JP2729615B2 - Composite surface treatment material having high corrosion resistance and high heat resistance and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a composite surface treatment material having high corrosion resistance and high heat resistance as a container or tube for use in a highly corrosive gas atmosphere at a high temperature. . (Prior art) There are plastic products as containers and tubes with corrosion resistance, but due to thermal and strength restrictions, stainless steel products that are satisfactory in strength lack durability for highly corrosive substances. . Quartz products and graphite products are used when high corrosion resistance and high heat resistance are required.
It is extremely expensive and low in strength. There are glass lining containers and tubing materials that are strong and have corrosion resistance and heat resistance.There is no problem as long as they are used for general household use, but if they are used in processes that involve special chemical reactions, they have high corrosion resistance And heat resistance is required, the manufacturing process becomes extremely complicated, for example, the glass lining process is repeated three to four times, and the manufacturing cost is accordingly increased. Under such circumstances, the present applicant has filed a patent application No. 54-7810.
No. 0 (Japanese Patent Publication No. 59-13590), a method for easily producing glass-lined containers and pipes exhibiting high corrosion resistance at high temperatures was provided, and Japanese Patent Application No. 54-91687 (Japanese Unexamined Patent Publication No. 166
No. 82) to provide a method for manufacturing containers and pipes in which the above-mentioned glass lining method is performed after forming a permeated alloy layer and a coating by infiltrating the material metal surface with a predetermined element or its alloy. did. When the prior arts according to the above two inventions are combined, for example, chromium, aluminum, silicon or an alloy thereof is formed by using a known solid method, a liquid method and a gas method and any of a certain infiltration alloy forming method. Inexpensive low-alloy steel is subjected to infiltration treatment to form an infiltrated alloy layer and a coating on the surface of the material, thereby imparting high-temperature oxidation resistance to the surface of the material metal. Suppression of generated gas and formation of appropriate surface roughness ensure good wettability with the frit. Then, water is added to make the mud-like frit on the surface of the infiltration material, dried and coated with the frit coating. The layer is made so that the vapor contained in the frit coating layer easily escapes from the inside to the surface through the preheating of the metal material by the induction heating means and the main heating. Melt using methods, it is baked to be double the surface treatment material and its manufacturing method. The product obtained by the above method has strength, of course,
Excellent peel resistance, for example, for tube products,
In the smelting of aluminum with a melting point of 659 ° C, when used as a blowing pipe for blowing chlorine gas by being inserted into the molten metal, the tip is consumed at 500 mm while always maintaining the tip at 300 mm in the molten metal. When the service life is defined as the standard for the service time, a product having high temperature and high corrosion resistance can be manufactured while ensuring a service time of 20 hours or more. (Problems existing in the prior art) The above-mentioned products according to the prior art can guarantee the service life as described above up to a temperature of about 800 ° C. However, the service life is significantly reduced at a temperature of 900 to 1,000 ° C. There has been a demand for an increase in high temperature resistance. An object of the present invention is to meet the above demand. (Constitution of the Invention) The gist of the composite surface treatment material of the present invention is that a surface layer of a base metal is infiltrated with a high-temperature oxidation-resistant element and that the element or an alloy thereof covers the surface of the infiltrated alloy layer. A first layer comprising a coating of
A glass lining layer is formed as a second layer on the surface of the layer, and a refractory material layer is formed as a third layer on the second layer;
In the second layer, the refractory material particles are mixed in such a distribution that the surface direction becomes high concentration, and the refractory material particle high concentration distribution portion of the surface layer of the second layer and the bottom layer of the third layer are continuous. A composite surface treatment material having high corrosion resistance and high heat resistance. FIG. 1 schematically shows an enlarged cut surface of a surface layer portion of a composite surface treatment material according to the present invention, where M is a metal material portion, and a predetermined element or a permeated alloy of an alloy thereof is formed on the surface layer of the metal material. A layer s is formed, and the surface of the infiltrated alloy layer s is covered with a coating e of a thin element or an alloy thereof. The first layer (I) is formed by the infiltrated alloy layer s and the coating e. A glass lining layer of a second layer (II) is further formed on the first layer (I), which is a surface, and a third layer (II) made of a refractory material.
I) are stacked. The second layer (II) is composed of a lower pure glass lining layer indicated by G and a mixed layer u in which the distribution concentration of the refractory material particles increases toward the surface of the upper layer. Incidentally, the spherical cavity shown as b is a void having a diameter of 10 μm or less generated and formed in the glass lining layer. The present invention is a composite surface treatment material obtained by laminating a first layer (I) to a third layer (III) in a state as shown in FIG. Alumina, graphite, magnesia and the like are used as the refractory material forming the third layer (III). Of these various refractory materials, a material having an appropriate property according to the purpose of use is used. Powder is used selectively. For example, temperature conditions,
Conditions such as difficulty reacting with the contact object must be considered. When the material metal is a small-diameter tube material and it is difficult to form the third layer on the inner peripheral surface by the manufacturing method described later and only the outer peripheral surface comes into contact with a high-temperature material, the inner peripheral surface is Having a certain level of heat resistance by having one layer and a second layer,
The first to third layers may be provided only on the outer peripheral surface. The present invention also provides a manufacturing method particularly suitable for obtaining a composite surface treatment material having the above-mentioned high corrosion resistance and heat resistance. There are two production methods according to the present invention, but the gist of the first method is that the surface of the base metal is subjected to a permeation treatment using a high-temperature oxidation-resistant element to form a permeated metal layer and the permeated alloy layer. During the process of forming a coating of the element or its alloy covering the surface, applying water to the coating to form a mud-like frit, forming a frit coating layer, and drying the frit coating layer. High-pressure refractory material particles are sprayed onto the surface in a state before solidification, and a portion of the refractory material particles is coated so as to penetrate into the frit-coating layer. In a method for producing a composite surface treatment material having corrosion resistance and high heat resistance, characterized in that sintering is performed through heating of a metal material by an induction heating means. That is, the first method of the present invention is the same as the above-mentioned prior art, ie, the step of manufacturing the double surface treatment material and the step of forming the first layer (I), but the steps after the formation of the second layer (II) are the same as those of the prior art. Differently from this, in the process of drying the frit and coating layer at the time of forming the second layer (II), when the muddy frit is in a semi-dry state, the refractory powder is sprayed at a high pressure by using a spraying device for the coating layer. As a result, a part of the refractory material particles are injected into the soft layer, and are distributed in the surface of the frit coating layer at a low concentration as the surface direction is directed toward a high concentration / central direction. Is wet and adheres to and covers the surface of the frit coating layer in a thin layer. When the frit coating layer and the refractory powder coating layer formed in the above step are dried, they are subjected to a heating step and fired. The sintering is performed through preheating of the metal material by the induction heating means and main heating as in the case of the double surface treatment material manufacturing process of the prior art. The first method of the present invention comprises the steps as described above,
As described in detail above, a composite surface treatment material having high corrosion resistance and high heat resistance obtained by laminating the first to third layers so as to enter each boundary is obtained. Note that the material metal is a small-diameter tube material, and it is difficult to inject high-pressure refractory powder particles into the frit coating layer on the inner peripheral surface of the tube material, and only the outer peripheral surface of the tube comes into contact with a high-temperature substance such as a molten metal. When used in such a situation, high-pressure injection of refractory material particles may be performed only on the outer peripheral surface of the pipe material. As a result, a composite surface treatment material having an outer peripheral surface up to the third layer and an inner peripheral surface up to the second layer can be obtained. The second method of the present invention is realized in a step different from that of the first method, and the gist of the present invention is that the surface of the material metal in the prior art is infiltrated with a predetermined high-temperature oxidation-resistant element or an alloy thereof. The steps of forming the first layer (I) composed of the infiltrated alloy layer and the coating and the step of forming the frit coating layer and drying the same are the same, but by increasing the temperature of the metal material using induction heating means. In the process of firing the frit / coating layer, when the frit / coating layer reaches a molten state, refractory material particles are injected at a high pressure into the molten layer, and a part of the refractory material particles is injected into the molten layer. There is provided a method for producing a composite surface treatment material having high corrosion resistance and high heat resistance, characterized in that it is coated and fired while being radiated. That is, when the metal material is induction-heated in the process of firing the frit-coating layer, the frit is sequentially heated from the inside in contact with the metal material by heat conduction, and is contained in the layer in the preheating process described above. Drives water vapor, etc. toward the surface,
Next, in the main heating process, the material is fired sequentially from the inside to the surface through a molten state. When the surface reaches the above-mentioned molten state, predetermined refractory material particles are sprayed with a high pressure using a spraying device to apply the refractory material powder. Part of the grains is caused to enter the molten layer. As a result, a part of the refractory material particles is injected into the frit-coating layer in a soft molten state, and the surface direction of the frit-coating layer in the surface layer of the frit-coating layer increases toward the high concentration / central direction. It is distributed at a low concentration and partly adheres as a thin layer to the surface of the frit coating layer and is baked together with the frit in a state of covering the thin layer, and the second layer (II) and the second layer (II) are formed on the first layer (I). A third layer (III) is formed. The second method of the present invention comprises the steps as described above,
This is to obtain a composite surface treatment material having high corrosion resistance and high heat resistance in which the first to third layers described in detail in the first method described above are laminated with their respective boundaries inserted. In the second method, when the material metal is a small-diameter tube, the high-pressure injection of the refractory material particles may be performed only on the outer peripheral surface of the tube similarly to the case of the first method described above. Good. As a result, a composite surface treatment material having an outer peripheral surface up to the third layer and an inner peripheral surface up to the second layer can be obtained. (Example 1) When the above-mentioned second method of the present invention is applied to a container, first, a first layer (I) composed of a penetrating alloy layer and a coating layer is formed on the inner and outer surfaces of the container by a penetrating alloy forming method. In forming the second layer (II) and the third layer (III), an induction heating means is used. If the container is small in diameter, a multi-turn heating coil with a small winding diameter in the direction facing the bottom and a large winding diameter in the direction facing the outer circumference is used. The shape, number, and number of turns of the coil are arbitrarily set within a range of design items, such as using a multi-turn heating coil capable of facing the coil. A frit coating layer is formed on the first layer (I) composed of the infiltrated alloy layer and the coating, and the dried container is placed in a state where the opening is upward (to promote the diffusion and rise of water vapor generated during heating). In the step (1), the heating coil is opposed to the heating coil, and the heating coil is preheated and main-heated by applying an electric current to the heating coil after stopping the energization for a predetermined time. The main heating includes a heating step divided into two steps, and when the frit / coating layer on the surface of the container is in a molten state, the container is removed from the position facing the heating coil, and high-pressure refractory material particles are injected, After that, the main heating is continued again by facing the heating coil, and the firing is completed to form the second layer (II) and the third layer (III). (Example 2) When the second method of the present invention is carried out on a small-diameter pipe, the first method comprising a permeated alloy layer and a coating on the inner and outer surfaces of the pipe is used.
The layer (I) is formed by using an infiltration alloy forming method, and then a frit coating layer is formed on the surface of the first layer (I).
After the drying, as shown in FIG. 2, the heating coil having the structure of C1 for preheating, C2 for first heating, and C3 for second heating, as shown in FIG. The refractory material powder injector composed of the annular nozzle R interposed between the second main heating coils C2 and C3 is relatively moved from the upper end direction to the lower end direction of the suspended tube W (the same as in Example 1.1). Similarly, in order to prevent the water vapor generated during heating from escaping and rising, and to raise the water vapor toward the inner peripheral surface of the fired pipe to prevent the adhesion and absorption of the water vapor to the unfired frit / coating layer.) The refractory material particles are injected at a high pressure from the annular nozzle R toward the frit coating layer on the outer peripheral surface which has passed through the inside of the heating coil C1 and the inside of the first heating coil C2 and has become molten. Finish firing by passing through heating coil C3 , A second layer (II) and third
Form a layer (III). According to the above method, the refractory material particles can be injected deep into the surface of the frit coating layer. However, if it is not necessary to inject the particles so deeply, the second heating coil C3 is omitted. Is also good. FIG. 3 shows a cross-sectional micrograph of a sample prepared from the product obtained by the above manufacturing method. The lower white portion is a metal material, and the first layer (I) is not so clearly shown in the photograph, but has a predetermined rough surface, and the second layer is formed on the rough surface of the first layer (I). It is observed that the layer (II) is formed by digging in, and the refractory material particles are injected into the surface of the second layer (II). The dark band, which divides the photograph into upper and lower parts, is that the third layer (III), which had existed on the second layer (II), fell into a cavity during polishing because the cut pieces were buried in resin during sample preparation. The upper half shows the resin part. (Experimental example) ☆ Specimen: Using the following tube material as the base metal, chrome infiltration treatment, and divided into 2 groups of 5 each for A and B,
A group A is prepared by forming a frit-coated layer by applying a conventional method of forming a frit-coating layer and then firing. A group B is formed with a frit-coated layer and subjected to high-pressure injection of refractory powder during firing. Specimen B group was prepared by performing the second method of the present invention. The refractory used in Group B was alumina. Material metal: JIS G3444 Dimensions: Outer diameter 33mm Inner diameter 25mm Length 4000mm ☆ Experimental method: Use each specimen group A and B as aluminum smelting chlorine blowing tubing and measure the service life under the same experimental conditions below. Then, the average value of each group was determined. Experimental conditions: The tip of the specimen was immersed in the molten aluminum at approximately 800 ° C at a constant temperature of 300 mm, and chlorine was blown into the molten metal through the specimen tube. measure. ☆ Experimental results: The average value of the specimen A group (performed by the conventional method) was 25 hours, and that of the specimen B group (performed by the method of the present invention) was 55 hours. In addition, not only the specimen A group but also the specimen B group subjected to the experiment did not show any peeling phenomenon of the refractory material layer. (Function of the Invention) The present invention provides a first layer (I) and a second layer (II) each having high corrosion resistance and high heat resistance on a metal surface layer and a third layer having higher heat resistance suitable for the intended use. The layer (III) is formed by laminating the first layer (I) and the second layer (II).
As described in the description of the invention of the prior application, "laminate" has a good wettability and is a composite surface treatment material in which the boundary between the second layer (II) and the third layer (III) is inserted. This is a manufacturing method capable of bringing the laminated state. Therefore, compared with the case where the refractory material particles are simply mixed and evenly distributed into the mud frit which is applied to the material metal surface and fired, the effective high heat resistance can be obtained by using a small amount of the refractory material particles. And high corrosion resistance, and compared to the case where refractory powder is applied to the surface of a product obtained by carrying out the present invention, the high temperature and high corrosion resistance brought by the present invention is further improved. The heat resistance is increased, and the risk of peeling of the refractory material layer is eliminated. (Effect of the Invention) By implementing the present invention, the heat resistance is further increased as compared with the conventional product, the service temperature is raised from about 800 ° C to about 1,000 ° C, and the service time is doubled,
This will contribute to the expansion of the application range of the product and the reduction of the running cost for the user of the product.Furthermore, the manufacturing equipment only needs to add a simple refractory material powder high-pressure injection mechanism, so no significant capital investment is required. In addition, the material cost is low, and the production is possible without incurring the rise of the production cost. The effects are numerous and extremely rewarding.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an enlarged sectional view schematically showing a composite surface treatment material having high corrosion resistance and high heat resistance according to the present invention, and FIG. 2 shows one embodiment of the method of the present invention. FIG. 3 is a partially sectional front view, and FIG. 3 is a sectional micrograph of the product of the present invention. (I)... First layer s... Infiltration alloy layer e... Element or alloy coating (II)... Second layer G... Pure glass lining layer u. Surface layer (III) of the third layer

Claims (1)

(57) [Claims] The surface layer of the base metal is a first layer made of a permeated alloy layer impregnated with a high-temperature oxidation-resistant element and a film of the element or its alloy covering the surface of the permeated alloy layer, and the surface of the first layer is glass-lined. A layer is formed as a second layer, a refractory layer is formed as a third layer on the second layer,
In the second layer, the refractory material particles are mixed in such a distribution that the surface direction becomes high concentration, and the refractory material particle high concentration distribution portion of the surface layer of the second layer and the bottom layer of the third layer are continuous. A composite surface treatment material with corrosion resistance and high heat resistance. 2. The surface layer of each of the inner and outer peripheral surfaces of the tube material formed of the material metal is a first layer composed of a permeated alloy layer impregnated with a high-temperature oxidation-resistant element and a film of the element or its alloy covering the surface of the permeated alloy layer. A glass lining layer is formed as a second layer on the surface of the first layer on the inner and outer peripheral surfaces, and a refractory material layer is formed as a third layer only on the second layer on the outer peripheral surface side of the tube material; and In the second layer on the outer peripheral surface side of the pipe material, refractory material particles are mixed in such a distribution that the surface direction becomes high concentration, and the refractory material particle high concentration distribution portion of the second layer surface layer and the bottom layer of the third layer are formed. Is a composite surface treatment material with corrosion resistance and high heat resistance characterized by being continuous. 3. The surface of the base metal is subjected to infiltration treatment using a high-temperature oxidation-resistant element to form a permeated metal layer and a film of the element or its alloy covering the surface of the permeated alloy layer, and then water is added to the film. The frit coating layer is formed by applying a mud-like frit to form a frit coating layer, and during the process of drying the frit coating layer, high-pressure spraying of refractory material particles onto a surface in a state before solidification is performed. It is characterized in that a part of the particles is coated so as to penetrate into the frit coating layer, and the layer formed by the above process is baked through the heating of the metal material by the induction heating means. A method for producing a composite surface treatment material with corrosion resistance and high heat resistance. 4. The surface of the base metal is subjected to infiltration treatment using a high-temperature oxidation-resistant element to form a permeated metal layer and a film of the element or its alloy covering the surface of the permeated alloy layer, and then water is added to the film. A frit-coated layer is formed by applying a frit in a mud-like state, and the frit-coated layer is dried, and then the metal material is heated by using an induction heating means, thereby firing the frit-coated layer. In the firing step, when the frit-coating layer reaches a molten state, the refractory material particles are injected at high pressure onto the surface of the molten layer, and a part of the refractory material particles enter the molten layer. A method for producing a composite surface treatment material having corrosion resistance and high heat resistance, wherein the material is fired while being coated as described above.