that becomes the hard phase in the cermet sprayed layer. Have In addition, when a part of V is used as a cermet sprayed layer, it dissolves in the binder phase in the cermet sprayed layer, thereby improving the wear resistance. As described above, in the present invention, by adding Fe to the thermal spray layer forming powder, magnetism can be imparted to the obtained cermet thermal spray layer. On the other hand, in order to impart magnetism, Fe When the content ratio is increased, the hardness of the obtained cermet sprayed layer tends to decrease. Therefore, in the present invention, by adding V to the thermal spray layer forming powder and balancing the contents of Fe and V in the thermal spray layer forming powder, the hardness is increased while imparting magnetism to the obtained cermet thermal spray layer. Can be improved. If the V content is too small, it is difficult to obtain the effect of adding V. On the other hand, if the V content is too large, borides such as VB are formed in the obtained cermet sprayed layer, resulting in a decrease in mechanical strength. End up.

Si (silicon) is an element constituting a binder phase in the cermet sprayed layer when it is used as a cermet sprayed layer, and has an effect of lowering the melting temperature of the obtained cermet sprayed layer. When the content ratio of Si is too low, the effect of lowering the melting temperature of the obtained cermet sprayed layer cannot be sufficiently obtained, and when performing fusing treatment at the melting temperature of the cermet sprayed layer, excessive heat causes There is a risk that deformation or characteristic deterioration may occur. On the other hand, if the content ratio of Si is too high, the effect of lowering the melting temperature of the obtained cermet sprayed layer cannot be obtained, and the content of silicide increases and the characteristics such as toughness may be reduced. is there.

As described above, each element contained in the thermal spray layer forming powder acts.

In the thermal spray layer forming powder of the present invention, the Fe content may be in the range of 6.0 to 10.0% by weight as described above, but preferably 6.0 to 8.0. % By weight. By setting the content ratio of Fe in the thermal spray layer forming powder within the above range, the magnetism imparted to the obtained cermet thermal spray layer can be made moderate. If the content ratio of Fe in the thermal spray layer forming powder is too low, sufficient magnetism cannot be imparted to the obtained cermet thermal spray layer. On the other hand, when the content ratio of Fe is too high, the hardness of the obtained cermet sprayed layer is lowered.

In the thermal spray layer forming powder of the present invention, the V content may be in the range of 1.0 to 3.0% by weight as described above, but preferably in the range of 1.0 to 2.0. % By weight. By setting the content ratio of V in the thermal spray layer forming powder within the above range, the hardness of the obtained cermet thermal spray layer can be appropriately improved. In the present invention, as described above, by adding Fe and V to the thermal spray layer forming powder, it is possible to achieve both imparting magnetism and improving hardness in the obtained cermet thermal spray layer. In that case, it is preferable to adjust the content ratio of V according to the content ratio of Fe.

In the thermal spray layer forming powder of the present invention, the Si content may be in the range of 1.8 to 2.5% by weight as described above. By setting the content ratio of Si in the sprayed layer forming powder within the above range, the melting temperature of the obtained cermet sprayed layer can be lowered, and the heating temperature necessary for fusing the cermet sprayed layer can be reduced. Can be lowered.

In the thermal spray layer forming powder of the present invention, the effect of imparting magnetism to the obtained cermet sprayed layer, the effect of improving hardness, and the effect of lowering the melting temperature of the cermet sprayed layer are unavoidable. The element which mixes in may be contained.

<Base material>
The substrate for spraying the thermal spray layer forming powder of the present invention is not particularly limited, and various metal materials can be used, but from the viewpoint of excellent material strength, alloy steel, carbon steel, stainless steel, Tool steel, powdered high-speed steel, and the like are mentioned. Among these, alloy steel, carbon steel, and stainless steel are preferably used from the viewpoint of relatively low hardness and easy formation of a sprayed layer.

<Cermet sprayed layer>
The cermet sprayed layer of the present invention is obtained by spraying the above-mentioned powder for forming a sprayed layer on a base material, and has a hard phase containing a Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride. The balance is a binder phase mainly composed of a Ni-based alloy.

Here, the hard phase of the cermet sprayed layer is a phase contributing to the hardness of the cermet sprayed layer, that is, the wear resistance.

The content ratio of the hard phase in the cermet sprayed layer is preferably 55.0 to 75.0% by weight, more preferably 65.0 to 75.0% by weight, and further preferably 70.0 to 75.0% by weight. . By making the content rate of a hard phase into the said range, the corrosion resistance and abrasion resistance of the cermet coating | covering material obtained can be improved more. If the content ratio of the hard phase is too low, the cermet sprayed layer becomes too soft and wear resistance is reduced. On the other hand, if the content ratio of the hard phase is too high, the dispersibility of the hard phase becomes too bad and the strength is lowered. In addition, the content rate of the hard phase in a cermet sprayed layer is controllable by adjusting the content rate of Mo and B in the powder for thermal spray layer formation for forming a cermet sprayed layer, for example.

Further, the binder phase of the cermet sprayed layer is a phase that forms a matrix for binding the hard phase.

The binder phase of the cermet sprayed layer is mainly composed of a Ni-based alloy, and such a Ni-based alloy is formed from Ni contained in the sprayed layer forming powder. The Ni-based alloy is not particularly limited, and examples thereof include an alloy of Ni and at least one metal selected from Co, Cr, Mo, W, Fe, Mn, and V.

In the present invention, since the cermet sprayed layer is formed using the above-mentioned sprayed layer forming powder, the content ratio of Fe and V in the cermet sprayed layer is usually the same as the content ratio of Fe and V in the sprayed layer forming powder. Similarly, Fe: 6.0 to 10.0% by weight, and V: 1.8 to 2.5% by weight. Therefore, in the cermet sprayed layer of the present invention, it is possible to achieve both imparting magnetism and improving hardness by the above-described effects of Fe and V. Here, Fe and V contained in the cermet sprayed layer may be contained in either the hard phase or the binder phase in the cermet sprayed layer, or may be contained in both the hard phase and the binder phase.

As the hardness of the cermet sprayed layer, Vickers hardness (HV) is preferably 1200 or more, more preferably 1250 or more. By setting the Vickers hardness of the cermet sprayed layer within the above range, excellent wear resistance can be imparted to the cermet sprayed layer.

Furthermore, since the cermet sprayed layer of the present invention is formed using the above-mentioned sprayed layer forming powder, the Si content in the cermet sprayed layer is usually the same as the Si content in the sprayed layer forming powder. Si: 1.8 to 2.5% by weight. Therefore, in the cermet sprayed layer of the present invention, the heating temperature in performing the fusing treatment can be made relatively low due to the above-described action of Si. Here, Si contained in the cermet sprayed layer may be contained in either the hard phase or the binder phase in the cermet sprayed layer, or may be contained in both the hard phase and the binder phase.

In addition, as a cermet sprayed layer formed on a base material, a cermet sprayed layer containing Mo ₂ NiB ₂ type double boride as a component of a hard phase has been conventionally used. However, the cermet sprayed layer containing such a Mo ₂ NiB ₂ type double boride has a problem that the adhesion to the substrate may be lowered. On the other hand, in order to improve the adhesion between the cermet sprayed layer and the base material, a method of performing a fusing treatment after the cermet sprayed layer is formed on the base material is used. _Since the cermet sprayed layer containing ₂ NiB ₂ type double boride usually has a melting temperature of 1200 ° C. or higher, the heating temperature in performing the fusing treatment needs to be 1200 ° C. or higher. Further, there has been a problem that excessive heat may cause deformation of the base material or deterioration of characteristics.

On the other hand, the cermet sprayed layer of the present invention includes Si in a cermet sprayed layer containing Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride and lowers its melting temperature. Therefore, it becomes possible to perform a fusing treatment at a low temperature, and while preventing deformation and deterioration of properties of the base material, the cermet sprayed layer is thermally diffused with the base material to form a diffusion layer, and the base material and the cermet sprayed layer are formed. Can be effectively improved.

The melting temperature of the cermet sprayed layer of the present invention can be controlled, for example, by changing the content ratio of Si in the binder phase. The melting temperature is preferably 1000 to 1150 ° C., more preferably 1000 to 1100 ° C.

In the case where the cermet sprayed layer of the present invention is subjected to a fusing treatment, the heating temperature during the fusing treatment can be set according to the melting temperature of the cermet sprayed layer, preferably 1000 to 1150 ° C., more preferably 1000 to 1100 ° C. In the present invention, by setting the heating temperature in the fusing treatment to the above range, when the fusing treatment is performed on the cermet sprayed layer, it is possible to effectively prevent the deformation of the base material and the deterioration of the characteristics due to heat. In addition, although it does not specifically limit about the heating time at the time of performing a fusing process, What is necessary is just to set suitably according to the thickness etc. of a cermet sprayed layer.

<Cermet coating material>
The cermet coating material of the present invention is obtained by forming the above-described cermet sprayed layer on a substrate. Therefore, the cermet coating material of the present invention includes a base material and a cermet sprayed layer formed on the base material. In the cermet coating material of the present invention, in addition to these, the base material and the cermet A diffusion layer formed by thermally diffusing the thermal spray layer may be further provided. The diffusion layer can be formed by subjecting the cermet sprayed layer of the cermet coating material to a fusing treatment under the above-described conditions and thermally diffusing the base material and the cermet sprayed layer.

<Method for producing cermet covering material>
Next, the manufacturing method of the cermet coating | covering material of this invention is demonstrated.

First, raw material powder for producing a thermal spray layer forming powder is prepared. As the raw material powder, B: 5.5 to 6.5% by weight, Mo: 48.8 to 57.7% by weight, Si: 1.8 to 2.5% by weight, Cr: 6.0 to 10.0 A powder mixed in such a ratio as to be wt%, V: 1.0 to 3.0 wt%, Fe: 6.0 to 10.0 wt%, Ni: 17.0 wt% or more is prepared.

Next, the prepared raw material powder is processed into a thermal spray layer forming powder. The method of processing the raw material powder into the thermal spray layer forming powder may be any method as long as a Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride is formed from the raw material powder. A binder and an organic solvent are added to the raw material powder, these are mixed and pulverized using a pulverizer such as a ball mill, and the mixed and pulverized raw material powder is granulated with a spray drier, etc. The method of classifying later is mentioned. Thus, in the present invention, a Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride is contained, the composition is B: 5.5 to 6.5 wt%, Mo: 48.8 to 57.7 wt%, Si: 1.8 to 2.5 wt%, Cr: 6.0 to 10.0 wt%, V: 1.0 to 3.0 wt%, Fe: 6.0 to 10. A thermal spray layer forming powder of 0 wt% and Ni: 17.0 wt% or more is obtained. In addition, in the powder for thermal spray layer formation of this invention, the element mixed unavoidable may be contained in the range which does not inhibit the effect of lowering the melting temperature of the obtained cermet thermal spray layer.

When mixing and pulverizing with a ball mill or the like, the particle size of the raw material powder after mixing and pulverizing is not particularly limited. When the raw material powder after mixing and pulverizing is granulated and sintered, Mo ₂ (Ni , Cr, V, Fe) formation reaction of B ₂ type complex boride may be a particle size such as to proceed properly.

The sintering conditions may be within a range in which the formation reaction of the Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride proceeds appropriately. For example, the temperature is 1000 to 1150. C., sintering time: 30 to 90 minutes, heating rate: 0.5 to 60.degree. C./min.

The size of the powder for forming a thermal spray layer to be produced is preferably 10 to 200 μm, more preferably 32 to 150 μm, in view of easy spraying.

Next, the powder for forming the sprayed layer is sprayed onto the base material by a spraying method to form a cermet sprayed layer. Thereby, in this invention, the cermet coating | covering material formed by coat | covering a cermet sprayed layer on a base material is manufactured. As the thermal spraying method, either flame flame spraying with a low thermal effect at the time of cermet spraying layer formation or high-speed flame spraying may be adopted, but since the spraying speed of the powder for thermal spraying layer formation is high, a dense film can be formed. High speed flame spraying is preferred.

Further, the thickness of the cermet sprayed layer to be formed is preferably 0.05 mm to 2.0 mm, and more preferably 0.2 mm to 1.0 mm. If the thickness of the cermet sprayed layer to be formed is less than 0.05 mm, pores may remain in the cermet sprayed layer, and the cermet sprayed layer may be peeled off from the base material due to the pores, and the cermet sprayed layer is thin. Therefore, the wear resistance tends to decrease. On the other hand, if the thickness of the cermet sprayed layer to be formed is larger than 2.0 mm, the residual stress due to heat at the time of forming the cermet sprayed layer increases, so the adhesion between the cermet sprayed layer and the substrate tends to decrease. .

As described above, the cermet coating material using the thermal spray layer forming powder of the present invention is manufactured.

In the present invention, it is preferable that the cermet coating material thus manufactured is further subjected to a fusing treatment. By subjecting the cermet coating material to a fusing treatment, the cermet sprayed layer is thermally diffused with the base material to form a diffusion layer, and the adhesion between the base material and the cermet sprayed layer is improved. The fusing treatment method is not particularly limited, and for example, a method such as heating by a flame torch using acetylene and oxygen as fuel, high-frequency induction heating, heating by an atmospheric furnace, or heating by a vacuum furnace can be used. From the viewpoint that the cermet sprayed layer can be thermally diffused stably, it is preferable to use a heating method using a vacuum furnace. In addition, the heating temperature at the time of performing a fusing process is the same as the conditions mentioned above.

According to the present invention, the composition of the thermal spray layer forming powder containing the Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride has a composition of B: 5.5 to 6.5% by weight, Mo : 48.8 to 57.7% by weight, Si: 1.8 to 2.5% by weight, Cr: 6.0 to 10.0% by weight, V: 1.0 to 3.0% by weight, Fe: 6 By setting the content to 0.0 to 10.0% by weight and Ni: 17.0% by weight or more, a cermet sprayed layer having excellent corrosion resistance and wear resistance can be formed by thermal spraying.

In addition, the cermet coating material of the present invention obtained using such a thermal spray layer forming powder can be heated at a relatively low temperature even in the fusing treatment, so that the base material is deformed by heat. In addition, it is possible to effectively improve the adhesion between the base material and the cermet sprayed layer by forming the diffusion layer by thermally diffusing the cermet sprayed layer with the base material while preventing deterioration of characteristics. Moreover, since the heating temperature at the time of performing a fusing process can be made into comparatively low temperature, the cermet coating | covering material of this invention becomes the thing excellent in productivity. Furthermore, the cermet coating material of the present invention was used as a consumable member because the base material and the cermet sprayed layer were in close contact with each other by fusing treatment and had durability capable of withstanding high load loads. In such a case, the replacement frequency can be reduced, and as a result, the amount of discarded consumable members can be reduced, contributing to environmental protection.

In addition, the cermet coating material of the present invention obtained by using such a powder for forming a thermal spray layer has magnetism due to the action of Fe contained in the cermet coating material, and therefore is used as a member for resin molding machines and the like. In the case where cracks and delamination occur in the cermet sprayed layer and fragments of the cermet sprayed layer are mixed in the resin, if the fragments of the cermet sprayed layer have magnetism, use a magnet. Debris can be easily collected, thereby preventing contamination of the resin produced by the resin molding machine and failure of the resin molding machine.

In particular, when an insulating resin is used as a resin to be molded by a resin molding machine, if the cermet sprayed particles are mixed into the insulating resin, the insulating properties of the resin are affected by the conductivity of the metal contained in the fragments. Will be reduced. On the other hand, according to the present invention, the debris of the cermet sprayed layer mixed in the resin can be easily collected using a magnet. Maintained and superior quality, and improved yield.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1
B: 6.0 wt%, Mo: 53.25 wt%, V: 2.0 wt%, Fe: 8.0 wt%, Cr: 8.0 wt%, Si: 2.5 wt%, Ni: 5 parts by weight of paraffin was added to 100 parts by weight of the raw material mixed at a ratio of 20.25% by weight, and this was pulverized in acetone by a vibration ball mill for 25 hours. . Next, the prepared pulverized powder was dried at 150 ° C. for 18 hours in a nitrogen atmosphere. Then, after mixing the dried pulverized powder with acetone in a weight ratio of 1: 1, the powder is granulated by a spray dryer, and the granulated powder is held at 1150 ° C. in vacuum for 1 hour to sinter the powder. By classifying this, a thermal spray layer forming powder containing a Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride was produced.

Next, the melt temperature was measured for the produced sprayed layer forming powder. Specifically, the melting temperature was measured by pulverizing the thermal spray layer forming powder to a particle size of 10 to 300 μm and measuring the melting temperature with a differential thermal analyzer (manufactured by Rigaku Corporation, model number: TG8120). The results are shown in Table 1.

Next, a SUS304 steel plate, which is a non-magnetic base material, is prepared, and the prepared thermal spray layer forming powder is sprayed on the prepared base material using a high-speed flame spraying machine (TAFA, model number: JP8000). Thus, a cermet coating material obtained by coating a cermet sprayed layer on a substrate was obtained. The cermet sprayed layer was formed under the conditions of spraying distance (distance between substrate and spraying gun): 300 mm, kerosene amount: 5.5 gph, oxygen flow rate: 1900 scfh. And the fusing process was performed with respect to the obtained cermet coating | covering material on the conditions of heating temperature: 1150 degreeC and heating time: 60 minutes in a vacuum furnace.

Next, for the cermet coating material that has been subjected to fusing treatment, a magnet (ferrite magnet) is brought close to the surface cermet sprayed layer, and whether or not the magnet is adsorbed by the magnetic force to the cermet sprayed layer is checked. The presence or absence of was evaluated. The results are shown in Table 1.

Furthermore, the Vickers hardness (HV) of the surface cermet sprayed layer was measured for the cermet coating material subjected to the fusing treatment using a Vickers hardness meter (manufactured by Akashi Seisakusho, model number: MVK-G2). The results are shown in Table 1.

<< Examples 2 to 12 >>
Except that the mixing ratio of V, Fe, Cr, Si, and Ni in the raw materials is as shown in Table 1, a sprayed layer forming powder and a cermet coating material were obtained and evaluated in the same manner as in Example 1. Went. The results are shown in Table 1.

<< Comparative Examples 1 to 23 >>
Except that the mixing ratio of B, Mo, V, Fe, Cr, Si, and Ni in the raw materials was as shown in Table 2, a sprayed layer forming powder and a cermet coating material were obtained in the same manner as in Example 1. The same evaluation was performed. The results are shown in Table 2. In Table 2 and Table 3 to be described later, the portion where the melting temperature is higher than 1150 ° C. in the measurement result of the melting temperature is displayed in gray. Similarly, the portion where the magnetism is absent in the evaluation result of the presence / absence of magnetism and the portion where the hardness is less than 1200 HV in the result of measuring the Vickers hardness of the cermet sprayed layer are also displayed in gray. did.

<< Comparative Examples 24-44 >>
Except that the mixing ratio of B, Mo, V, Fe, Cr, Si, and Ni in the raw materials was as shown in Table 3, a sprayed layer forming powder and a cermet coating material were obtained in the same manner as in Example 1. The same evaluation was performed. The results are shown in Table 3.

Next, using the cermet coating material of Example 6 described above, the wear resistance of the surface cermet sprayed layer was evaluated. That is, the evaluation of wear resistance is a method in which a rotating ring member is pressed against the cermet coating material of Example 6 to measure the volume of wear marks formed on the surface of the cermet coating material (Ogoshi wear test). It went by. In addition, as a ring member pressed against the cermet covering material, martensitic stainless steel (SUS440C, surface Vickers hardness 650HV), cermet sintered body A (manufactured by Toyo Kohan Co., Ltd., product number: KH-C50, surface Vickers hardness 1150HV) ) And cermet sintered body B (manufactured by Toyo Kohan Co., Ltd., product number: KH-N51, surface Vickers hardness of 1280 HV) were used. The test conditions were final load: 19.8 kg, sliding distance: 200 m, and the sliding speed was evaluated under three conditions of 0.2, 0.9, and 4.21 m / s. The measurement results of the volume of wear marks (wear volume) formed on the surface of the cermet covering material are shown in FIGS. 1 (A) to 1 (C). 1A shows martensitic stainless steel as a ring member, FIG. 1B shows the cermet sintered body A as a ring member, and FIG. 1C shows the cermet firing as a ring member. The result at the time of using the ligature B is each shown.

<< Comparative Examples 45 to 47 >>
As a comparison with the cermet coating material of Example 6, it was also used as an alumina sintered body (Comparative Example 45), a WC-based self-fluxing alloy (Comparative Example 46) having a WC content of 50% by weight, and the ring member. The cermet sintered body A (Comparative Example 47) was prepared, and the abrasion resistance was evaluated in the same manner as in Example 6 described above. The results are shown in FIGS. 1 (A) to 1 (C).

Next, the adhesion when the thermal spray layer forming powder was sprayed onto a steel material was evaluated using the thermal spray layer forming powder of Example 6 described above. Specifically, first, a test piece 100 made of steel (SKD11) and having the shape shown in FIG. 2 was prepared as a base material for performing thermal spraying. 2 has a cylindrical shape with a diameter of 20 mm at both ends (the fixed portion 10 and the rotating portion 30 in FIG. 2), and the central portion (the cermet sprayed layer forming portion 20 in FIG. 2) is It has a cylindrical shape with a diameter of 10 mm. Then, of the prepared test piece 100, the thermal spraying of Example 6 prepared above was performed on the cermet sprayed layer forming portion 20 in FIG. 2 using a high-speed flame sprayer (TAFA, JP-5000). A cermet sprayed layer was formed on the cermet sprayed layer forming portion 20 by spraying the layer forming powder. The cermet sprayed layer was formed under the conditions of spraying distance: 300 mm, kerosene amount: 6 gph, oxygen flow rate: 1850 scfh. Next, the test piece 100 on which the cermet sprayed layer is formed is subjected to a fusing treatment in a vacuum furnace under the conditions of a heating temperature of 1100 ° C. and a heating time of 60 minutes, thereby obtaining the cermet coating material shown in FIG. It was.

And the adhesiveness evaluation was performed about the cermet coating | covering material shown in FIG. 2 obtained as mentioned above. That is, the adhesion is evaluated by applying a torsional torque to the cermet covering material by rotating the rotating part 30 while the fixing part 10 of the test piece 100 is fixed by a torsion tester (manufactured by Shimadzu Corporation, UET-300). When the target value of the torsional torque is set to three conditions of 200 N · m, 300 N · m, and 400 N · m, it was observed whether cracks and delamination occurred in the cermet sprayed layer, and the following criteria It was done by evaluating with. The results are shown in Table 4 and FIGS. 3 (A) to 3 (C). 3A is evaluated with a torsional torque value of 196 N · m, FIG. 3B is evaluated with a torsional torque value of 294 N · m, and FIG. 3C is evaluated with a torsional torque value of 401 N · m. It is a photograph which shows the cermet coating | covering material of Example 6 in performing.
○: Cracks and peeling of the cermet sprayed layer were not confirmed.
X: Cracks and peeling of the cermet sprayed layer occurred.

<< Comparative Example 48 >>
A steel material (SKD11) having the shape shown in FIG. 1 is coated with cermet coating by spraying a powder for forming a sprayed layer of WC-12% Co under the conditions of spraying distance: 380 mm, kerosene amount: 6 gph, oxygen flow rate: 2100 scfh. A material was prepared, and in the same manner as in Example 6 described above, the adhesion was evaluated when the target value of the torsional torque value was 200 N · m. The results are shown in Table 4 and FIG. FIG. 3D is a photograph showing the cermet covering material of Comparative Example 48 when the torsion torque value is 191 N · m.

As shown in Table 1, it contains Mo ₂ (Ni, Cr, V, Fe) B ₂ type double boride, the composition is B: 5.5 to 6.5 wt%, Mo: 48.8 to 57 0.7 wt%, Si: 1.8 to 2.5 wt%, Cr: 6.0 to 10.0 wt%, V: 1.0 to 3.0 wt%, Fe: 6.0 to 10.0 The thermal spray layer forming powders of Examples 1 to 12 each having a weight% of Ni: 17.0% by weight or more had a melting temperature of 1000 to 1150 ° C. As a result, when the fusing treatment is performed on the thermal spray layer forming powders of Examples 1 to 12 after the cermet thermal spray layer is formed by thermal spraying, the heating temperature for thermally diffusing the cermet thermal spray layer can be suppressed. As a result, it can be determined that the base material is prevented from being deformed or deteriorated in characteristics and has excellent adhesion to the base material. In particular, as shown in Table 4 and FIGS. 3 (A) to 3 (C), the thermal spray layer forming powder of Example 6 was subjected to a torsional torque after becoming a cermet thermal spray layer by thermal spraying. It can be determined that the cermet sprayed layer does not crack or peel off and has excellent adhesion to the substrate.

Further, as shown in Table 1, since the sprayed layer forming powders of Examples 1 to 12 all have magnetism, the cermet coating material obtained using such a sprayed layer forming powder is When used as a member of a resin molding machine or the like, even when cracks and peeling of the cermet sprayed layer occur, it is possible to easily collect the debris of the cermet sprayed layer with a magnet. In this way, it is possible to prevent contamination of the resin to be manufactured and failure of the resin molding machine.

Further, as shown in Table 1, all the cermet coating materials obtained using the thermal spray layer forming powders of Examples 1 to 12 have a high Vickers hardness of 1200 HV or more and excellent wear resistance. Can be determined. In particular, as shown in FIGS. 1 (A) to 1 (C), the cermet coating material obtained using the thermal spray layer forming powder of Example 6 has a wear volume of wear marks when the Daikoshi wear test is performed. From this fact, it can be determined that the wear resistance is excellent.

On the other hand, as shown in Tables 2 and 3, the thermal spray layer forming powders of Comparative Examples 1 to 44 in which the content ratio of each element is outside the predetermined range of the present invention has at least a melting temperature exceeding 1150 ° C. Either it did not have magnetism or the Vickers hardness was less than 1200 HV. In Tables 2 and 3, for the evaluation results of each comparative example, the part where the melting temperature exceeds 1150 ° C., the part where the magnetism is lost, and the part whose hardness is less than 1200 HV are filled with gray. Is displayed.

And in each comparative example, in the comparative example in which the melting temperature exceeds 1150 ° C., when the obtained thermal spray layer forming powder is sprayed onto the base material to form a cermet coating material, a fusing treatment is performed. In addition, since it is necessary to set the heating temperature for thermally diffusing the cermet sprayed layer to a high temperature exceeding 1150 ° C., it can be determined that the base material is deformed or deteriorated due to the fusing treatment.

Further, among the comparative examples, in the comparative examples that did not have magnetism, the obtained thermal spray layer forming powder was sprayed on the base material to form a cermet coating material, which was then used as a member for a resin molding machine or the like. In this case, if debris generated by cracking and peeling of the cermet sprayed layer is mixed in the resin, the mixed debris does not have magnetism and cannot be recovered by a magnet. This is considered to cause contamination and failure of the resin molding machine, leading to deterioration of the quality and yield of the obtained resin molding. In addition, in the cermet coating materials of Comparative Examples 1, 2, and 10, as shown in Tables 2 and 3, although it did not contain Fe, it resulted in having magnetism, this is due to the action of Ni That is, although Ni is weak in magnetism as compared with Fe, the content thereof is increased, and as a result, the obtained cermet covering material becomes magnetized.

Furthermore, in each comparative example, in the comparative example in which the Vickers hardness is less than 1200 HV, the obtained thermal spray layer forming powder has a low hardness, so it can be determined that the wear resistance is inferior. .

Claims

A powder for forming a thermal spray layer containing a Mo 2 (Ni, Cr, V, Fe) B 2 type double boride,
Composition: B: 5.5 to 6.5 wt%, Mo: 48.8 to 57.7 wt%, Si: 1.8 to 2.5 wt%, Cr: 6.0 to 10.0 wt%, V: 1.0 to 3.0% by weight, Fe: 6.0 to 10.0% by weight, Ni: 17.0% by weight or more.
A cermet sprayed layer formed by spraying the powder for forming a sprayed layer according to claim 1,
The hard phase containing the Mo 2 (Ni, Cr, V, Fe) B 2 type double boride in a proportion of 55.0-75.0% by weight, with the balance being a Ni-based alloy as the main component A cermet sprayed layer characterized by being a phase.
A cermet coating material in which the cermet sprayed layer according to claim 2 is formed on a substrate.
The diffusion layer formed by thermally diffusing the base material and the cermet sprayed layer by subjecting the cermet sprayed layer to a melting treatment by heating at 1000 to 1150 ° C. The described cermet coating material.
The cermet covering material according to claim 3 or 4, wherein the base material is alloy steel, carbon steel, or stainless steel.
A cermet having a step of forming a cermet sprayed layer on a base material by spraying a powder for forming a sprayed layer containing Mo 2 (Ni, Cr, V, Fe) B 2 type double boride on the base material. A method of manufacturing a covering material,
As the powder for forming the thermal spray layer, the composition is B: 5.5 to 6.5% by weight, Mo: 48.8 to 57.7% by weight, Si: 1.8 to 2.5% by weight, Cr: 6. Using powder of 0 to 10.0 wt%, V: 1.0 to 3.0 wt%, Fe: 6.0 to 10.0 wt%, Ni: 17.0 wt% or more,
The hard phase containing the Mo 2 (Ni, Cr, V, Fe) B 2 type double boride in a proportion of 55.0-75.0% by weight, with the balance being a Ni-based alloy as the main component A method for producing a cermet coating material, comprising forming a cermet sprayed layer as a phase.
The cermet coating material according to claim 6, further comprising a step of performing a melting treatment of heating the cermet sprayed layer at 1000 to 1150 ° C after forming the cermet sprayed layer on the substrate. Method.