JP5400194B2 - Molten zinc corrosion resistant metallic glass - Google Patents

Description

  The present invention relates to a metallic glass, particularly a metallic glass having corrosion resistance against molten zinc.

Hot-dip plating is widely used as a method for forming a metal film on a substrate using molten metal of lead, tin, zinc and aluminum or their alloys, and steel materials are widely used for members that come into contact with molten metal such as plating baths. .
However, since molten zinc reacts with iron of the steel material to easily form a zinc-iron alloy layer, the erosion property to the steel material is extremely higher than that of molten lead or molten tin, and damage (melting loss) is remarkable.
For this reason, increasing the corrosion resistance of steel members in contact with hot dip galvanized steel galvanized steel sheet production lines and soaking galvanizing equipment, etc., and extending the life of the members will increase productivity and reduce costs. This is an important issue.

First, as an improvement in the corrosion resistance of steel by composition, for example, C is 0.12 to 0.30%, Si is 0.05% or less, Mn is 0.2 to 2.0%, and P is 0. A steel material for a galvanizing kettle composed of .015% or less and the balance of iron and impurities is known (Patent Document 1), and is commercially available as NAGP ^(R) steel plate (Nippon Nippon Steel Co., Ltd.). However, the corrosion resistance was not satisfactory.

Therefore, two methods are generally used for the purpose of preventing member erosion due to contact with molten zinc.
The first is a method of coating (coating) a member with a sprayed coating of a cermet material (such as WC-12% Co) that is harder to wet with zinc than steel and is hard, such as carbide, boride, and nitride. is there.
However, since the metal (Co or the like) that is the bonding layer (binder) of the cermet sprayed coating reacts with the molten zinc, the bonding layer disappears and the ceramic particles in the sprayed coating fall off, and the erosion gradually proceeds. The corrosion resistance was not satisfactory.

The second is a method using ceramics. Ceramics are excellent in molten metal corrosion resistance, so they are used in plating baths and immersion heating tubes that maintain the temperature of plating baths. However, they are very expensive and do not have the toughness of metal materials, and mechanical shocks. And is vulnerable to thermal shock.
Therefore, it has been desired to develop a corrosion-resistant metal material that is less damaged by molten zinc.

Amorphous alloys generally have higher corrosion resistance than crystalline alloys because they have fewer element localizations and grain boundaries than crystalline alloys.
In recent years, metallic glass has been known as an alloy that has a very high ability to form amorphous compared to conventional amorphous alloys and can obtain bulk amorphous from a molten state at a relatively slow cooling rate. Has also been reported.

For example, Patent Document 2 describes a high corrosion resistance Fe—Cr based metallic glass.
However, although Patent Document 2 shows excellent acid resistance against an aqueous HCl solution (25 ° C.), it does not describe any corrosion resistance against molten metal, particularly molten zinc.

Further, Patent Document 3 describes a metal glass sprayed coating having excellent corrosion resistance against molten lead-free solder, and Fe ₄₃ Cr ₁₆ Mo ₁₆ C ₁₅ B ₁₀ as a specific example.
However, as described above, molten zinc has a very high reactivity with iron compared to molten lead-free solder containing molten tin as a main component, and according to the study by the present inventors, it has excellent molten lead-free solder corrosion resistance. Even with the Fe ₄₃ Cr ₁₆ Mo ₁₆ C ₁₅ B ₁₀ metallic glass, the corrosion resistance against molten zinc was insufficient.
In addition, although amorphous alloys are generally considered to have higher corrosion resistance than crystalline alloys, depending on the composition, even amorphous glass metallic glass is more resistant to molten zinc than crystalline alloys such as NAGP steel. Sometimes it was inferior.

JP 49-130310 A JP 2009-24256 A JP 2006-97132 A

  This invention is made | formed in view of the said background art, The objective is to provide the metal material excellent in the corrosion resistance with respect to molten zinc, and the molten zinc corrosion-resistant member using the same.

As a result of intensive studies by the present inventors, it has been found that a metal glass having a specific composition is very excellent in corrosion resistance against molten zinc, and has completed the present invention.
That is, the molten zinc corrosion-resistant metallic glass according to the present invention has a composition represented by the following formula (1), the supercooled liquid temperature region (ΔTx) is 30 ° C. or higher, and the glass transition temperature (Tg) is higher than the molten zinc temperature. Is characterized by being 20 ° C. or higher.
(Fe, Cr) _{100- (a + b + c)} W _a TM _b (C, B, P) _c (1)
(In the formula, TM is at least one selected from Mo, Ta, V, and Nb, a is 2 to 20 atom%, b is 0 to 15 atom%, c is 20 to 30 atom%, and Fe is 35 to 55 atoms. %.)

  In the present invention, “hot zinc” means a molten metal containing zinc as one main component, and is usually used in hot dip galvanization in these melts as well as pure zinc and zinc alloy melts. Also included are those added with an additive element (for example, Al, Sn, etc.). For example, 97.5% or more of pure zinc specified in JIS H8641 “hot dip galvanizing”, JIS G3317 “5% aluminum alloy plated steel sheet and steel strip”, JIS G3321 “molten 55% aluminum-zinc alloy plated steel sheet and steel” This includes zinc-aluminum alloys defined in “Zone” and tin-zinc-based lead-free solder defined in JIS Z3182 “Solder, Chemical Composition and Shape”.

The present invention also provides a molten zinc corrosion-resistant metallic glass characterized in that the metallic glass is an amorphous phase solid.
Moreover, this invention provides the molten zinc corrosion-resistant metallic glass characterized by having a glass transition temperature (Tg) of 600 ° C. or higher in any of the metallic glasses described above.

The present invention also provides a hot-dip zinc corrosion-resistant sprayed coating comprising any one of the above-described metallic glasses.
The present invention also provides a molten zinc corrosion-resistant sprayed coating characterized in that the sprayed coating has a porosity of 2% or less and no pinholes.

Further, the present invention is the spray coating according to any one of the above, characterized in that it is a spray coating formed by high-speed flame spraying or a spraying method having a sprayed particle flying speed equal to or higher than this. A coating is provided.
Further, according to the present invention, in any one of the thermal spray coatings described above, an amorphous phase metal glass powder having the composition of the formula (1) is used as a thermal spray raw material, and at least a part of the thermal spray raw material is not melted. A molten zinc corrosion-resistant sprayed coating characterized by being an amorphous phase sprayed coating formed by spraying in a cooling liquid state.

In addition, the present invention provides the one-part room temperature curing, wherein the thermal spray coating according to any one of the above, further comprises the following components (a) and (b), and the viscosity of the component (a) at 25 ° C. is 20 to 1000 mPa · s. Provided is a hot-dip zinc corrosion-resistant sprayed coating which is sealed with a mold sealant.
(A) At least one compound selected from an alkoxysilane compound represented by the following formula (2) and a partial hydrolyzate thereof:
R ¹ _n Si (OR ² ) _4-n (2)
(In the formula, each R ¹ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² is each independently an alkyl group having 1 to 4 carbon atoms, and n is 0 to 3) Is an integer).
(B) Curing catalyst.

  Moreover, this invention provides the molten zinc corrosion-resistant member characterized by the contact surface with molten zinc, or the base layer of this contact surface having the metal glass or sprayed coating as described above.

  Since the metallic glass concerning this invention exhibits the outstanding corrosion resistance with respect to molten zinc, it can utilize suitably for a molten zinc corrosion-resistant member. Moreover, this metallic glass can also be used for hot-dip zinc corrosion-resistant coating. For example, a hot-dip zinc-corrosion-resistant member can be obtained by coating the surface of a member that requires hot-zinc corrosion-resistant material by thermal spraying. Moreover, the molten zinc corrosion resistance can be further improved by subjecting the metal glass sprayed coating of the present invention to a sealing treatment.

It is a schematic diagram of the cross section of the metallic glass sprayed coating of this invention. It is the schematic of the molten zinc immersion test method of a ribbon material sample. Of _{Fe 43 Cr 16 Mo 1 W 15} C 15 B 10 rod-like samples coated with the sprayed film metallic glass (sample 2-1), which is a photograph after molten zinc immersion test. Of _{Fe 43 Cr 16 Mo 16 C 15} B 10 coated rod-like sample in the thermal sprayed coating of metallic glass (Sample 2-a), an appearance photograph after molten zinc immersion test.

A rod-shaped sample (Sample 2-1) coated with a sprayed coating of Fe ₄₃ Cr ₁₆ Mo ₁ W ₁₅ C ₁₅ B ₁₀ metallic glass, and a rod-shaped sample coated with a sprayed coating of Fe ₄₃ Cr ₁₆ Mo ₁₆ C ₁₅ B ₁₀ metallic glass It is an EDS-SEM analysis result of the cross-sectional structure after the molten zinc immersion test of (Sample 2-a) It is an EDS-SEM analysis result of the cross-sectional structure | tissue after the hot-dip zinc immersion test of a NAGP steel plate. Melting of a plate-like sample (Sample 3-1) coated with a sprayed coating of Fe ₄₃ Cr ₁₆ Mo ₁ W ₁₅ C ₁₅ B ₁₀ metal glass and a sample (Sample 3-d) coated with a WC-12Co sprayed coating It is a photograph which shows the wetting test result with respect to zinc (480 degreeC).

Fe ₄₃ Cr ₁₆ Mo ₁ W ₁₅ C ₁₅ B ₁₀ Metallic glass sprayed coating (Sample 4-1) and EDS-SEM analysis of the cross-sectional structure after the molten zinc immersion test of the sealed coating (Sample 5-1) It is a result. Molten zinc immersion of metal glass sprayed coatings of Fe ₄₃ Cr ₁₆ Mo ₁ W ₁₅ C ₁₅ B ₁₀ and Fe ₄₃ Cr ₁₆ Mo ₁₆ C ₁₅ B ₁₀ (Sample 5-1 and Sample 5-a), respectively. It is an EDS-SEM analysis result of the cross-sectional structure after the test.

The metallic glass concerning this invention is the Fe-Cr-W group metallic glass shown by the composition of following formula (1).
(Fe, Cr) _{100- (a + b + c)} W _a TM _b (C, B, P) _c (1)

In Formula (1), Fe is a main component and is 35-55 atomic%. Since Fe is inexpensive, the cost increases as it decreases. On the other hand, if the amount is too large, the amount of other elements is limited, and the corrosion resistance and amorphous forming ability become insufficient.
In addition, although the sum total of Fe and Cr is 35-78 atomic%, Preferably it is 50-70 atomic%.

  Cr is an element which is the basis of the corrosion resistance of the Fe-based alloy, and is preferably 10 to 20 atomic%. If the amount of Cr is too small, the effect may not be obtained sufficiently, and if it is too large, the ability to form an amorphous state may be lowered.

  W is an essential component for the molten zinc corrosion resistance of the metallic glass of the present invention. a represents atomic percent of W, and preferably 2 to 20 atomic percent. If a is too small, sufficient molten zinc corrosion resistance cannot be obtained, and if a is too large, other components are limited and the amorphous forming ability is lowered.

  In formula (1), TM is at least one element selected from Mo, Ta, V, and Nb, and b represents the total atomic% of TM. The element group of TM improves molten zinc corrosion resistance and amorphous forming ability. The metallic glass of the present invention can exhibit molten zinc corrosion resistance without containing TM, but it is desirable to contain TM as necessary. However, if there is too much TM, other components are limited, the amorphous forming ability is lowered, a crystal phase is likely to be generated, and corrosion resistance of molten zinc may be impaired, so TM is 15 atomic% or less. Preferably it is.

  C and B contribute to the amorphous forming ability when used in combination. P is an element that can increase the amorphous forming ability when used in combination with B and C, and can be contained as required. c represents the total atomic% of C, B, and P, and is preferably 20 to 30 atomic%. If c is too little or too much, sufficient amorphous forming ability may not be obtained. As a more preferable range, C is 5 to 20 atomic%, B is 5 to 15 atomic%, and P is 0 to 5 atomic%.

Metallic glasses are characterized by a distinct glass transition and a wide supercooled liquid region before crystallization when heated from an amorphous phase solid, which is clearly distinguished from ordinary amorphous alloys in thermal behavior. .
In the metallic glass of the present invention, the temperature interval ΔTx of the supercooled liquid region represented by the formula ΔTx = Tx−Tg (where Tx is the crystallization start temperature and Tg is the glass transition temperature) is 30 ° C. or more, It is suitable that it is 50 degreeC or more. The metal glass having such a large ΔTx is excellent in amorphous forming ability and workability, and is advantageous in obtaining a dense amorphous sprayed coating as described later. Note that ΔTx≈0 in a normal amorphous alloy.

  Metallic glass becomes a viscous fluid at temperatures above Tg. Therefore, the glass transition temperature Tg of the Fe—Cr—W-based metallic glass of the present invention needs to be higher than the temperature of the target molten zinc, and is desirably 20 ° C. or higher. The operating temperature (hot dip zinc temperature) in hot dip galvanizing is usually 450 to 550 ° C., and can be used without any problem in most hot dip galvanizing if the glass transition temperature Tg is 600 ° C. or higher.

  If the crystal phase is contained in the metal glass, the corrosion resistance is liable to be adversely affected. Therefore, the crystal phase content in the metal glass is preferably as low as possible, for example, 20% or less, more preferably 10% or less. More preferably, the metallic glass is an amorphous single phase.

The metallic glass can be produced into an amorphous phase solid by a known production method. For example, a raw metal is melted to create a master alloy, which is then cooled and solidified using various rapid cooling methods such as single roll method, twin roll method, spinning in spinning liquid, atomizing method, etc. , Powder and the like.
The Fe—Cr—W-based metallic glass of the present invention has a ΔTx of 30 ° C. or higher, preferably 50 ° C. or higher and high amorphous forming ability. It can also be formed as a bulk body of an amorphous phase by a method.

As a method for coating the surface of the substrate with metal glass, physical vapor deposition methods such as sputtering, ion plating, and CVD are generally performed.
However, although these methods can form a metallic glass thin film, it takes a very long time to obtain a sufficient film thickness, and it is difficult to increase the area.
In addition, in wet systems such as electrolytic plating, precipitation conditions are difficult, the composition is not stable, and wastewater treatment is required.

On the other hand, spraying is a dry process that does not require wastewater treatment, and is advantageous in terms of simplicity, large area, thick film, and adhesion to a substrate.
Therefore, by spraying using the Fe—Cr—W-based metallic glass of the present invention, a thick hot-dip zinc corrosion-resistant sprayed coating can be easily formed on the surface of a large area substrate.
It is desirable in terms of corrosion resistance that the thermal spray coating is an amorphous phase, is dense with few pores, and has no pinholes.

  The thermal spraying method is not particularly limited, but as one of the methods for forming a thermal spray coating having a uniform metal glass amorphous solid phase and almost no pores and no pinholes, for example, amorphous phase metal glass A method in which powder is used as a spraying raw material and sprayed in a supercooled liquid state without melting metal glass particles is suitable.

In the supercooled liquid state, the metal glass exhibits a viscous flow and becomes a fluid having a higher viscosity than the melt. For this reason, when the metallic glass particles in the supercooled liquid state collide with the base material surface, they can be crushed instantly and spread on the base material surface with little splash, forming a very thin splat. it can. And, by depositing such splats, it is possible to form a dense thermal spray coating without pinholes.
Moreover, since the splat is cooled in the supercooled liquid state, a crystalline phase is not generated, and only an amorphous phase is obtained.

In general, in the case of thermal spraying in the atmosphere, since the thermal spray material is melted and collided with the base material, the oxide of the thermal spray material is included in the coating, which adversely affects the properties of the coating. If the metallic glass particles are heated to the supercooled liquid state without being melted and collided, even if sprayed in the atmosphere, there is almost no influence of oxidation.
Therefore, when the amorphous phase metallic glass particles are heated to a supercooled liquid state by thermal spraying and solidified and laminated on the surface of the substrate, the amorphous solid phase of the uniform metallic glass consists of almost no pores and no pinholes. It is advantageous to obtain a sprayed coating.

In a crystalline alloy which is a general thermal spray material, solidification shrinkage of several percent occurs when cooled from a melt to a solid.
On the other hand, when the metallic glass is cooled from the melt to the solid, if the cooling rate is appropriate, it can be in a supercooled liquid state without solidification shrinkage due to crystallization, and its volume is the supercooled liquid. It shrinks continuously and slightly according to the thermal expansion coefficient of the region. When the metallic glass is cooled from the supercooled liquid state without melting below the melting point, the amount of shrinkage is further reduced as compared with the case where the metallic glass is cooled from the melt.
Therefore, if the metal glass is sprayed in a supercooled liquid state without melting, the residual stress generated on the joint surface between the base material and the sprayed coating becomes very small. It is also effective in preventing deformation and destruction in the case of materials.

By such a method, a metal glass sprayed coating having a very dense and amorphous phase can be formed on the substrate surface. The presence of high porosity and pinholes reduces corrosion resistance, but according to the above method, for example, a metal glass sprayed coating having a porosity of 2% or less and no pinholes can be obtained.
In addition, as such a method, the method described in Unexamined-Japanese-Patent No. 2006-214000 is employable.
Regarding the porosity, an arbitrary cross section of the metal glass layer can be image-analyzed, and the maximum area ratio of the pores can be adopted as the porosity. Further, the absence of pinholes can be confirmed by image analysis of an arbitrary cross section of the metal glass sprayed coating.

Examples of the thermal spraying method include atmospheric pressure plasma spraying, reduced pressure plasma spraying, flame spraying, high-speed flame spraying (HVOF, HVAF), and cold spraying, and are not particularly limited.
In order to obtain a dense amorphous sprayed coating having a small number of pores with a metallic glass coating, a thermal spraying method in which the metallic glass sprayed particles can be heated to a supercooled liquid state and the sprayed particle speed can be increased to 300 m / s or more is desirable. One suitable thermal spraying method includes high-speed flame spraying using metal glass particles, and a high-quality thermal spray coating can be obtained. Further, a thermal spraying method capable of imparting a thermal spray particle velocity equal to or higher than that of high-speed flame spraying to metal glass particles is also preferably used. In recent years, an apparatus capable of thermal spraying at the same speed and temperature range as high-speed flame spraying has been developed by an atmospheric plasma apparatus.

Standard plasma spraying has a particle velocity of 150 to 300 m / s, a flame temperature in the range of 10,000 to 15,000 K, and a plasma jet (flame) of about 5,000 K even at a distance of about 40 mm from the heat source. . Flame spraying has a particle velocity of 100 to 200 m / s and a flame temperature of 2,300 to 2,900K. Arc spraying has a particle velocity of 180-220 m / s, a flame temperature of about 4,000 K, and a velocity equivalent to flame spraying. Cold spray accelerates the particles with a gas heated to about 573 to 773 K, and the particle collision speed is set to 500 m / s or more.
On the other hand, in high-speed flame spraying (HVOF, HVAF), the flame temperature is equivalent to flame spraying, the particle velocity is 300 m / s or more, and it can be more than twice that of standard flame spraying.
Therefore, the porosity when spraying a general spray material metal is about 12% for flame spraying, about 8% for arc spraying, and about 7% for plasma spraying, whereas it is 4% for high-speed flame spraying. High-speed flame spraying is excellent in adhesion.

  In other words, when it is desired to produce a high-quality sprayed coating with low porosity and high adhesion, amorphous phase metallic glass powder is used as the thermal spraying material, and the amount of heat applied to the thermal spraying material is at least one of the metallic glass powder. By setting the amount of heat to a minimum at which the part becomes a supercooled liquid state, it is preferable to reduce the amount of heat as compared with the case of a normal thermal spray material. Further, regarding the particle velocity, since the sprayed particles are not sufficiently crushed and the porosity is increased by a low-speed spraying method with a particle velocity of less than 300 m / s, it is necessary to shorten the spraying distance in order to make the sprayed coating dense. Yes, the substrate is susceptible to thermal spray frame heat sources. In order not to be affected by the flame, a high-speed flame spraying method that can take a sufficient spray distance and has a low porosity, or a spraying method that gives a particle velocity equal to or higher than that of the high-speed flame spraying method is preferable.

When the thermal spray heat source is combustion energy, kerosene, acetylene, hydrogen, propane, propylene, or the like can be used as the thermal spray fuel. When electric energy is used as the thermal spraying heat source, argon, hydrogen, helium, or the like can be used as the plasma gas.
In spraying, N ₂ gas is usually used as a carrier gas, but the formation of nitrides may affect the coating composition and denseness. This can be improved by using air (dry air), oxygen, inert gas (Ar, He, etc.) as the carrier gas. Since air or oxygen has an effect of oxidation, it is preferable to use an inert gas as a carrier gas when a dense thermal spray coating with a low oxide or crystallization rate is required.

  The particle diameter of the metallic glass particles is preferably 1 to 65 μm in order to make the sprayed coating dense. When the shape of the substrate is not flat, 5 to 25 μm is more preferable. If the particle diameter is too small, the productivity tends to decrease, for example, the molten particles tend to adhere to the thermal spray barrel, or the number of thermal sprays increases to achieve a desired film thickness. Further, when the particles adhered and solidified in the barrel are peeled off and sprayed from the barrel, the uniformity of the sprayed coating is lowered.

  The shape of the metal glass particles is not particularly limited, and examples thereof include a plate shape, a chip shape, a granular shape, and a powder shape. The shape that can uniformly apply heat from a high-speed sprayed frame is granular or powdery shape. It is. In particular, in the case of a substrate having low rigidity, it is necessary to avoid damage to the substrate and to reduce the load when it collides with the substrate during thermal spraying. As a method for preparing the metallic glass particles, there are an atomizing method, a chemical alloying method, a mechanical alloying method, and the like, and those prepared by the atomizing method are particularly preferable in consideration of productivity and spheroidization.

The base material is not particularly limited, and heat-resistant materials such as metals, particularly steel materials such as stainless steel, and heat-resistant plastics such as ceramics, glass, and polyimide can be used.
Various materials, materials, and shapes that are usually used for hot dip galvanizing can be used as the base material. In particular, steel materials for galvanizing pots such as NAGP steel ^(R) and ceramics are generally used.
Moreover, in order to improve the bondability of a metal glass sprayed coating, it is preferable that the base material is used after the surface of the base material is roughened by a known method such as blasting.

The thermal sprayed coating of metal glass can be formed on the surface of a substrate having various shapes, and may be, for example, one having an uneven shape, a cylindrical shape, a pipe shape, a roll shape, or a sheet shape. The material of the substrate may be porous.
Further, the metal glass sprayed coating can be formed by patterning by masking or the like.

  The thickness of the metal glass sprayed coating can be 5 μm or more, preferably 10 μm or more, and more preferably 100 μm or more. The upper limit is not particularly limited, but if it becomes too thick, the economic efficiency is lowered. Therefore, it is typically about 500 μm, but a maximum of 2 mm is sufficient for corrosion resistance.

  Furthermore, after forming a sprayed coating on the surface of the substrate, a metal glass sprayed coating can be die-pressed to transfer and form a desired shape such as unevenness or mirror surface (see, for example, JP-A-2006-122918). . Metallic glass exhibits viscous flow in a supercooled liquid state and is excellent in workability. Of course, it can be processed into various shapes integrally with the base material as well as the sprayed coating.

  In addition, after forming a metallic glass sprayed coating on the surface of the substrate, the metallic glass sprayed coating is subjected to a sealing treatment to eliminate slight stacking faults and pores on the surface of the sprayed coating that can be the starting point for the reaction with molten zinc. It is possible to further improve the molten zinc corrosion resistance of the coating by blocking, particularly with a SiO-based polymer that is difficult to wet with zinc. In addition, when the SiO-based polymer is a low viscosity / low surface tension sealing agent, it penetrates not only to the surface layer portion of the sprayed coating but also to the back of the micropores of the sprayed coating, The effect of blocking the pores with the SiO-based polymer can be enhanced.

  That is, as described above, the metallic glass of the present invention is extremely excellent in molten zinc corrosion resistance. Using this metallic glass as a thermal spray material, there is no pinhole and the porosity is 2% or less, which is a very dense amorphous phase metal. Although a glass sprayed coating can be obtained, even such a sprayed coating may be inferior in corrosion resistance as compared to an amorphous phase metallic glass ribbon material having the same composition prepared by a single roll method. This is because even in the case of such a sprayed coating, fine oxides derived from the sprayed material and minute pores between the stacked particles are scattered at the interface between the stacked particles, and such a layered particle is present on the surface of the sprayed coating. If the interface is exposed, it is considered that erosion proceeds along the interface starting from this.

For example, FIG. 1 is a diagram schematically showing a cross section of a metal glass sprayed coating of the present invention, in which a sprayed coating 14 composed of laminated particles 12 is formed on the surface of a substrate 10. The laminated particles 12 are laminated in close contact with each other, and the thermal spray coating 14 has no through holes (pinholes) and almost no pores.
In the sprayed coating 14, there are some cases where the interface between the laminated particles 12 disappears due to the formation of a new surface at the time of collision, and a plurality of the laminated particles are integrated, but a new surface is not formed between the adjacent laminated particles 12. In some cases, the interface 16 remains or there are minute pores. Such an interface 16 may extend from the surface of the thermal spray coating 14 to the inside, and possibly to the surface of the substrate 10.

The interface 16 is weaker against erosion of molten zinc than the laminated particles 12. For this reason, it is considered that the erosion of the molten zinc proceeds along the interface 16 extending into the sprayed coating 14 starting from the interface 16 including fine oxides and pores exposed on the surface of the sprayed particles.
Therefore, the erosion of the molten zinc along the interface 16 can be inhibited by closing the interface 16 that is the starting point of the erosion by the molten zinc exposed on the surface of the thermal spray coating 14.

In practice, the interface 16 exposed on the surface of the thermal spray coating 14 usually exists as a very fine depression (micropore). Therefore, it is necessary to firmly seal such micropores against molten zinc.
According to the study by the present inventors, an alkoxysilane curable sealant having a low viscosity and a high solid content was effective for such blocking.

As a suitable example of such an alkoxysilane-based sealing agent, a one-component room temperature curable seal comprising the following components (a) and (b), wherein the viscosity of the component (a) at 25 ° C. is 20 to 1000 mPa · s. A pore agent is mentioned.
(A) At least one compound selected from an alkoxysilane compound represented by the following formula (2) and a partial hydrolyzate thereof:
R ¹ _n Si (OR ² ) _4-n (2)
(In the formula, each R ¹ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² is each independently an alkyl group having 1 to 4 carbon atoms, and n is 0 to 3) Is an integer).
(B) Curing catalyst.

  Component (a) has a low viscosity and is not fully hydrolyzed. The sealing agent can be used as it is without being diluted with a solvent. For this reason, even when the solid content is increased, the sealant smoothly penetrates into the fine pores on the surface of the metal glass sprayed coating of the present invention, and after the penetration, it is cured by the component (b) to form fine pores. It can be almost completely sealed with a silicone polymer. And this silicone polymer is hard to get wet with molten zinc, and when cured, it is chemically bonded to the metallic glass sprayed coating of the present invention and does not peel off in molten zinc. Demonstrate over a long period of time.

As such a one-component room temperature curable sealing agent, those described in JP-A No. 2002-363539 can be used. Moreover, as a commercial item, Permeate HS series (Corporation D & D) etc. are mentioned.
Japanese Patent Application Laid-Open No. 2002-363539 describes that the salt resistance and acid resistance of the sprayed coating are improved by treating the sealing agent with respect to the zinc sprayed coating or the zinc alloy sprayed coating. However, there is no description of the blocking effect on molten zinc.

The alkoxysilane compound of the said component (a) says the silicon type compound shown by following formula (2).
R ¹ _n Si (OR ² ) _4-n (2)
In Formula (2), each R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and each R ² independently represents an alkyl group having 1 to 4 carbon atoms. R ¹ may be the same or different. N is an integer of 0 to 3, preferably 1 or 2. When n is 4, it is not an alkoxysilane compound. When n is 1 or 2, a flexible condensate is easily obtained.

  Examples of such alkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane. , Phenyltrimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, and the like, or a mixture thereof.

  The partially hydrolyzed condensate of component (a) means that water is added to the alkoxysilane compound and heated while stirring in the presence of a catalyst to cause partial hydrolysis and condensation. It was obtained by this.

  The degree of hydrolysis and condensation of the partial hydrolyzate can be defined by viscosity. The viscosity of the component (a) is preferably 20 to 1000 mPa · s, more preferably 25 to 500 mPa · s at 25 ° C. If it is less than 20 mPa · s, the sealing agent may diffuse during application and a sufficient sealing effect may not be obtained. On the other hand, if it is larger than 1000 mPa · s, it becomes difficult for the sealing agent to penetrate into the fine pores, and the sealing effect may not be obtained.

  In the present invention, the viscosity is 25 ° C. as described above using a Brookfield type rotational viscometer (BM type, manufactured by Tokimec Co., Ltd.). The value measured at 2 rotors and 60 rpm.

When performing said hydrolysis and condensation, a component (a) can be diluted with a diluent and can be performed. When this diluent is used, a hydrolysis reaction and a condensation reaction can be performed more easily. The diluent is not particularly limited as long as it can dissolve the component (a). For example, alcohols such as methanol, ethanol, propanol and butanol, aromatic compounds such as benzene and toluene, methyl cellosolve, butyl cellosolve And cellosolves such as cellosolve acetate.
In addition, after the hydrolysis-condensation reaction, it is preferable to use, for component (a), not only the water and diluent used in the reaction but also the alcohol produced by the hydrolysis-condensation reaction.

  As component (a), preferably an alkoxysilane selected from methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane and mixtures thereof Examples thereof include a partial hydrolysis-condensation product obtained by hydrolyzing and condensing a compound or the alkoxysilane compound until the generated methanol is no longer distilled.

  The component (b) curing catalyst refers to a catalyst for sufficiently condensing and curing the component (a), for example, one selected from an organic tin compound, an organic titanium compound, an organic aluminum compound, or the like, or The mixture of these 2 or more types is mention | raise | lifted.

  Among the above curing catalysts, the use of a catalyst that cures the component (a) at room temperature is more preferable because it does not affect the sprayed coating and the curing time can be adjusted according to the use conditions. Examples of such catalysts include organotin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, organotitanium compounds such as tetraisopropyl titanate, tetrabutyl titanate and oligomers thereof, aluminum triisopropoxide, aluminum trisec. -Organoaluminum compounds such as butoxide.

  The amount of the curing catalyst used is preferably 0.1 to 10 parts by mass, and preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the component (a). When the amount is less than 0.1 parts by mass, the curing rate after coating is slow, and in some cases, a considerably long time may be required. On the other hand, when the amount is more than 10 parts by mass, the blended sealing agent may become non-uniform, or the curing may be too fast, and workability may deteriorate.

Next, a sealing treatment method using such a sealing agent will be described.
First, the sealing agent is applied to the surface of the metal glass sprayed coating by any method such as spraying, dipping, brushing, or roller coating, and the pores on the surface of the sprayed coating are impregnated with the sealing agent. Further, the sprayed coating may be impregnated with a sealing agent after degassing under reduced pressure.
Next, the material is left at room temperature for 5 to 20 hours. Thereby, a component (a) reacts with the water | moisture content in air | atmosphere, hydrolysis and condensation further advance, polysiloxane hardens | cures in a micropore, and sealing is performed. Further, when heating is performed, curing due to condensation of the component (a) is promoted.
The sealing treatment can be performed a plurality of times as necessary, but usually once or twice is sufficient. Moreover, after apply | coating a sealing agent, it is preferable to wipe off the surplus with a waste etc. before a sealing agent hardens | cures completely (for example, after 5 minutes-1 hour after application | coating).

  Since the Fe—Cr—W-based metallic glass of the present invention is excellent in corrosion resistance against molten zinc, the molten zinc of a facility or apparatus in which molten zinc is used, such as a galvanized facility, a galvanized steel sheet production line, and zinc die casting, It is useful for a member that may come into contact and its surface coating. For example, a soaking bath equipment, a sink roll or a support roll of a hot dip galvanized steel sheet production line can be mentioned, but the invention is not limited to these. In addition, the metal glass of the present invention can be used as an underlayer for the contact surface with molten zinc, and the surface of the underlayer can be further treated with the above-mentioned sealing agent, or can be coated with ceramics, cermet, or other corrosion-resistant materials. Good.

  Further, in the manufacture of hot dip galvanized steel sheet, Zn-Al alloy hot dipping with 5% Al added to zinc (JIS G3317), Zn-Al alloy hot dipping with 55% Al added to zinc (JIS G3321: so-called galvalume) Steel sheets) are made to have high corrosion resistance. However, the metallic glass of the present invention can be applied to such a Zn-Al alloy melt as a corrosion resistant material.

  Hereinafter, the present invention will be described with specific examples, but the present invention is not limited thereto. The measurement method used in the present invention is as follows.

Measurement method (1) DSC measurement The glass transition temperature Tg and the crystallization temperature Tx of the tested metal glass were determined by using a differential scanning calorimeter (DSC8270, manufactured by Rigaku Corporation) at a heating rate of 20 ° C./min. .

(2) X-ray diffraction Whether it was amorphous or not was confirmed by an X-ray diffractometer (SmartLab, manufactured by Rigaku Corporation). In the X-ray diffraction pattern, when there was no crystal peak and only a halo pattern was observed, it was defined as an amorphous single phase.

(3) Microscope observation and EDS-SEM analysis About reaction with a test material and molten zinc, it observed with the scanning electron microscope (JEOL Co., Ltd. product JSM-7001F type, energy dispersion type | formula X-ray analyzer attachment).

Test example 1
Mixing raw materials such as electrolytic iron, metallic chromium, niobium, molybdenum, tungsten thin plate, chrome carbide, ferroboron, etc. so as to have the material composition shown in Table 1, a high frequency melting furnace (manufactured by Nisshin Giken Co., Ltd., small size) An alloy base material was obtained by alloying with a vacuum melting apparatus (NEV-M04C type)).
Using the alloy base material, a ribbon material having a thickness of about 20 μm was produced in an argon gas atmosphere with a single roll device (liquid rapid solidification device (NEV-A05 type) manufactured by Nisshin Giken Co., Ltd.), and the width was 8 mm. A sample with a length of 30 mm was used. Each ribbon material showed a halo pattern with no crystal peak in X-ray diffraction, and was confirmed to be an amorphous single phase. Table 1 shows the DSC measurement results (Tg, Tx, ΔTx) of the produced ribbon material.

An immersion test was performed using the obtained ribbon material. Specifically, as shown in FIG. 2, after putting the ribbon material in a glass tube, it is filled with zinc particles (zinc purity of 99.995% or more (manufactured by Toho Zinc Co., Ltd.)) Heated and melted in an electric furnace to make a zinc bath, and kept as it is for 72 hours at 480 ° C. Then, the ribbon material was taken out and allowed to cool, and it was investigated whether the zinc adhering to the ribbon material could be easily peeled and removed. It was.
The results are shown in Table 1. However, “no zinc adhesion” means that the zinc adhered in the immersion test could be easily peeled and removed, which means that the ribbon material did not react with the molten zinc and was not eroded. Yes.

Sample 1-a (corrosion-resistant material against molten tin described in Patent Document 2) and ribbon material of Sample 1-c are extremely difficult to peel due to the adhesion of zinc, and react with molten zinc. It was confirmed that the metallic glass ribbon materials (Sample 1-1 to Sample 1-7) of the present invention had no adhesion of zinc and had very low reactivity with molten zinc and excellent corrosion resistance.
Sample 1-b containing 23 at% W has no zinc adhesion and does not react with molten zinc, but is amorphous with no glass transition temperature Tg, so it can be made amorphous with a ribbon material with a fast cooling rate, but all with atomization. It could not be made amorphous.

Furthermore, the taken-out ribbon material was embedded in resin, and the cross section of the ribbon material was observed by EDS-SEM to confirm the presence or absence of reaction with molten zinc inside the ribbon material.
As a result, in any of Sample 1-1 to Test Example 1-7, zinc was not observed not only on the ribbon material surface but also inside the ribbon material, and it was confirmed that it did not react with molten zinc.

  Similarly, the immersion test (480 degreeC x 72 hours) by a zinc-5% aluminum bath and the EDS-SEM observation were performed. As a result, in any of the ribbon materials of Samples 1-1 to 1-7, there was no adhesion of zinc-aluminum on the ribbon material surface as in the immersion test result in the pure zinc bath, and even in EDS-SEM observation. Zinc and aluminum were not observed on the ribbon material surface and inside.

Test example 2
A rod covered with a thermal spray coating having a thickness of 250 to 400 μm obtained by thermal spraying an amorphous phase metal glass powder having the composition shown in Table 2 using a rod-shaped SS400 steel (surface blasted finish) having a diameter of 20 mm as a base material. As a sample, an immersion test was performed as follows.
A sample was immersed in a zinc bath (zinc purity of 99.995% or more (manufactured by Toho Zinc Co., Ltd.)) heated by a heater and maintained at 480 ° C. for a certain period of time, then taken out and allowed to cool to give a thermal shock. The total immersion time was 210 hours, and the number of thermal shocks was 3. After the test, the reactivity of the sprayed coating with zinc and the presence or absence of cracking or peeling of the coating due to thermal shock were visually confirmed.

  As the powder for thermal spraying, atomized powder of metal glass (particle size: 10 μm to 25 μm) was used. Since the thermal spraying powder showed a halo pattern without crystal peaks in X-ray diffraction, it was confirmed to be an amorphous single phase.

The spraying conditions are as follows.
(Spraying conditions)
HVOF device: JP-5000 manufactured by Nihon Utec Co., Ltd.
Powder carrier gas: N ₂
Fuel: Kerosene, 5.1GPH
Oxygen: 1800 SCFH
Thermal spray distance (distance from spray gun tip to substrate surface): 380 mm
Spray gun moving speed: 40m / min

  It was confirmed that any of the thermal spray coatings of Sample 2-1 and Sample 2-a was an amorphous single phase from a halo pattern having no crystal peak of X-ray diffraction. Moreover, from the observation of the structure of the sample cross section, the porosity of any sprayed coating was 2% or less and no pinholes were observed.

  In the thermal spray coating (Sample 2-1) of the metallic glass according to the present invention, although zinc was thinly adhered when pulled up from the zinc bath, it can be easily peeled and removed by lightly scratching after cooling and sprayed after removal. No change was observed on the surface of the coating as compared to before the test, as shown in FIG. 3, there was no adhesion of zinc, and there was no cracking or peeling.

  On the other hand, in the sprayed coating of metal glass containing no W (Sample 2-a), zinc is adhered when pulled up from the zinc bath after completion of the test. The film was extremely adhered to the surface and could not be removed. This was thought to be because the sprayed coating of Sample 2-a reacted with molten zinc to form an alloy. The thermal spray coating was not cracked or peeled off.

FIG. 5 shows the results of EDS-SEM analysis of the cross-sectional structure after cutting each sample after the immersion test at a position 30 mm from the tip.
As can be seen from FIG. 5, in Sample 2-a, the reaction with Zn was observed from the surface of the sprayed coating to the vicinity of the center, although it did not reach the substrate surface.
On the other hand, in sample 2-1, a slight reaction with Zn was observed on the surface portion of the sprayed coating, but no reaction with Zn in the sprayed coating was observed.
From this, it is understood that the thermal spray coating of the metallic glass of the present invention has very low reactivity with molten zinc and is excellent in corrosion resistance.

As another comparative example, FIG. 6 shows a NAGP steel plate (manufactured by Nippon Steel Corporation, 0.5 mm thickness, 1 mm thickness) widely used as a hot dip galvanized steel plate in a pure zinc bath. The EDS-SEM analysis result after 72-hour and 96-hour immersion at ° C is shown.
As can be seen from FIG. 6, in the NAGP steel sheet, the dissolution (reaction) of Fe component from the steel sheet to Zn is clearly recognized as the immersion time increases to 72 hours and 96 hours.

Test example 3
In general, wettability increases when the molten metal reacts with the sample at the contact surface to form an alloy. Therefore, a wettability test was conducted to easily examine the reactivity.
After forming a sprayed coating of about 200 μm in thickness on the 10 × 10 mm SUS304 substrate under the spraying conditions in Test Example 2, the surface of the sprayed coating was polished to a mirror surface, and a wetting test was performed as follows. It was.
About 0.2 g of zinc particles (zinc purity 99.995% or more (manufactured by Toho Zinc Co., Ltd., the same below)) is placed on the surface of the sprayed coating of the sample and heated to 480 ° C. in a furnace in an air atmosphere. The state of zinc grains after being held for 96 hours was observed.

The result of the wetting test is shown in FIG. In FIG. 7, sample 3-1 is a sample in which a sprayed coating is formed using Fe ₄₃ Cr ₁₆ Mo ₁ W ₁₅ C ₁₅ B ₁₀ which is the metal glass of the present invention. Sample 3-d is a comparative material, and a WC-12Co sprayed coating used as a sink roll coating in a galvanized steel sheet production line is obtained using WC-12Co powder (5-25 μm, manufactured by Fujimi Incorporated). This is a sample formed under the thermal spraying conditions of Test Example 2.
FIG. 7 (a) shows a sample 3-1, which was held at 480 ° C. for 96 hours and then taken out of the furnace and allowed to cool, and FIG. 7 (b) was obtained by scratching zinc particles from the sample 3-1 in FIG. 7 (a). It has been peeled off.
FIG. 7C shows the sample 3-d before the test, and FIG. 7D shows the sample 3-d which was held at 480 ° C. for 96 hours and then taken out from the furnace and allowed to cool.

As can be seen from FIG. 7, the WC-12Co sprayed coating (Sample 3-d) was wet with the molten zinc particles (FIG. 7 (d)), whereas the metallic glass sprayed coating of the present invention. (Sample 3-1) was hardly wetted by the molten zinc particles (FIG. 7A). This also suggests that the metal glass spray coating (Sample 3-1) of the present invention has very low reactivity.
In the metal glass sprayed coating of the present invention (Sample 3-1), the zinc particles can be easily peeled and removed only by lightly scratching, and the surface of the sprayed coating after the removal of the zinc particles was not changed from that before the wetting test (Fig. 7 (b)). On the other hand, with the WC-12Co sprayed coating (Sample 3-d), the sprayed coating and zinc particles could not be peeled off at all (FIG. 7D). As a result of observing the cross section of this sample 3-d by EDS-SEM, it was confirmed that zinc was observed inside the sprayed coating and reacted with molten zinc inside the sprayed coating. This also confirmed that the metal glass sprayed coating of the present invention has very low reactivity with molten zinc and excellent corrosion resistance.

Test example 4
According to Test Example 2, a 50 mm square SUS304 (surface polished) was prepared using amorphous phase metallic glass powder having a composition of Fe ₄₃ Cr ₁₆ Mo ₁ W ₁₅ C ₁₅ B ₁₀ and Fe ₄₃ Cr ₁₆ Mo ₁₆ C ₁₅ B _10. On the base material, a thermal spray coating was laminated to a thickness of about 500 μm, and the thermal spray coating was peeled off to prepare bulk material samples 4-1 and 4-a comprising thermal spray films of 10 mm × 50 mm. Both Sample 4-1 and Sample 4-a were amorphous single phase metallic glass sprayed coatings with no pinholes and a porosity of 2% or less.

Test Example 5
For Samples 4-1 and 4-a produced in Test Example 4, fine pores and particle interfaces near the surface of the sprayed coating with a sealing agent (trade name Permeate HS-80, manufactured by D & D Co., Ltd.) Sealing treatment was performed for the purpose of blocking the defects by infiltrating the sample, and Samples 5-1 and 5-a were obtained. The processing procedure is as follows.
(1) A sealant (stock solution) is applied to the entire surface of the sprayed coating by brush.
(2) After naturally drying for about 10 minutes, the excess of the sealing agent on the coated surface is wiped off with a waste cloth.
(3) In the same manner as in the above (1), the sealing agent is applied again and dried for about 30 minutes, and then the excess on the coated surface is wiped off with a waste cloth.
(4) Air dry for about 16 hours to complete.

  FIG. 8 shows that Sample 4-1 (the metal glass spray coating of the present invention, without sealing treatment) and Sample 5-1 (the metal glass spray coating of the present invention, with sealing treatment) were immersed in a pure zinc bath (480). It is the EDS-SEM analysis result of the cross-sectional structure | tissue after carrying out (degreeC * 336 hours).

As shown in FIG. 8, when immersed in molten zinc for a very long time, Zn was sometimes observed in the surface layer portion in the metal glass sprayed coating of the present invention (Sample 4-1). By treating, Zn was not recognized in the sprayed coating (Sample 5-1), and the corrosion resistance was remarkably improved.
On the other hand, as shown in FIG. 9, in the sample 5-a in which the metallic glass sprayed coating containing no W (Comparative Example) was sealed, the cross-sectional structure after being immersed (480 ° C. × 336 hours) in a pure zinc bath As a result of the EDS-SEM analysis, Zn was found in the sprayed coating, and particles dropped off in the vicinity of the coating surface, and the corrosion resistance was remarkably inferior to that of Sample 5-1. This is considered because the metal glass sprayed coating film of the comparative example exposed on the surface of the sample 5-a is eroded by the molten zinc.
From this, it is understood that the thermal spray coating of the metallic glass of the present invention has very low reactivity with molten zinc and is excellent in corrosion resistance.

Claims (15)

Has a composition represented by the following formula (1), the supercooled liquid temperature region (Delta] Tx) is 30 ° C. or higher, the thermal sprayed coating having a glass transition temperature (Tg) consist 20 ° C. or more higher than metallic glass than the molten zinc temperature, further comprising a following components (a) and (b), molten zinc, characterized in that the viscosity at 25 ° C. of component (a) has sealing treatment with one solution cold-setting sealing agent is 20~1000mPa · s Corrosion resistant sprayed coating.
(Fe, Cr) _{100- (a + b + c)} W _a TM _b (C, B, P) _c (1)
(In the formula, TM is at least one selected from Mo, Ta, V, and Nb, a is 2 to 20 atom%, b is 0 to 15 atom%, c is 20 to 30 atom%, and Fe is 35 to 55 atoms. %.)
(A) At least one compound selected from an alkoxysilane compound represented by the following formula (2) and a partial hydrolyzate thereof:
R ¹ _n Si (OR ² ) _4-n (2)
(In the formula, each R ¹ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² is each independently an alkyl group having 1 to 4 carbon atoms, and n is 0 to 3) Is an integer).
(B) Curing catalyst.   The molten zinc corrosion-resistant thermal spray coating according to claim 1, wherein the glass transition temperature (Tg) of the metallic glass is 600 ° C. or higher.   The molten zinc corrosion resistant thermal spray coating according to claim 1 or 2, wherein the thermal spray coating to be sealed has a porosity of 2% or less and no pinholes. The contact surface with the molten zinc or the underlying layer of the contact surface has the composition represented by the following formula (1), the supercooled liquid temperature region (ΔTx) is 30 ° C. or more, and the glass transition temperature (Tg) is molten. A molten zinc corrosion-resistant member comprising a metallic glass having a temperature of 20 ° C. or more higher than a zinc temperature or a thermal spray coating made of the metallic glass .
(Fe, Cr) _{100- (a + b + c)} W _a TM _b (C, B, P) _c (1)
(In the formula, TM is at least one selected from Mo, Ta, V, and Nb, a is 2 to 20 atom%, b is 0 to 15 atom%, c is 20 to 30 atom%, and Fe is 35 to 55 atoms. %.) 5. The hot dip zinc corrosion resistant member according to claim 4, wherein the hot galvanized corrosion resistant member is a hot dip galvanizing bath, or a sink roll or a support roll for hot dip galvanizing.   The molten zinc corrosion-resistant member according to claim 4 or 5, wherein the metallic glass is an amorphous phase solid.   The molten zinc corrosion-resistant member according to any one of claims 4 to 6, wherein the glass transition temperature (Tg) of the metallic glass is 600 ° C or higher.   The molten zinc corrosion-resistant member according to any one of claims 4 to 7, wherein the thermal spray coating has a porosity of 2% or less and no pinholes.   The molten zinc corrosion-resistant member according to any one of claims 4 to 8, wherein the sprayed coating further comprises the following components (a) and (b), and the viscosity of the component (a) at 25 ° C is 20 to 1000 mPa · s. A molten zinc corrosion-resistant member which is sealed with a one-component room-temperature curable sealant.
(A) At least one compound selected from an alkoxysilane compound represented by the following formula (2) and a partial hydrolyzate thereof:
        R ¹ _n Si (OR ² ) _4-n       ... (2)
(Wherein R ¹ Are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² Are each independently an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 3).
(B) Curing catalyst. The surface of the member scheduled to contact with molten zinc has a composition represented by the following formula (1), the supercooled liquid temperature region (ΔTx) is 30 ° C. or higher, and the glass transition temperature (Tg) is higher than the molten zinc temperature. Forming a molten zinc corrosion-resistant sprayed coating by thermally spraying a metallic glass that is 20 ° C. or higher to produce a molten zinc corrosion-resistant member having the sprayed coating as a contact surface with the molten zinc or an underlayer of the contact surface. A method for producing a hot-dip zinc corrosion-resistant member.
(Fe, Cr) _{100- (a + b + c)} W _a TM _b (C, B, P) _c (1)
(In the formula, TM is at least one selected from Mo, Ta, V, and Nb, a is 2 to 20 atom%, b is 0 to 15 atom%, c is 20 to 30 atom%, and Fe is 35 to 55 atoms. %.) The manufacturing method according to claim 10, wherein the thermal spray coating has a porosity of 2% or less and no pinholes. 12. The method of manufacturing a molten zinc corrosion-resistant member according to claim 10 or 11 , wherein the sprayed coating is formed by high-speed flame spraying or a spraying method having a sprayed particle flying speed equal to or higher than that. In the manufacturing method in any one of Claims 10-12 , it supercools, without making at least one part of the said thermal spray raw material melt | dissolve by making the amorphous-phase metal glass powder which has the composition of said Formula (1) into a thermal spray raw material. A method for producing a molten zinc corrosion-resistant member, characterized by forming a molten zinc corrosion-resistant thermal spray coating in an amorphous phase by spraying in a liquid state. 14. The method according to claim 10 , wherein the sprayed coating further comprises the following components (a) and (b), and the viscosity of the component (a) at 25 ° C. is 20 to 1000 mPa · s. A method for producing a hot-dip zinc corrosion-resistant member, characterized in that a sealing treatment is performed with a room-temperature curable sealing agent.
(A) At least one compound selected from an alkoxysilane compound represented by the following formula (2) and a partial hydrolyzate thereof:
R ¹ _n Si (OR ² ) _4-n (2)
(In the formula, each R ¹ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² is each independently an alkyl group having 1 to 4 carbon atoms, and n is 0 to 3) Is an integer).
(B) Curing catalyst.   The manufacturing method according to any one of claims 10 to 14, wherein the glass transition temperature (Tg) of the metallic glass is 600 ° C or higher.