JP6226285B1 - PROCESSING EQUIPMENT AND ITS MANUFACTURING METHOD, STRUCTURE AND ITS MANUFACTURING METHOD - Google Patents

Abstract

The present invention provides a processing apparatus capable of obtaining excellent corrosion resistance and melt resistance in an environment in contact with molten metal, molten salt, high-temperature corrosive gas, and the like, and a method for producing the same. A processing apparatus includes a metal substrate 100 and a protective film provided on the surface of the metal substrate 100. The protective film includes a barrier layer 200 containing a metal carbide on the metal substrate 100, and at least one element selected from the group consisting of iron, cobalt, and nickel, and aluminum, chromium, and silicon on the barrier layer 200. A reservoir layer 300 containing at least one element selected from the group and containing no metal carbide; and a coating layer 400 made of a long-fiber ceramic fabric on the reservoir layer 300. [Selection] Figure 1

Description

  The present invention relates to a processing apparatus, a manufacturing method thereof, a structure, and a manufacturing method thereof. For example, a metal base material that is in contact with molten metal such as molten aluminum and molten zinc, molten salt, or high-temperature corrosive gas (combustion gas, etc.) It is suitable for application to various processing devices including, for example, a metal melting tank, a molten metal plating tank, a scraper, a thermocouple protective tube, and the like.

  Equipment required for melting and casting of metals such as aluminum and zinc is immersed in molten metal such as melting furnaces and holding furnaces for melting metals, and thermocouple protection tubes for inserting thermocouples for temperature measurement. In addition to the components that are used in this state, the ladle that transports the molten metal from the holding furnace to the mold, etc., and the scraper that removes the slag that floats on the surface of the molten metal in the holding furnace. There are members that are repeatedly immersed in a molten metal bath, such as a handle for scooping molten metal, and a blowing lance for gas / powder.

  In such a member, generally, the aluminum melting pot or bath is a cast iron or cast steel base material, the thermocouple protection tube is a stainless steel base material, and the ladle, blade scraping and blowing lance are based on carbon steel. Zinc melting pot or melting tank is made of ordinary steel base material, and the coating film and molten metal mold release agent are applied to the surface to suppress dissolution in the molten metal. Prevent sticking.

  However, the inner surface of the melting pan made of cast iron or cast steel is eroded by molten aluminum alloy, and the inner surface of the melting pan made of ordinary steel is eroded by molten zinc alloy. However, there is a problem that the outer surface is deteriorated by high-temperature oxidation. Furthermore, during melting and holding, the iron components of cast iron, cast steel and ordinary steel are eluted into the molten metal and become harmful elements of the aluminum alloy and zinc alloy. Therefore, it is desired to reduce the elution of iron into the molten metal. Yes.

  Conventionally proposed protective films such as melting pots, melting tanks, thermocouple protection tubes, ladles, scrapers, handle rods, blow lances, etc. are roughly divided into ceramic coatings, ceramic coatings and metal coatings. The

  Techniques for forming a ceramic coating are proposed in Patent Documents 1 to 4. Patent Document 1 proposes protecting a thermocouple protective tube with a ceramic outer sheath that is less soluble in molten aluminum. The conventional stainless steel protective tube is covered with a silicon carbide protective tube, and molten aluminum and stainless steel are covered. The protective tube is not in direct contact with each other. Patent Document 2 discloses thermocouple protection for a ceramic cylinder in which a thin plug portion made of ceramic having excellent thermal conductivity is inserted into an opening on one end side of a cylindrical main body portion having both ends opened made of ceramic. It has been proposed that when a thermocouple protection tube is immersed in a molten metal (Fe, Al, Zn or the like), the molten metal does not enter the inside by using it as a tube. Patent Document 3 proposes a continuous temperature measuring probe for a ladle having a double-tube structure sealed at one end, a protective tube made of cermet on the inside, and a protective sleeve made of refractory on the outside. Patent Document 4 proposes a technique in which a protective sheath is composed of a refractory metal oxide and graphite.

A technique for forming a ceramic coating is proposed in Patent Document 5. In Patent Document 5, MgAl ₂ O ₄ is formed on a stainless steel surface by sol-gel coating and firing, and an FeCr ₂ O ₄ layer is formed by oxidation treatment between the stainless steel and the MgAl ₂ O ₄ layer. Thus, a method for suppressing direct contact between molten aluminum and stainless steel has been proposed. Patent Document 6 proposes a lightweight and durable metal melt member in which aluminum is hot-plated on the surface of a titanium base material and the plated layer is oxidized to form an aluminum oxide film. ing.

  Patent Documents 7 to 8 propose techniques for forming a metal film. Patent Document 7 describes that a nickel-phosphorus alloy film formed by plating on the surface of a metal substrate exhibits excellent hot metal erosion with respect to molten aluminum and / or molten zinc. There have been proposed aluminum and / or melting members using aluminum, aluminum and / or zinc melting furnaces, and molten aluminum and / or hot dip galvanizing equipment equipped with the members. Patent Document 8 proposes a method of forming a Ti—Al intermetallic compound layer by promoting diffusion of titanium and aluminum on a surface of a base material made of titanium or a titanium alloy, after hot-plating aluminum. Compared to the hot dipping process described in No. 6, it is reported that a longer durability can be obtained.

However, the above-described conventional techniques proposed in Patent Documents 1 to 8 have the following problems.
(1) Ceramic coating is inferior in adhesion to a metal substrate and easily peels off due to impact or the like, so that it is difficult to work and handle.
(2) When peeling or cracking occurs in the ceramic coating, the molten metal enters from that portion and melts the metal base material, and the thickness reduction of the base material proceeds to promote further peeling of the ceramic coating.
(3) When titanium is used as the base material, the base material and molten aluminum react with each other to grow a Ti-Al compound layer, thereby reducing the thickness of the titanium base material. Since the layer is fragile and titanium oxide tends to become unstable and decompose by Al, it easily breaks.
(4) Nickel-phosphorus alloy plating film is inferior in oxidation resistance in a high-temperature atmosphere. On the other hand, in molten aluminum bath, nickel of nickel-phosphorus alloy plating film is easily eluted into molten aluminum and is deficient in the film. Then, hot water erosion of the base material occurs and the anticorrosion property is lost.

  Ceramics have excellent resistance to molten metal, molten salt, and high temperature corrosive gas, but are brittle, and have the disadvantage of being cracked or broken by heating / cooling or impact force. On the other hand, woven fabrics of ceramic fibers have excellent resistance in molten metal, molten salt, and high-temperature corrosive atmospheres. Furthermore, they are flexible and can be bent freely without being bent, and breakage due to rapid heating / cooling occurs. Since it has the property of being difficult, a method of covering the surface of the metal substrate with a woven fabric of ceramic fibers is considered, and protective films made of woven fabric of ceramic fibers are proposed in Patent Documents 9 to 14. . In Patent Document 9, it is proposed that the outer ceramic sleeve is formed in a laminated structure, and the outermost layer contains a water-repellent boron nitride (BN) to improve durability. Patent Document 10 proposes a molten metal thermocouple having a protective tube made of non-oxide ceramic or cermet with its tip closed and an insulating ceramic sleeve inserted into the protective tube. In Patent Document 11, it is proposed to insert an alumina protective tube containing a thermocouple into a high melting point protective tube, and to protect the outer periphery of the high melting point protective tube excluding the bottomed end with a fireproof protective sleeve. . Patent Document 12 proposes a temperature measuring probe that improves the bondability in the boundary region between the outer peripheral wall surface of the cermet tube and the inner peripheral wall surface of the protective sleeve and is advantageous in extending the life. In Patent Document 13, a hollow flexible sleeve formed of a woven fabric or a nonwoven fabric of ceramic fibers is covered so as to wrap a metal base material, and a ceramic liquid binder or a ceramic aggregate is mixed with the sleeve. There has been proposed a molten metal member in which a slurry is impregnated and the sleeve is cured. Furthermore, it has been proposed to secure a gap corresponding to the expansion allowance of the metal substrate between the metal substrate and the inner surface of the cured ceramic woven fabric and the metal substrate. Thus, covering the metal substrate with a woven fabric of ceramic fibers is an excellent method for protecting the metal substrate from molten metal, molten salt, high temperature corrosive gas, and the like. However, the woven fabric of ceramic fiber has a defect that voids are contained between the fibers, and molten metal or the like enters through the voids. The ceramic fiber woven fabric proposed in Patent Document 14 prevents the intrusion of molten metal or the like by filling this gap with a ceramic bainter. However, as a result, the fiber woven fabric is cured and loses its flexibility, and there is a problem that cracks and breaks occur due to heating / cooling and impact force, etc., as in the case of a dense ceramic. Furthermore, since a gap is provided between the inner surface of the cured ceramic fiber woven fabric and the metal substrate, molten metal, molten salt, high-temperature corrosive gas, etc. intrude, and the metal substrate melts and becomes hot. There is also a drawback that corrosion proceeds.

JP-A-8-75563 JP 2013-19772 A JP 2011-99840 A JP 2006-53128 A JP 2014-16216 A Japanese Patent Application Laid-Open No. 8-199322 JP 2003-239057 A JP 2013-36070 A JP 2001-194245 A JP 2002-372463 A JP 2005-241394 A JP 2011-169798 A Japanese Patent Laid-Open No. 11-132862 Japanese Patent No. 4264301

H.Okamoto; Desk Handbook Phase Diagrams for Binary Alloys, ASM International ISBN 0-87170-682-2

  The problem to be solved by the present invention is to provide a processing apparatus capable of obtaining excellent corrosion resistance and erosion resistance in an environment in contact with molten metal, molten salt, high temperature corrosive gas, and the like, and a method for producing the same. It is to be.

  The problem to be solved by the present invention is, more generally, various corrosion resistance and erosion resistance that can be obtained in an environment in contact with molten metal, molten salt, hot corrosive gas, etc. And a manufacturing method of the structure including various members that do not correspond to the processing equipment.

In order to solve the above problems, the present invention provides:
A metal substrate;
Having a protective coating provided on the surface of the metal substrate,
The protective film is
A barrier layer containing a metal carbide on the metal substrate;
A reservoir containing at least one element selected from the group consisting of iron, cobalt and nickel and at least one element selected from the group consisting of aluminum, chromium and silicon on the barrier layer and containing no metal carbide. Layers,
A coating layer made of a long-fiber ceramic fabric on the reservoir layer;
It is the processing equipment which has.

  In the present invention, the protective film is provided on at least a part, preferably all, of the surface of the metal substrate on the side in contact with the molten metal, molten salt, hot corrosive gas, or the like.

  The metal substrate is, for example, at least one element selected from the group consisting of steel materials (Fe-based alloys), non-ferrous metal materials, iron (Fe), cobalt (Co), and nickel (Ni), and tungsten (W). An alloy containing chromium (Cr), or further containing at least one element selected from the group consisting of molybdenum (Mo), tantalum (Ta), and rhenium (Re), but is not limited thereto. It is not something. Examples of the steel material include, but are not limited to, mild steel, carbon steel, cast iron, cast steel, stainless steel, and the like. The non-ferrous metal material is, for example, titanium, heat-resistant titanium alloy (titanium-aluminum alloy, etc.), but is not limited thereto. An alloy containing at least one element selected from the group consisting of Fe, Co and Ni and W and Cr, or further containing at least one element selected from the group consisting of Mo, Ta and Re is excellent. In addition to having a diffusion barrier capability, addition of W, Ta, Mo or Re also has an effect of increasing the strength. An alloy containing at least one element selected from the group consisting of Fe, Co, and Ni and W and Cr includes, for example, a Cr—W alloy layer, a Cr—W—Ta (tantalum) alloy layer, Cr -W-Mo (molybdenum) alloy layer, Cr-W-Ta-Mo alloy layer, Cr-W-Ta-Mo-Re (rhenium) alloy layer, etc. Absent. More specifically, it contains at least one element selected from the group consisting of Fe, Co and Ni and W and Cr, or further contains at least one element selected from the group consisting of Mo, Ta and Re. In the case of Fe-Cr-W alloys, the alloy containing W is 10 atomic% to 21 atomic%, Cr is 23 atomic% to 53% atomic, and Fe is 25 atomic% to 66 atomic% ( 100 atom% in total), W containing 30 atom% to 45 atom%, Cr containing 10 atom% to 40 atom%, Fe containing 30 atom% to 59 atom% (total 100 atom%), W containing 35 atom% to 45 atom%, Cr containing 0.1 atom% to 50 atom%, Fe containing 15 atom% to 64 atom% (total of 100 atom%), W 0.1 Atomic% or more 0 atom% or less, Cr containing 70 atom% or more and 99 atom% or less, Fe containing 0.1 atom% or more and 29 atom% or less (total of 100 atom%), W: 77 atom% or more and 99 atom% or less, Cr containing 0.1 atomic% or more and 20 atomic% or less, Fe containing 0.1 atomic% or more and 2 atomic% or less (total of 100 atomic%), etc. 0.1 atomic% to 3 atomic%, Cr 52 atomic% to 65 atomic%, Co 30 atomic% to 54 atomic% (total 100 atomic%), W 3 atomic% to 25 Atomic% or less, Cr containing 30 atomic% or more and 65 atomic% or less, Co containing 25 atomic% or more and 55 atomic% or less (total of 100 atomic%), W 25 atomic% or more and 35 atomic% or less, Cr 20 Atomic% to 40 atomic%, Co at 30 atomic% or less Containing 50 atomic% or less (total 100 atomic%), W 30 atomic% to 55 atomic%, Cr 0.1 atomic% to 50 atomic%, Co 20 atomic% to 60 atomic% (100% in total), W containing 0.1 atomic% to 25 atomic%, Cr containing 65 atomic% to 99 atomic%, and Co containing 0.1 atomic% to 25 atomic% ( 100 atomic% in total), W is 75 atomic% to 99 atomic%, Cr is 0.1 atomic% to 25 atomic%, and Co is 0.1 atomic% to 3 atomic% (total 100) In the Ni—Cr—W-based alloy, W is contained in an amount of 2 to 20 atom%, Cr is contained in an amount of 40 to 65 atom%, and Ni is contained in an amount of 30 to 40 atom%. Things (100 atom% in total), W 0.1 atom% 20 atomic% or less, Cr 70 atomic% or more and 99 atomic% or less, Ni 0.1 atomic% or more and 30 atomic% or less (100 atomic% in total), W 80 atomic% or more and 99 atomic% or less , Cr containing 0.1 atomic% to 20 atomic% and Ni containing 0.1 atomic% to 3 atomic% (total of 100 atomic%).

Specific examples of the metal substrate are shown in Table 1.

  The barrier layer containing metal carbide on the metal substrate uses the high melting point of the metal carbide to prevent molten metal, molten salt, high-temperature corrosive gas, etc. from entering the metal substrate. Is to do. The metal carbide is, for example, at least one selected from the group consisting of tungsten carbide, molybdenum carbide, niobium carbide, aluminum carbide, and chromium carbide, but is not limited thereto. The concentration of the metal carbide is typically 35% by weight to 95% by weight, and preferably 50% by weight to 90% by weight, but is not limited thereto. The components other than the metal carbide of the barrier layer are typically at least one element selected from the group consisting of iron (Fe), cobalt (Co), and nickel (Ni), silicon (Si), boron (B) However, the present invention is not limited to this. These metal carbides are generally available, and there is no particular limitation on the shape and purity thereof, but the particle size is preferably 1 μm or more and 50 μm or less, and more preferably 3 μm or more and 25 μm or less.

  The reactivity of the barrier layer containing metal carbide with molten metal, molten salt, high temperature corrosive gas, etc. is different from each other. For this reason, it is necessary to take measures for suppressing various reactions. At least one element selected from the group consisting of iron (Fe), cobalt (Co) and nickel (Ni) on the barrier layer and selected from the group consisting of aluminum (Al), chromium (Cr) and silicon (Si) A reservoir layer that contains at least one element that does not contain metal carbide is provided to achieve such a purpose, and is a barrier layer made of molten metal, molten salt, hot corrosive gas, etc. By protecting the metal layer, the function of the barrier layer is exhibited over a long period of time, and as a result, the metal substrate is protected over a long period of time. When the reservoir layer contains aluminum (Al), the content is typically 1% by weight to 15% by weight. When the reservoir layer contains chromium (Cr), the content is typically 1% by weight or more. When it contains 30% by weight or less and silicon (Si), its content is typically 1% by weight or more and 15% by weight or less. The reservoir layer may further contain 10 wt% or more and 15 wt% or less of titanium (Ti). In this case, it is effective for molten metal, particularly molten aluminum. The reservoir layer preferably contains 90% by weight or more and less than 100% by weight of nickel (Ni). In this case, the reservoir layer is effective for a molten salt, particularly a molten salt of chloride and cyanide. The reservoir layer preferably contains 7 wt% or more and 15 wt% or less of aluminum (Al). In this case, the reservoir layer is effective for a combustion gas atmosphere, particularly an atmosphere containing oxygen. The reservoir layer preferably contains 5% by weight to 15% by weight of silicon (Si). In this case, the reservoir layer is effective for a combustion gas atmosphere, particularly an atmosphere containing sulfur.

  The coating layer made of long fiber ceramic fabric on the reservoir layer has a continuous and continuous structure over the entire surface and covers the surface of the reservoir layer, so that it can be used for molten metal, molten salt, hot corrosive gas, etc. Excellent resistance to. It is desirable that the gap between the coating layer and the reservoir layer is narrow, but it is not necessary that both are in close contact. The gaps between the fibers of the long fiber ceramic fabric exist without being filled with ceramic slurry or the like, and thus the coating layer remains flexible. That is, the coating layer made of the long-fiber ceramic fabric on the reservoir layer has voids between the fibers of the long-fiber ceramic fabric, and thus remains flexible. For this reason, even if the metal substrate is heated, cooled, etc., the coating layer can be bent freely and can follow changes in the shape of the metal substrate, thereby preventing destruction, breakage, etc. Can do. On the other hand, molten metal, molten salt, high-temperature corrosive gas, etc. enter through the gaps between the fibers of the long-fiber ceramic fabric, but since the reservoir layer and the barrier layer exist in the lower layer of the coating layer, these Reservoir layer and barrier layer can prevent molten metal, molten salt, high temperature corrosive gas, etc. from entering the metal substrate side. It is possible to prevent high temperature corrosion of the metal substrate due to gas or the like. The long fiber ceramic fabric is, for example, a cloth knitted with long fiber ceramics, a knit, a sleeve, or the like, but is not limited thereto. The type, length, shape, and the like of the long fiber ceramic fabric are not particularly limited as long as the ceramic long fiber is processed into a fabric and has a gap between the fibers. The long fiber ceramic fabric is desirably 50% by weight or more and 90% by weight or less.

In applications where the processing equipment is used in contact with molten metal, it is preferable that molten metal such as molten aluminum penetrates the metal substrate side through the gaps between the fibers of the long fiber ceramic fabric constituting the coating layer. In order to prevent this, a release agent layer for the molten metal is provided on the surface of the coating layer, and more preferably, a release agent layer for the molten metal is also provided on the surface (inner surface) of the coating layer on the reservoir layer side. . Thus, by providing the release agent layer on the surface of the coating layer or further on the surface on the reservoir layer side, it is possible to reduce the residence of the molten metal in the gaps between the fibers of the long-fiber ceramic fabric. There is no particular limitation on the release agent layer, and commercially available products can be used. Desirably, water glass containing sodium silicate as a main component is used. The amount of the release agent layer is not particularly limited as long as the voids between the fibers of the long fiber ceramic fabric constituting the coating layer are not excessively filled and the flexibility of the coating layer is not lost. To be elected. For example, when a release agent layer is applied on the coating layer, the application amount is preferably 0.1 g / cm ² or more and 0.2 g / cm ² or less.

  The processing equipment is not particularly limited as long as it is used in contact with molten metal, molten salt, high temperature corrosive gas, or the like in some form. Here, the treatment is understood in the broadest sense, melting the metal, plating with the molten metal, storing the molten metal, transporting the molten metal, and removing suspended matter on the surface of the molten metal. , Protecting from molten metal, measuring the temperature of the molten metal, storing molten salt, treating high temperature corrosive gas, and so on. The equipment includes all kinds of machines, instruments, instruments, and the like. Specifically, the processing equipment includes, for example, a metal melting tank, a metal melting pot, a metal plating tank, a thermocouple protection tube, a molten metal stirring rod, a ladle for transporting the molten metal, and a float floating on the surface of the molten metal. However, the present invention is not limited to these. Examples include, but are not limited to, a scraping tool for removing metal, a hot pot for scooping molten metal, a handle for scooping molten metal, and a gas / powder blowing lance.

  Examples of the molten metal include molten aluminum and molten zinc, but are not limited thereto. The molten salt is, for example, a molten salt of chloride and cyanide, but is not limited thereto. The high temperature corrosive gas is, for example, an atmosphere containing oxygen, an atmosphere containing sulfur, or the like, but is not limited thereto.

In addition, this invention
A metal substrate;
Having a protective coating provided on the surface of the metal substrate,
The protective film is
A barrier layer containing a metal carbide on the metal substrate;
A reservoir containing at least one element selected from the group consisting of iron, cobalt and nickel and at least one element selected from the group consisting of aluminum, chromium and silicon on the barrier layer and containing no metal carbide. Layers,
A coating layer made of a long-fiber ceramic fabric on the reservoir layer;
It is a structure which has.

  The structure is a broader concept including various structures that do not correspond to the processing equipment in addition to the processing equipment. For example, the structure includes a turbine blade composed of a metal base material made of a titanium-aluminum alloy that is effective for significantly reducing the weight of an aircraft jet engine. By applying the protective coating of the present invention to this turbine blade, the life of the turbine blade, and hence the jet engine, can be extended. In the invention of this structure, what has been described in relation to the invention of the processing apparatus is valid as long as it is not contrary to the nature of the structure.

In addition, this invention
After applying a slurry-like powder containing a mixed powder of a powder made of a first alloy having a melting point lower than that of the metal substrate and a metal carbide powder on the surface of the metal substrate, the melting point is higher than the melting point of the first alloy. Forming a barrier layer containing the metal carbide by heating at a first temperature lower than the melting point of the metal substrate;
A powder composed of a second alloy containing at least one element selected from the group consisting of iron, cobalt and nickel on the barrier layer and having a melting point lower than that of the metal substrate and the barrier layer, and aluminum, chromium and silicon After applying a slurry-like powder containing a mixed powder with a powder comprising at least one element selected from the group consisting of: higher than the melting point of the second alloy, lower than the melting points of the metal substrate and the barrier layer By heating at a second temperature, containing at least one element selected from the group consisting of iron, cobalt and nickel and at least one element selected from the group consisting of aluminum, chromium and silicon; Forming a reservoir layer containing no metal carbide;
Forming a coating layer made of a long-fiber ceramic fabric on the reservoir layer;
Is a method of manufacturing a processing apparatus having

  Typically, the first alloy includes at least one element selected from the group consisting of iron, cobalt, and nickel and silicon and boron, such as an iron-based self-fluxing alloy, a cobalt-based self-fluxing alloy, and a nickel-based alloy. Although it is at least 1 type of alloy selected from the group which consists of self-fluxing alloys, it is not limited to this. The first temperature is, for example, 1100 ° C. or more and 1200 ° C. or less, the heating time is, for example, 30 minutes or more and 4 hours or less, and preferably 1125 ° C. or more and 1175 ° C. or less, and the heating time is, for example, 1 hour or more and 2 hours or less. However, the present invention is not limited to this. When heating at the first temperature, since the melting point of the metal carbide is higher than the melting point of the metal substrate, the metal carbide itself in the slurry powder does not melt, but the first alloy having a lower melting point than the metal substrate First, it melts, and then a part of the surface of the metal carbide particles is dissolved in the melt to form a dense barrier layer containing the metal carbide particles. Typically, the second alloy includes at least one element selected from the group consisting of iron, cobalt, and nickel and silicon and boron, such as an iron-based self-fluxing alloy, a cobalt-based self-fluxing alloy, and a nickel-based alloy. At least one alloy selected from the group consisting of self-fluxing alloys. The second temperature is, for example, 1050 ° C. to 1175 ° C., the heating time is, for example, 30 minutes to 4 hours, and preferably 1100 ° C. to 1175 ° C., and the heating time is, for example, 1 hour to 2 hours. However, the present invention is not limited to this.

  The method for forming the barrier layer and the reservoir layer is not particularly limited and may be selected as necessary. Examples thereof include physical vapor deposition, thermal spraying, diffusion penetration, chemical vapor deposition, and electroplating.

  By implementing this processing apparatus manufacturing method, the above processing apparatus can be easily manufactured. In the invention of the method for manufacturing a processing device, what has been described in relation to the invention of the processing device is valid as long as it is not contrary to the nature thereof.

In addition, this invention
After applying a slurry-like powder containing a mixed powder of a powder made of a first alloy having a melting point lower than that of the metal substrate and a metal carbide powder on the surface of the metal substrate, the melting point is higher than the melting point of the first alloy. Forming a barrier layer containing the metal carbide by heating at a first temperature lower than the melting point of the metal substrate;
A powder composed of a second alloy containing at least one element selected from the group consisting of iron, cobalt and nickel on the barrier layer and having a melting point lower than that of the metal substrate and the barrier layer, and aluminum, chromium and silicon After applying a slurry-like powder containing a mixed powder with a powder comprising at least one element selected from the group consisting of: higher than the melting point of the second alloy, lower than the melting points of the metal substrate and the barrier layer By heating at a second temperature, containing at least one element selected from the group consisting of iron, cobalt and nickel and at least one element selected from the group consisting of aluminum, chromium and silicon; Forming a reservoir layer containing no metal carbide;
Forming a coating layer made of a long-fiber ceramic fabric on the reservoir layer;
It is a manufacturing method of the structure which has this.

  By implementing this structure manufacturing method, the above structure can be easily manufactured. In the invention of the manufacturing method of the structure, what has been described in relation to the invention of the processing equipment and the invention of the processing equipment manufacturing method is valid as long as it is not contrary to the nature.

  According to the present invention, the coating layer made of the long fiber ceramic fabric on the reservoir layer has not only excellent resistance to molten metal, molten salt, hot corrosive gas, etc., but also the long fiber ceramic fabric. Due to the presence of air gaps between the fibers and flexibility, it is possible to follow the shape of the metal substrate that changes during expansion / contraction due to heating / cooling. Even if added, cracks, destruction and peeling can be prevented. On the other hand, molten metal or the like enters the metal substrate side through the gaps between the fibers of the coating layer made of the long fiber ceramic fabric, but the barrier contains a metal carbide in the lower layer of the coating layer made of the long fiber ceramic fabric. By providing the layer, it is possible to prevent reaction with the metal substrate, and on the barrier layer, at least one element selected from the group consisting of iron, cobalt and nickel and aluminum, chromium and silicon By providing the reservoir layer containing at least one element selected from the group consisting of the above, the protective function of the barrier layer can be exhibited for a long time. For this reason, various processing equipment or structures capable of obtaining excellent corrosion resistance and erosion resistance in an environment in contact with molten metal such as molten aluminum and molten zinc, molten salt, high temperature corrosive gas, etc. Can be realized.

It is sectional drawing which shows the processing equipment by 1st Embodiment of this invention. It is sectional drawing which shows the processing equipment by 1st Embodiment of this invention. It is sectional drawing which shows the processing equipment by 2nd Embodiment of this invention. It is sectional drawing which shows the processing equipment by the 3rd Embodiment of this invention. It is a basic diagram which shows the result of the immersion test in the Al-Si alloy bath of the various thermocouple protective tubes by Examples 1-4 and Comparative Examples 1-7. FIG. 6 is a drawing-substituting photograph showing a cross section of the thermocouple protection tube according to Example 4 after being immersed in an Al—Si alloy bath for 90 hours.

  Hereinafter, modes for carrying out the invention (hereinafter simply referred to as “embodiments”) will be described.

<First Embodiment>
[Processing equipment]
In the first embodiment, a processing apparatus used by being immersed in molten metal or the like will be described.

  FIG. 1 shows this processing equipment. As shown in FIG. 1, in this processing apparatus, a barrier layer 200 and a reservoir layer 300 are sequentially provided on the outer peripheral surface of the rod-shaped metal substrate 100 over the entire circumference of the metal substrate 100. A long fiber ceramic fabric covering layer 400 is provided over the entire circumference. A protective film is formed by the barrier layer 200, the reservoir layer 300, and the long fiber ceramic fabric covering layer 400. This protective coating is a predetermined part including at least a part of the outer peripheral surface of the metal substrate 100 that comes into contact with the molten metal when the processing apparatus is used, or high temperature oxidation with the molten metal. It is provided in a predetermined part including at least a part in contact with the meniscus region coexisting with the atmosphere, a part where the molten metal fluctuates and flows with respect to the metal base material 100, a part where adhesion / separation of noro and the like repeatedly occurs. The metal substrate 100 may be columnar or cylindrical depending on the processing equipment, but FIG. 1 shows a case where the metal substrate 100 is columnar as an example. FIG. 2 shows a case where the metal substrate 100 is cylindrical. Moreover, in FIG. 1 and FIG. 2, the case where the protective film is provided in the outer peripheral surface of the whole longitudinal direction of the column-shaped metal base material 100 as an example is shown.

  The metal substrate 100 can be appropriately selected from, for example, the processing equipment, the required function, the formation method of the barrier layer 200 and the reservoir layer 300, etc., from among those exemplified above. It may be made of any non-ferrous metal material, and the presence / absence or concentration of carbon is not particularly limited. Specifically, for example, when the processing device is a heat treatment device using a molten salt, or the processing device is a melting pot, a melting tank, a thermocouple protection tube, a stirring rod, a non-scraping, In the case of a molten metal processing apparatus such as a steel, it is generally a steel material from the viewpoint of cost effectiveness, and is preferably a mild steel, carbon steel, cast steel, stainless steel, or the like.

  The barrier layer 200 contains, for example, 35 wt% or more and 95 wt% or less of metal carbide, preferably 50 wt% or more and 90 wt% or less, and is selected from the group consisting of Fe, Co, and Ni as components other than metal carbide. It contains at least one, typically B and Si in addition to this. For example, the metal carbide can be appropriately selected from those exemplified above according to the use of the processing equipment, the required function, the formation method of the barrier layer 200 and the reservoir layer 300, and the like. Preferably, the metal carbide is tungsten carbide (WC), and the WC concentration of the barrier layer 200 is not less than 35% by weight and not more than 95% by weight, and more desirably not less than 66% by weight and not more than 90% by weight. The barrier layer 200 is firmly bonded to the metal substrate 100 and can prevent molten metal, molten salt, high-temperature corrosive gas, and the like from entering the metal substrate 100 side.

  The reservoir layer 300 contains at least one element selected from the group consisting of Fe, Co, and Ni and at least one element selected from the group consisting of Al, Cr, and Si, and does not contain a metal carbide.

The long fiber ceramic fabric covering layer 400 is made of a fabric, knit, sleeve, or the like knitted with long fiber ceramics, and has resistance to molten metal, molten salt, high temperature corrosive atmosphere, and the like, and oxidation resistance. The long fiber ceramic of the long fiber ceramic fabric is, for example, Al ₂ O ₃ , ZrO ₂ , SiC, or the like, and is selected from these as necessary. The long fiber ceramic is preferably Al ₂ O ₃ containing SiO ₂ , more preferably (28-40) wt% SiO ₂ —Al ₂ O ₃ ceramic. The long fiber ceramic fabric covering layer 400 has a gap between the fibers of the long fiber ceramic fabric and maintains a flexible state. The long fiber ceramic fabric covering layer 400 is a structure in which, for example, a thermocouple protection tube and a lance tube are covered with a long fiber ceramic woven fabric having a sleeve structure having an inner diameter larger than the outer diameter at a target portion thereof. Then, a structure in which a knit-structured long fiber ceramic woven fabric is attached to a target portion is selected. The thickness of the long fiber ceramic woven coating layer 400 is selected as necessary. However, when the processing device is a thermocouple protective tube, it is desirable that the thickness is smaller in order to ensure temperature responsiveness. For example, it is selected from 0.5 mm to 5 mm, and more preferably from 1 mm to 3 mm.

[Processing device manufacturing method]
First, the metal substrate 100 is prepared. The shape, length, diameter, etc. of the metal substrate 100 are determined according to the processing equipment to be manufactured.

  Next, after applying a slurry-like powder containing a mixed powder of a first alloy powder having a melting point lower than that of the metal substrate 100 and a metal carbide powder to the surface (outer peripheral surface) of the metal substrate 100, the above-mentioned first The barrier layer 200 containing the metal carbide is formed by heating at a first temperature higher than the melting point of the alloy 1 and lower than the melting point of the metal substrate 100. More specifically, for example, raw material powder (first alloy powder and metal carbide powder) is weighed, kneaded in a mortar, and then poured into a slurry liquid containing an organic solvent and ethanol to produce a slurry powder. To do. The viscosity of the slurry is adjusted by adding ethanol, for example. This slurry powder is applied to the surface of the metal substrate 100. For example, the slurry-like powder can be applied to the entire surface of the metal substrate 100 by immersing the entire metal substrate 100 in the slurry-like powder and then pulling it up. Next, the metal base material 100 thus coated with the slurry-like powder is heated in, for example, an electric heating oven heated to 60 to 80 ° C. and then heated. The heating method is not particularly limited, but heating in an electric furnace in a reduced pressure atmosphere (exhaust by an oil rotary pump) and an inert gas atmosphere, and so-called fusion treatment with a combustion gas flame is desirable. In the examples described later, a heating method using an electric furnace was employed in a reduced pressure atmosphere and an inert gas (Ar) atmosphere. The barrier layer 200 may be formed by spraying a mixed powder of a powder made of a first alloy having a melting point lower than that of the metal substrate 100 and a metal carbide powder on the surface of the metal substrate 100. The first alloy includes at least one element selected from the group consisting of Fe, Co, and Ni, and Si and B. Typically, for example, an Fe-based self-fluxing alloy, a Co-based self-fluxing alloy, and Ni It is at least one alloy selected from the group consisting of base self-fluxing alloys. The first temperature is, for example, 1100 ° C. or more and 1200 ° C. or less, the heating time is, for example, 30 minutes or more and 4 hours or less, and preferably 1125 ° C. or more and 1175 ° C. or less, and the heating time is, for example, 1 hour or more and 2 hours or less. . Fe-based self-fluxing alloys, Co-based self-fluxing alloys and Ni-based self-fluxing alloys are commercially available from, for example, New Metals End Chemical Corporation. Examples of the Fe-based self-fluxing alloy include trade name 6AB-325, examples of the Co-based self-fluxing alloy include trade name HMSP-2345-00, and examples of the Ni-based self-fluxing alloy include trade name HMSP-1360-20. Further, a Co-based self-fluxing alloy powder in which Co-based self-fluxing alloy powder and WC powder are mixed in advance +35 wt% WC is also commercially available under the trade name HMSP-1660 + 35% 44712-10, and Ni-based self-fluxing alloy powder and WC powder Is also commercially available under the trade name HMSP-1660-02 + 50% 46712-10. For example, when a Ni-based self-fluxing alloy is used as the first alloy and WC is used as the metal carbide, a mixed layer of Ni-based self-fluxing alloy powder and WC powder can be obtained when the WC concentration is less than 35% by weight. 200 is inferior in its ability as a diffusion barrier, and if it exceeds 95% by weight, the resulting barrier layer 200 is insufficiently densified, so the WC concentration is preferably 35% by weight or more and 95% by weight or less, more preferably It is 50 weight% or more and 90 weight% or less. Further, when the mixed powder of Ni-based self-fluxing alloy powder and WC powder is used in this way, the first temperature is preferably 1100 ° C. or higher and 1175 ° C. or lower, and most preferably 1150 ° C. For example, when the metal substrate 100 is an Fe-containing alloy, for example, stainless steel, a slurry powder containing a mixed powder of Ni-based self-fluxing alloy powder and WC powder is applied to the surface of the metal substrate 100 and the first temperature is reached. When heating, the Ni-based self-fluxing alloy powder dissolves, and thereby part of the metal substrate 100 dissolves. Further, according to Non-Patent Document 1, the WC C dissolved in the molten alloy forms a liquid phase with Fe in the metal substrate 10 at about 1150 ° C., so that the barrier layer 200 containing high-concentration WC is dense. And the WC content can be increased to 95% by weight. Thus, the barrier layer 200 containing the high concentration WC is formed in a state of being firmly bonded to the surface of the metal substrate 100.

  Heating for forming the barrier layer 200 may be performed in two stages. For example, assume that a heating method using an electric furnace is employed in a reduced-pressure atmosphere. The first stage heating is performed at 600 ° C. for 30 minutes to 1 hour, and then the second stage heating is performed at a temperature of 1100 ° C. to 1175 ° C. for 30 minutes to 4 hours. Preferably, the second stage heating is performed at 1150 ° C. for 2 hours. In the first stage heating, the sublimation component contained in the slurry-like powder is removed, and subsequently, the bonding between the metal substrate 100 and the barrier layer 200 containing the metal carbide is ensured by the second stage heating. When the heating temperature is less than 1100 ° C. and the heating time is less than 30 minutes, the slurry powder is insufficiently melted and sintered, so that the adhesion with the metal substrate 100 is inferior and the heating temperature exceeds 1175 ° C. If the time exceeds 4 hours, the metal substrate 100 will be excessively melted.

  Next, a powder composed of a second alloy containing at least one element selected from the group consisting of Fe, Co and Ni on the barrier layer 200 and having a melting point lower than that of the metal substrate 100 and the barrier layer 200, and Al, After applying a slurry-like powder containing a mixed powder with a powder comprising at least one element selected from the group consisting of Cr and Si, the melting point of the metal substrate 100 and the barrier layer 200 is higher than the melting point of the second alloy. Containing at least one element selected from the group consisting of Fe, Co and Ni and at least one element selected from the group consisting of Al, Cr and Si by heating at a lower second temperature; A reservoir layer 300 containing no metal carbide is formed. The method for preparing the slurry powder is the same as that for forming the barrier layer 200. The second alloy includes at least one element selected from the group consisting of Fe, Co, and Ni, and Si and B. Typically, for example, an iron-based self-fluxing alloy, a cobalt-based self-fluxing alloy, and a nickel base At least one alloy selected from the group consisting of self-fluxing alloys. The second temperature is, for example, 1050 ° C. to 1175 ° C., the heating time is, for example, 30 minutes to 4 hours, and preferably 1100 ° C. to 1175 ° C., and the heating time is, for example, 1 hour to 2 hours. However, the present invention is not limited to this. As the Fe-based self-fluxing alloy, the Co-based self-fluxing alloy, and the Ni-based self-fluxing alloy, those commercially available can be used.

  Heating for forming the reservoir layer 300 may be performed in two stages. For example, assume that a heating method using an electric furnace is employed in a reduced-pressure atmosphere. The first stage heating is performed at 600 ° C. for 30 minutes to 1 hour, and then the second stage heating is performed at a temperature of 1100 ° C. to 1175 ° C. for 30 minutes to 4 hours. Preferably, the second stage heating is performed at 1150 ° C. for 2 hours. In the first stage heating, the sublimation component contained in the slurry-like powder is removed, and subsequently, the reservoir layer 300 is formed by the second stage heating, and the bonding with the barrier layer 200 is ensured. When the heating temperature is less than 1100 ° C. and the heating time is less than 30 minutes, the slurry powder is insufficiently melted and sintered, resulting in poor adhesion to the barrier layer 200, the heating temperature exceeding 1175 ° C., and the heating time. Exceeds 4 hours, the melting of the barrier layer 200 proceeds, and the metal carbide enters the reservoir layer 300.

Next, the long fiber ceramic fabric covering layer 400 is formed on the reservoir layer 300. Specifically, for example, by covering the rod-shaped metal substrate 100 having the barrier layer 200 and the reservoir layer 300 formed on the surface thereof with a sleeve-like or knit-like long fiber ceramic fabric, A long fiber ceramic fabric covering layer 400 is formed. As an example of the long fiber ceramic fabric coating layer 400, a specific example of a sleeve-shaped material is as follows.
(1) Nichibi Corporation Alumina long fiber sleeve
Part No. SV-20 Original yarn fiber condition (tex) = 200,
Standard inner diameter = 20mm Weight = 44g / m Number of strokes = 84
72 wt% Al ₂ O ₃ -28 wt% SiO ₂
(2) Ninomiya Electric Cable Co., Ltd. Ceramic yarn sleeve ceramic l
60 wt% Al ₂ O ₃ -40 wt% SiO ₂
(3) Kanamori Tohei Trading Co., Ltd. Alumina long fiber sleeve
72 wt% Al ₂ O ₃ -28 wt% SiO ₂

  As described above, the target processing apparatus shown in FIG. 1 or FIG. 2 is manufactured.

  As described above, according to the first embodiment, the protective film composed of the barrier layer 200, the reservoir layer 300, and the long fiber ceramic fabric covering layer 400 is provided on the surface of the metal substrate 100. Corrosion resistance and erosion resistance of the processing equipment used in contact with molten metal, molten salt, high temperature corrosive gas, etc. can be greatly improved, and the life of the processing equipment can be extended. In addition, this processing equipment is used in an environment where the molten metal is exposed to a meniscus region in which a high-temperature oxidizing atmosphere coexists, in a state where the molten metal fluctuates and flows, or in an environment in which adhesion and peeling of noro etc. occur repeatedly. Thus, excellent hot water erosion resistance and high temperature oxidation resistance can be obtained.

<Second Embodiment>
[Processing equipment]
In the second embodiment, a rod-shaped processing device will be described as in the first embodiment.

FIG. 3 shows this processing equipment. As shown in FIG. 3, in this processing apparatus, a release agent layer 500 is provided on the surface of the long fiber ceramic fabric covering layer 400. As the release agent for the release agent layer 500, for example, water glass mainly composed of sodium silicate, mixed powder of BN powder and Al ₂ O ₃ powder, or the like is used. When the release agent layer 500 is formed by coating, the coating amount, etc. of the long fiber ceramic woven fabric constituting the long fiber ceramic woven fabric coating layer 400 is lost without losing the flexibility of the long fiber ceramic woven fabric coating layer 400. Although it is selected so that the voids between the fibers can be appropriately filled, for example, 0.1 g / cm ² or more and 0.2 g / cm ² or less are desirable. The other configuration of the processing device is the same as that of the processing device according to the first embodiment.

[Processing device manufacturing method]
In this processing apparatus manufacturing method, as in the first embodiment, the barrier layer 200, the reservoir layer 300, and the long fiber ceramic fabric covering layer 400 are sequentially formed on the surface of the metal substrate 100, and then the long fiber ceramics are formed. A release agent layer 500 is formed on the fabric covering layer 400. For example, the release agent layer 500 is formed by applying a slurry liquid containing a powder release agent on the long fiber ceramic fabric coating layer 400. By forming the release agent layer 500 in this manner, the powdery release agent in the slurry liquid fills and closes the gaps between the fibers of the long fiber ceramic fabric constituting the long fiber ceramic fabric coating layer 400.

Specific examples of the release agent for the release agent layer 500 are as follows.
(1) NICHIAS CORPORATION Brand name TOMBO No. 9820 Lumibond Ingredient Adds high fire-resistant aggregate based on sodium silicate. Purpose of use Used as an adhesive for ceramics.
Standard usage 1-2 kg / m ² = 100-200 mg / cm ²
(2) NICHIAS Corporation Trade name TOMBO No. 4726-BN Zilcoat BN-A
Component 82 wt% BN-18 wt% Al ₂ O ₃
Purpose of use Coating material for protecting various refractories that come into contact with molten aluminum Standard usage 0.13-0.17 kg / m ² = 13-17 mg / cm ²

  According to the second embodiment, the following advantages can be obtained in addition to the same advantages as those of the first embodiment. That is, the amount of the release agent layer 500 applied by providing the release agent layer 500 on the surface of the long fiber ceramic fabric coating layer 400 that is in direct contact with molten metal such as molten aluminum or molten zinc when the processing equipment is used. By appropriately selecting the above, etc., it is possible to appropriately fill the gaps between the fibers of the long-fiber ceramic fabric constituting the long-fiber ceramic fabric coating layer 400 without losing flexibility. For this reason, even if it contacts with a molten metal at the time of use of a processing apparatus, it can prevent that a molten metal permeates into the space | gap between the fibers of the long fiber ceramic fabric which comprises the long fiber ceramic fabric coating layer 400.

<Third Embodiment>
[Processing equipment]
In the third embodiment, a rod-shaped processing device will be described as in the first embodiment.

  FIG. 4 shows this processing equipment. As shown in FIG. 4, in this processing apparatus, a release agent layer 500 is provided on the surface of the long fiber ceramic fabric covering layer 400, and the release agent layer is also provided on the surface of the long fiber ceramic fabric cover layer 400 on the reservoir layer 300 side. 500 is provided. That is, the release agent layer 500 is provided on both surfaces of the long fiber ceramic fabric covering layer 400. The release agent layer 500 is the same as that in the second embodiment. The other configuration of the processing device is the same as that of the processing device according to the first embodiment.

[Processing device manufacturing method]
In this processing apparatus manufacturing method, the barrier layer 200 and the reservoir layer 300 are formed on the surface of the metal substrate 100 and then the release agent layer 500 is formed on the reservoir layer 300 in the same manner as in the first embodiment. . Next, after forming the long fiber ceramic fabric coating layer 400 on the release agent layer 500, the release agent layer 500 is formed again on the long fiber ceramic fabric coating layer 400. The method for forming the release agent layer 500 is the same as in the second embodiment.

  According to the third embodiment, in addition to the same advantages as those of the first embodiment, the following advantages can be obtained. That is, not only is the release agent layer 500 provided on the surface of the long fiber ceramic fabric coating layer 400 that is in direct contact with molten metal such as molten aluminum or molten zinc when the processing equipment is used, but also the long fiber ceramic fabric coating layer. Since the release agent layer 500 is also provided on the inner surface of 400, flexibility is lost by appropriately selecting the application amount of the release agent layer 500 on both sides of the long-fiber ceramic fabric coating layer 400. The gap between the fibers of the long-fiber ceramic fabric constituting the long-fiber ceramic fabric coating layer 400 can be appropriately filled. For this reason, even if it contacts with a molten metal at the time of use of processing equipment, it prevents even more effectively that a molten metal penetrate | invades into the space | gap between the fibers of the long fiber ceramic fabric which comprises the long fiber ceramic fabric coating layer 400. I can.

  Hereinafter, it demonstrates in detail based on an Example.

<Structural observation and elemental analysis of coating film>
(1) Elemental analysis of the film surface was performed using a fluorescent X-ray apparatus (element analyzer manufactured by JEOL Ltd.). In this measurement, light elements such as oxygen, nitrogen, carbon, and boron are not analyzed.
(2) Using a scanning electron microscope (SEM) and an energy dispersive element analyzer (EDAX), the cross-sectional structure of the metal substrate 100 and the coating film was observed, and the concentration distribution of each element was measured. In this measurement method, the presence of carbon (C) and boron (B) can be confirmed, but it has been difficult to quantitatively measure their concentrations. Therefore, here, the phases in which carbon and boron are detected are referred to as carbides and borides. Moreover, peak separation between tungsten (W) and silicon (Si) is difficult.

<Example 1>
Example 1 corresponds to the first embodiment, but here, as one corresponding to the cylindrical metal base material 100, a thermoelectric tube that is sealed at one end of a heat-resistant alloy SUH447 tube having an outer diameter of 23 mm. A protective tube was used.

A protective film was formed on the surface of the thermocouple protection tube by steps 1 to 4.
(Process 1)
Ni-based self-fluxing alloy powder and WC powder (35 wt%, 50 wt%, 80 wt%) are mixed in ethanol and kneaded to form a slurry powder. The slurry powder is then added to the thermocouple protective tube. It was applied to the surface and dried. The coating amount was 100 ± 20 mg / cm ² . As Ni-based self-fluxing alloy powder, HMSP-1360-20 (0.9C-4.3Si-3.3B-4.2Fe-16.3Cr-bal.Ni in wt%) of New Metals End Chemical Corporation. Was used. Then, it heated on the conditions of pressure reduction atmosphere, 1150 degreeC, and 2 hours. Thus, the barrier layer 200 was formed on the surface of the thermocouple protection tube.

(Process 2)
Al powder, Cr powder, Si powder and Ni-based self-fluxing alloy powder were mixed in ethanol, kneaded to form a slurry powder, and the slurry powder was applied to the surface of the barrier layer 200 and dried. The coating amount was 80 ± 20 mg / cm ² . Then, it heated on the conditions of pressure reduction atmosphere, 1150 degreeC, and 2 hours. Thus, the reservoir layer 300 was formed on the surface of the barrier layer 200.

(Process 3)
As the long fiber ceramic fabric covering layer 400, the above-mentioned alumina long fiber sleeve with an inner diameter of 20 mm manufactured by Nichibi Corporation was used. The alumina long fiber sleeve is first compressed in the longitudinal direction to increase the inner diameter, and a thermocouple protective tube having a barrier layer 200 and a reservoir layer 300 formed on the surface is inserted into the alumina long fiber sleeve. The inner diameter was reduced by pulling the fiber sleeve, and the alumina long fiber sleeve was brought into close contact with the surface of the thermocouple protective tube. In this way, the surface of the thermocouple protection tube was covered with an alumina long fiber sleeve. The tip of the thermocouple protection tube was wrapped with a metal wire (Ni wire), and the tip of the thermocouple protection tube was covered with an alumina long fiber sleeve.

  Table 2 shows the result (wt%) of the concentration analysis of each element of the barrier layer 200 formed using a mixed powder obtained by adding (35, 50, 80) wt% WC powder to Ni-based self-fluxing alloy powder. The W concentration of the barrier layer 200 increases with the concentration of WC contained in the Ni-based self-fluxing alloy and varies from 30 wt% to 85 wt%. In addition, since carbon (C) is not measured in this analysis method, W shown in Table 2 exists as WC, and the concentration in terms of WC is 33, 65, and 95 wt%, respectively.

  Tables 3 to 5 show the respective elements of the reservoir layer 300 formed using a mixed powder obtained by adding (0, 10, 15, 20) wt% FeAl, 15 wt% Cr, 5 wt% Si to a Ni-based self-fluxing alloy. The result (wt%) of the concentration analysis is shown. In this analysis method, the peak separation between silicon (Si) and tungsten (W) is insufficient, and includes errors.

  From Tables 3 to 5, it can be seen that the Al concentration of the reservoir layer 300 increases to 19 wt% Al with 20 wt% FeAl together with the concentration of FeAl contained in the Ni-based self-fluxing alloy. The Cr concentration and Si concentration of the reservoir layer 300 increase in proportion to the amount of Cr or Si added to the Ni-based self-fluxing alloy.

<Example 2>
Example 2 corresponds to the first embodiment, but here, one end sealing of a tube made of Fe-25Cr stainless steel having an outer diameter of 23 mm, corresponding to the cylindrical metal substrate 100, is performed. The thermocouple protection tube of was used.

  Similarly to Example 1, the protective film was formed on the surface of the thermocouple protective tube by the above steps 1 to 4.

  The compositions of the barrier layer 200 and the reservoir layer 300 were the same as in Example 1.

<Example 3>
Example 3 corresponds to the second embodiment, but here, as an equivalent to the cylindrical metal base material 100, a thermoelectric tube sealed at one end of a heat-resistant alloy SUH447 tube having an outer diameter of 23 mm. A protective tube was used.

  In the same manner as in Example 1, a protective film was formed on the surface of the thermocouple protective tube by the above steps 1 to 4, and a release agent layer 500 was further formed on the reservoir layer 300. As a release agent for the release agent layer 500, the above-mentioned Lumibond manufactured by NICHIAS Corporation was used.

  The compositions of the barrier layer 200 and the reservoir layer 300 were the same as in Example 1.

<Example 4>
Example 4 corresponds to the third embodiment, but here, as an equivalent to the cylindrical metal substrate 100, a thermocouple protection for sealing one end of a tube made of SUS310 having an outer diameter of 23 mm. A tube was used.

  In the same manner as in Example 1, the barrier layer 200 and the reservoir layer 300 were formed on the surface of the thermocouple protection tube by the above steps 1 to 3, and then the release agent layer 500 was formed on the reservoir layer 300. After forming the long fiber ceramic woven fabric coating layer 400 on the release agent layer 500 in Step 4, the release agent layer 500 was formed on the long fiber ceramic woven fabric coating layer 400. As the release agent for these release agent layers 500, the above-mentioned Lumibond manufactured by Nichias Co., Ltd. was used.

  The compositions of the barrier layer 200 and the reservoir layer 300 were the same as in Example 1.

<Comparative example 1>
In Comparative Example 1, a thermocouple protective tube sealed at one end of a tube made of a heat-resistant alloy SUH447 having an outer diameter of 23 mm was used as an equivalent to the cylindrical metal substrate 100, but no protective film was formed.

<Comparative example 2>
Although the comparative example 2 used the thermocouple protective tube of the end sealing of the pipe | tube made from SUS310 with an outer diameter of 23 mm as what is corresponded to the cylindrical metal base material 100, the protective film is not formed.

<Comparative Example 3>
Although the comparative example 3 used the thermocouple protection tube of the end sealing of the pipe | tube made from Fe-25Cr with an outer diameter of 23 mm as what is corresponded to the cylindrical metal base material 100, the protective film is not formed.

<Comparative example 4>
In Comparative Example 4, a thermocouple protection tube sealed at one end of a heat-resistant alloy SUH447 tube having an outer diameter of 23 mm was used as an equivalent to the cylindrical metal base material 100, but only the barrier layer 200 was formed as a protective film. Not. The barrier layer 200 was formed in the same manner as in Example 1.

<Comparative Example 5>
In Comparative Example 5, a thermocouple protective tube sealed at one end of a tube made of Fe-25Cr having an outer diameter of 23 mm was used as an equivalent to the cylindrical metal substrate 100, but only the barrier layer 200 was formed as a protective coating. Not. The barrier layer 200 was formed in the same manner as in Example 1.

<Comparative Example 6>
In Comparative Example 6, a thermocouple protective tube sealed at one end of a tube made of a heat-resistant alloy SUH447 having an outer diameter of 23 mm was used as an equivalent to the cylindrical metal base material 100, but the barrier layer 200 and this barrier were used as protective films. Only the release agent layer 500 on the layer 200 is formed. The barrier layer 200 and the release agent layer 500 were formed in the same manner as in Example 1.

<Comparative Example 7>
In Comparative Example 7, a thermocouple protective tube sealed at one end of a heat-resistant alloy SUH447 tube having an outer diameter of 23 mm was used as an equivalent to the cylindrical metal substrate 100. Only the ceramic fabric covering layer 400 is formed. The barrier layer 200 and the long fiber ceramic fabric covering layer 400 were formed in the same manner as in Example 1.

<Immersion test in molten aluminum alloy>
The test pieces of Examples 1 to 4 and Comparative Examples 1 to 7 prepared as described above were inserted into an Al-Si alloy (ADC12) bath dissolved in an alumina crucible, and taken out after various time elapsed for observation. did. The conditions of the immersion test (bath temperature, immersion time) are as follows.
Comparative Example 1: 800 ° C 3 hours Comparative Example 2: 800 ° C 3 hours Comparative Example 3: 800 ° C 3 hours Comparative Example 4: 800 ° C 4 hours 20 minutes Comparative Example 5: 800 ° C 4 hours 20 minutes Comparative Example 6: 800 ° C 20 hours Comparative Example 7: 800 ° C. 69 hours Example 1: 800 ° C. 71 hours Example 2: 800 ° C. 24 hours Example 3: 800 ° C. 24 hours Example 4: 800 ° C. 90 hours and 800 ° C. 24 hours

FIG. 5: shows the change by the immersion time of the remaining thickness (original thickness = 3 mm) of the test piece of Examples 1-4 and Comparative Examples 1-7. The results of the immersion test shown in FIG. 5 are summarized as follows.
(1) In Comparative Examples 1 to 3, the average erosion rate of the metal substrate is 0.4 mm / hr, and the protective tube having a thickness of 3 mm dissolves and disappears in about 8 hours.
(2) In Comparative Examples 4 and 5, the average erosion rate of the metal base material / barrier layer is 0.11 mm / hr, and the erosion rate of the barrier layer is 1 compared to the erosion rate of the metal base material. / 3. That is, it can be seen that the tungsten carbide-containing barrier layer has a resistance to erosion with respect to the molten metal Al and can extend the life by three times.
(3) In Comparative Example 6, as a result of confirming the effect of the release agent layer, the release agent was applied to the surface of the barrier layer, and a large variation in the melting rate was observed. That is, when the immersion is performed for about 20 hours, the melting damage may not be observed. On the other hand, the melting speed is about 0.1 mm / hr, which is the same speed as that of the barrier layer alone, and the effect of the release agent. It can be seen that there are cases where almost no is seen. That is, when a release agent is applied to the barrier layer, the effect is limited. The
(4) Comparative Example 7 is a case in which a coating layer of a long fiber ceramic woven fabric is formed on the surface of the barrier layer, and there is a case where no erosion is observed and an erosion is observed when the immersion time is 69 hours. The erosion rate was about 0.01 mm / hr.
(5) Example 1 is a case in which a coating layer of a long fiber ceramic woven fabric is formed on the surface of the reservoir layer. In the immersion time of 71 hours, no erosion is observed and erosion may be observed. The erosion rate was about 0.01 mm / hr. It can be seen that in the protective film having the barrier layer, the reservoir layer, and the long fiber ceramic woven fabric coating layer proposed in the present invention, the melting rate is lowered. That is, the coating of the barrier layer 200 and the reservoir layer 300 covered with the long fiber ceramic fabric covering layer 400 proposed in the present invention has excellent resistance to melting regardless of the presence or absence of a release agent. confirmed. The erosion rate is close to zero, and the observed rate is 1/40 of the base material alone and 1/11 of the barrier layer alone, and the long fiber ceramic woven fabric effectively delays the erosion. You can see that
(6) In Examples 2, 3, and 4, the dissolution loss was negligible when the immersion time was 24 hours, and in Example 4, the dissolution loss was small even when the immersion time was 90 hours.

  A cross-sectional photograph of the thermocouple protective tube according to Example 4 after being immersed for 90 hours is shown in FIG. As shown in FIG. 6, it can be seen that the protective film covered with the long fiber ceramic fabric covering layer 400 remains and the metal substrate 100 is not melted.

<On-site test at Al recycling facility>
In an Al recycling facility, the thermocouple protective tube according to Example 4 was inserted into a 680 ° C. molten Al—Si alloy flowing through a bowl-shaped runner provided in an Al—Si alloy (ADC12) melting tank, and the service life was increased. It was measured. As a result, the lifetime of the thermocouple protection tube according to Example 4 was 8 to 10 weeks. For comparison, the same test was performed using the thermocouple protective tube according to Comparative Example 2 in which no protective film was formed, and the lifetime was measured. As a result, the lifetime was 1 week. That is, the lifetime of the thermocouple protection tube according to Example 4 was 8 to 10 times the lifetime of the thermocouple protection tube according to Comparative Example 2 in which no protective film was formed.

  Although the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to the above-described embodiments and examples, and various modifications based on the technical idea of the present invention. Is possible.

  DESCRIPTION OF SYMBOLS 100 ... Metal substrate, 200 ... Barrier layer, 300 ... Reservoir layer, 400 ... Long fiber ceramic textile coating layer, 500 ... Release agent layer

Claims (18)

A metal substrate made of a steel material ;
Having a protective coating provided on the surface of the metal substrate,
The protective film is
A barrier layer containing 35 wt% or more and 95 wt% or less of metal carbide on the metal substrate, and containing one kind of element selected from the group consisting of iron, cobalt and nickel ;
On the barrier layer, containing at least one element selected from the group consisting of the above-mentioned one element and aluminum, chromium and silicon, and when containing aluminum, its content is 1 wt% or more and 15 wt% or less In the case of containing chromium, the content is 1% by weight or more and 30% by weight or less, and in the case of containing silicon, the content is 1% by weight or more and 15% by weight or less, and a reservoir layer containing no metal carbide,
A coating layer made of a long-fiber ceramic fabric on the reservoir layer;
Having processing equipment.   2. The processing apparatus according to claim 1, wherein the long fiber ceramic fabric is a cloth, knit or sleeve knitted with long fiber ceramics.   The processing equipment according to claim 1 or 2, wherein the metal carbide is at least one selected from the group consisting of tungsten carbide, molybdenum carbide, niobium carbide, aluminum carbide, and chromium carbide. The processing apparatus according to any one of claims 1 to 3, wherein the reservoir layer further contains 10 wt% or more and 15 wt% or less of titanium. The processing apparatus according to claim 1, wherein the reservoir layer contains nickel in an amount of 90 wt% or more and less than 100 wt%. The processing apparatus according to any one of claims 1 to 3, wherein the reservoir layer contains 7 wt% or more and 15 wt% or less of aluminum. The processing apparatus according to any one of claims 1 to 3, wherein the reservoir layer contains 5 wt% or more and 15 wt% or less of silicon. The processing apparatus as described in any one of Claims 1-7 by which the releasing agent layer with respect to a molten metal is provided in the surface of the said coating layer. The processing apparatus according to claim 8, wherein a release agent layer for the molten metal is also provided on a surface of the coating layer on the reservoir layer side. The above processing equipment is a metal melting tank, metal melting pot, metal plating tank, thermocouple protection tube, molten metal stirring rod, ladle for transporting molten metal, and scraping to scoop off the floating on the surface of the molten metal. A processing apparatus according to any one of claims 1 to 9, which is a hot pot for smelting molten metal, a handle for squeezing molten metal, or a blow lance. A metal substrate made of a steel material;
Having a protective coating provided on the surface of the metal substrate,
The protective film is
A barrier layer containing 35 wt% or more and 95 wt% or less of metal carbide on the metal substrate, and containing one kind of element selected from the group consisting of iron, cobalt and nickel;
On the barrier layer, containing at least one element selected from the group consisting of the above-mentioned one element and aluminum, chromium and silicon, and when containing aluminum, its content is 1 wt% or more and 15 wt% or less In the case of containing chromium, the content is 1% by weight or more and 30% by weight or less, and in the case of containing silicon, the content is 1% by weight or more and 15% by weight or less, and a reservoir layer containing no metal carbide,
A coating layer made of a long-fiber ceramic fabric on the reservoir layer;
A structure having A metal substrate made of a steel material;
Having a protective coating provided on the surface of the metal substrate,
The protective film is
A barrier layer containing 35 wt% or more and 95 wt% or less of metal carbide on the metal substrate, and containing one kind of element selected from the group consisting of iron, cobalt and nickel;
On the barrier layer, containing at least one element selected from the group consisting of the above-mentioned one element and aluminum, chromium and silicon, and when containing aluminum, its content is 1 wt% or more and 15 wt% or less In the case of containing chromium, the content is 1% by weight or more and 30% by weight or less, and in the case of containing silicon, the content is 1% by weight or more and 15% by weight or less, and a reservoir layer containing no metal carbide,
A coating layer made of a long-fiber ceramic fabric on the reservoir layer;
A method of manufacturing a processing device having
A powder of metal carbide and a powder comprising a first alloy containing the above kind of element and silicon and boron contained in the barrier layer and the reservoir layer having a melting point lower than that of the metal substrate on the surface of the metal substrate. Forming a barrier layer by applying a slurry-like powder containing the mixed powder and heating at a first temperature higher than the melting point of the first alloy and lower than the melting point of the metal substrate; ,
On the barrier layer, powder and aluminum comprising the above-mentioned one kind of element contained in the barrier layer and the reservoir layer, silicon and boron, and consisting of the metal base material and a second alloy having a melting point lower than that of the barrier layer, aluminum, After applying a slurry-like powder containing a mixed powder with a powder containing at least one element selected from the group consisting of chromium and silicon, the melting point of the second alloy is higher than the melting point of the second alloy, Forming the reservoir layer by heating at a second temperature lower than the melting point;
Forming a coating layer made of a long-fiber ceramic fabric on the reservoir layer;
A method of manufacturing a processing apparatus having The first alloy includes an iron-based self-fluxing alloy when the one kind of element contained in the barrier layer and the reservoir layer is iron, and the one kind element contained in the barrier layer and the reservoir layer is cobalt. 13. The method of manufacturing a processing apparatus according to claim 12, wherein if present, the cobalt-based self-fluxing alloy, and the barrier layer and the reservoir layer are nickel-based self-fluxing alloys when the one kind of element is nickel. The method for manufacturing a processing apparatus according to claim 12 or 13, wherein the first temperature is 1100 ° C or higher and 1200 ° C or lower. The second alloy includes an iron-based self-fluxing alloy in the case where the one kind of element contained in the barrier layer and the reservoir layer is iron, and the one kind element contained in the barrier layer and the reservoir layer is cobalt. The processing equipment according to any one of claims 12 to 14, wherein if present, the cobalt-based self-fluxing alloy, and if the one kind of element contained in the barrier layer and the reservoir layer is nickel, the processing equipment is a nickel-based self-fluxing alloy. Manufacturing method. The said 2nd temperature is 1050 degreeC or more and 1175 degrees C or less, The manufacturing method of the processing equipment as described in any one of Claims 12-15. The method for manufacturing a processing apparatus according to any one of claims 12 to 16, wherein the barrier layer and the reservoir layer are formed by a physical vapor deposition method, a thermal spraying method, a diffusion penetration method, a chemical vapor deposition method, or an electroplating method. A metal substrate made of a steel material;
Having a protective coating provided on the surface of the metal substrate,
The protective film is
A barrier layer containing 35 wt% or more and 95 wt% or less of metal carbide on the metal substrate, and containing one kind of element selected from the group consisting of iron, cobalt and nickel;
On the barrier layer, containing at least one element selected from the group consisting of the above-mentioned one element and aluminum, chromium and silicon, and when containing aluminum, its content is 1 wt% or more and 15 wt% or less In the case of containing chromium, the content is 1% by weight or more and 30% by weight or less, and in the case of containing silicon, the content is 1% by weight or more and 15% by weight or less, and a reservoir layer containing no metal carbide,
A coating layer made of a long-fiber ceramic fabric on the reservoir layer;
A method of manufacturing a structure having
A powder of metal carbide and a powder comprising a first alloy containing the above kind of element and silicon and boron contained in the barrier layer and the reservoir layer having a melting point lower than that of the metal substrate on the surface of the metal substrate. Forming a barrier layer by applying a slurry-like powder containing the mixed powder and heating at a first temperature higher than the melting point of the first alloy and lower than the melting point of the metal substrate; ,
On the barrier layer, powder and aluminum comprising the above-mentioned one kind of element contained in the barrier layer and the reservoir layer, silicon and boron, and consisting of the metal base material and a second alloy having a melting point lower than that of the barrier layer, aluminum, After applying a slurry-like powder containing a mixed powder with a powder containing at least one element selected from the group consisting of chromium and silicon, the melting point of the second alloy is higher than the melting point of the second alloy, Forming the reservoir layer by heating at a second temperature lower than the melting point;
Forming a coating layer made of a long-fiber ceramic fabric on the reservoir layer;
The manufacturing method of the structure which has this.