KR20080043230A - Electrocast brick coated with metal film and method of manufacturing the same - Google Patents

Abstract

An electrocast brick coated with metal film is provided to prevent the metal film from being exfoliated by stress, to have high durability and heat resistance, and to be useful as a heat-resistant structural frame. An electrocast brick coated with metal film comprises an electrocast brick(1) in which a groove part(3) for regular anchors is formed on the surface, and a metal film(5) which covers the surface of the electrocast brick and is formed to reclaim the groove part for anchors. The metal film contains a platinum group metal. The electrocast brick has a porosity of 5 vol% or less and a glass phase ratio of 15% by mass or less. The film thickness(m) of the metal film ranges from 100 to 400 micron.

Description

Metal film-forming pole pole brick and its manufacturing method {ELECTROCAST BRICK COATED WITH METAL FILM AND METHOD OF MANUFACTURING THE SAME}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal film-forming electrode pole brick coated with a surface of a pole brick with a metal film, and a method of manufacturing the same. In particular, it requires heat resistance and durability, such as a portion in contact with molten glass in a glass manufacturing facility. The present invention relates to a metal film-forming pole brick which can be used as a member constituting a structural part to be formed and a method of manufacturing the same.

As a method of coating a base material with a metal film, there exist a thermal spraying method, such as a plasma spraying and an oxyhydrogen spraying (for example, refer following patent document 1). This is a thin film formation method in which molten metal is sprayed into a particle shape and sprayed onto a substrate, which can be applied to both conductive materials and insulating materials.

When coating a metal base material with a metal sprayed coating, generally, in order to improve the fixability of a metal base material and a sprayed coating, pretreatment, such as a blasting process, is given to the metal base surface. In detail, hard ceramic particles are ejected to impinge on the surface of the metal substrate, whereby unevenness of appropriate roughness is formed on the surface of the metal substrate. By forming such unevenness, the thermally sprayed metal particles enter the concave portion, so that the metal solidified in the concave portion exhibits an anchor effect, and the joining of the metal substrate and the sprayed metal film is realized.

The above method uses a metal substrate having high flexibility and plastic deformation properties, but in the case of a non-metal substrate such as brick, the hardness, brittleness, and plastic deformation of the substrate are low, so that it is difficult to apply the blasting treatment. .

For this reason, when brick is coat | covered with the thermal sprayed coating, the intermediate | middle layer of ceramic is formed in the brick surface by the sol-gel method etc., and it interposes and improves adhesiveness with a brick base material and a metal thermal sprayed coating. This intermediate | middle layer forms strong bonding by the chemical bonding of the glass (silica) phase in a ceramic and a brick, and the thermal spray metal particle penetrates into a ceramic intermediate | middle layer, and the thermal sprayed coating is fixed.

Further, by using the porosity of the material to fill pores present on the surface of the refractory base material by heating and baking the mixture of platinum fine particles and inorganic material, the surface is ground to expose a portion of the platinum fine particles to form a thermal spray coating, etc. This is proposed (patent document 2 below).

[Patent Document 1] British Patent Publication No. 1242996

[Patent Document 2] Japanese Patent Application Laid-Open No. 10-195623

However, the method using the ceramic intermediate layer mentioned above is not effective for the base material which does not contain a glass phase, since sticking by a chemical bond cannot be anticipated. Therefore, it is not suitable when coating the electroplated brick with few glass phases with a thermal sprayed coating.

Moreover, since the method of the said patent document 2 is applicable only to a porous material, it is difficult to apply generally to the pole brick with low porosity.

Due to such a situation, it is difficult to form a metal film by thermal spraying on a compacted glass pole having high glass density, and the thermal sprayed metal is easily peeled from the electrical pole brick during the spraying or during the cooling after the spraying.

Disclosure of Invention The present invention has developed a metal film technology capable of forming a metal film that is hardly adhered to a ceramic substrate having a small glass phase and is highly dense, and provides a metal film-forming pole brick which is highly durable and useful as a heat resistant structural material. do.

Another object of the present invention is to provide a method for producing a metal film-forming pole brick, which can easily and stably provide a metal film-forming pole brick that can be used as a heat-resistant structural material without the metal film to be coated be peeled off by stress. Shall be.

In order to solve the above problems, the present inventors earnestly studied, and as a result, by studying the irregularities formed on the surface of the pole brick, the thermal stress due to the difference in the amount of heat shrinkage between the metal and the brick is properly distributed, and the anchor effect is preferable. It was found out that the metal film that was easily exhibited can be formed on the surface of the pole brick, and thus the present invention was completed.

According to one aspect of the present invention, a metal film-forming pole pole brick has a pole pole brick having a regular anchor recess formed on its surface, and a metal film formed to cover the surface of the pole brick to fill the anchor recess, The metal film contains a platinum group metal, and the main pole brick has a porosity of 5% by volume or less and a glassy ratio of 15% by mass or less.

Moreover, according to one aspect of the present invention, in the method for producing a metal film-forming pole brick, a regular anchoring recess is formed on the surface of the pole brick having a porosity of 5% by volume or less and a glassy ratio of 15% by mass or less. It is a summary that a metal containing metal is sprayed on said pole brick to form a metal film which fills the said recessed part and covers the surface of the pole brick.

According to the present invention, in the regular concavities and convexities formed on the surface of the pole brick, the stress generated between the metal film and the pole brick is properly dispersed and acted, and the anchor effect is preferably exhibited without causing breakage of the convex portion or deformation of the metal film. . Therefore, the metal film formation pole brick in which heat resistance and durability are high, and peeling of the metal film by temperature change is suppressed is provided, and can be effectively used as a heat resistant structural material.

Refractory brick is used for the heat-resistant structural material for organic kilns heated at high temperatures, and among them, in the throat portion requiring durability, a refractory brick coated with a thermal spray coating of platinum or platinum alloy is used. Since the manufacture of high-strength pole bricks was established with recent advances in technology, the use of pole bricks instead of refractory bricks has been established for refractory for organic kilns.

Jeonju brick is a refractory material obtained by heating a refractory raw material to a temperature of 1900 to 2500 ° C. in a heroic arc furnace or the like, and casting a completely melted refractory raw material in a mold having a predetermined shape and slow-cooling it. High strength and durability However, since the pole brick generally has a small ratio of glassy phase, it is not effective to use the above-described ceramic intermediate layer as a method of improving the adhesiveness with the metal film. Moreover, since there are few pores and porosity is generally 5% or less, it is also difficult to use the filling with the pore of the metal containing paste like patent document 2 mentioned above. Moreover, when a pore is considered in the manufacturing method of a waste material, it exists not in periodicity but exists sparsely. Therefore, when the metal-containing paste is filled with pores, even if the filling paste has an anchor effect, the anchor effect naturally exists sparse. As a result, there exists a part from which the adhesiveness of a metal film and a furnace material differs in the part with an anchor effect, and the part without an anchor effect, and it is difficult to form the metal film which adhered stably over the whole film. For this reason, in order to improve the adhesiveness with a metal film, it is considered to perform a blasting process similarly to the case of a metal substrate, but actually, when platinum spraying is performed to the blasted pole brick, platinum is in or after spraying. The film is peeled off, making it difficult to fix the platinum film. Since the peeling of the platinum film occurs in a state where the convex portion of the brick surface formed by the blast treatment is broken by stress, the cause is that a large difference occurs in the amount of heat shrinkage due to the temperature difference between the metal during spraying and the pole brick. There arises in the thing which cannot produce the unevenness | corrugation which exhibits an effective anchor effect by the blast process.

In this fact, in order to suppress the breakage of the convex part of the electric pole brick surface, the tensile stress applied from the metal film is dispersed as uniformly as possible, and the irregular stone surface of which the anchor effect effectively acts on the electric pole brick surface is subjected to the electric pole brick surface. It is most important to carry on. In the present invention, regular irregularities are formed on the surface of the pole brick as anchoring recesses, and metal is sprayed on the surface of the bricks to fill the recesses and cover the surfaces. EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Metal spraying is a coating method that can form a metal film on not only a conductive substrate but also an insulating substrate, and can inject molten particles of various metals, and generally zinc, aluminum, tin, copper, petroleum, steel, etc. Although metal is used, in order to comprise the heat-resistant and durable metal-sprayed brick which can be used as a structural material for glass manufacture, alloys containing one or more platinum group metals, such as Pt, Ir, Ru, and Rh with high melting points, or a platinum group metal This is used. As an alloy, platinum alloys, such as Pt-5% Au, Pt-10% Ir, Pt-10% Rh, etc. are mentioned, for example. The thermal expansion coefficient of these platinum group metals and their alloys is about 8 * 10 <^-6> -15 * 10 <^-6> (20 degreeC) in general. The metal particles injected by the thermal spraying method fill in the recesses of the pole bricks and are deposited on the surface to form a film. The thickness of a metal sprayed coating can be suitably adjusted with the amount of spraying. Since an excessively thick film may not be able to withstand deformation due to tensile stress, the thickness of the film (thickness covering the brick surface except for the recessed part) is preferably about 100 to 400 μm, and more preferably 200 It is-350 micrometers.

Bricks are ceramics composed of alumina, alumina silicate, zircon-mullite, silica, titania, etc., which are obtained by hardening and firing raw materials such as clay, which are bonded and molded by chemical binders without performing heat treatment. While what is a refractory brick, electric pole brick is a brick which melt | dissolves a raw material completely in an electric furnace and casts. Examples of the pole bricks include AZS (A ₂ O ₃ -SiO ₂ -ZrO ₂ ) bricks, α alumina bricks, β alumina bricks, α β alumina bricks, alumina chrome bricks, and the like. Electric pole bricks have more improved bricks depending on the application, and include, for example, high zirconia-like bricks with a higher content of zirconia, void-free (VF) bricks with lower porosity, and the like. It is.

In the present invention, the pole brick has a porosity of 5% by volume or less, in particular 3% by volume or less, and a glassy proportion from the viewpoint of the strength of the brick when used as a structural material in glass production, the quality of the glass produced, and the like. It is preferred that it is at most 15% by volume, in particular at most 10% by volume. When the ratio of glass phase is high, when used as a structural material in glass manufacturing, there exists a possibility that the glassy component in a pole brick may elute with molten glass, and may adversely affect the composition of the glass produced, and the strength of pole brick itself may fall. . Moreover, although the ratio of the silicon oxide component of the pole brick also changes with a composition, it is preferable that it is about 8 mass% or less. It is preferable that the density of the pole brick is 3.5-5.5 g / cm <2>. In addition, AZS bricks have a high glass phase ratio in excess of 15% by volume in most cases, and are not preferably used in the present invention.

Although the above-mentioned electroplated bricks are difficult to carry out anchor joining using the thermal spraying and the metal containing paste which interpose a ceramic intermediate | middle layer, this invention can be applied to such a high density, low glass hard pole electroplating brick.

In general, the thermal expansion brick has a coefficient of thermal expansion of about 6 × 10 ^{−6 to} about 8 × 10 ⁻⁶ (average coefficient of thermal expansion at 20-800 ° C.), a bending strength of about 80 to 120 kg / cm 2, and a compressive strength of It has a high compressive strength exceeding 200 kg / cm 2 and exceeding 2500 kg / cm 2 in high zirconia pole pole bricks. However, it is not broken by the stress received from the metal film, and in order to fix the metal film, a study on the shape of the anchor recess formed on the surface of the pole brick is necessary.

In order to uniformly distribute the tensile stress applied to the pole brick from the metal film, it is necessary to form the recessed portion for anchoring so that the recesses are regularly finely dispersed on the surface of the pole brick. As an arrangement form of the recessed portion for anchor, for example, there is a form in which a plurality of grooves are arranged in parallel, and as an arrangement form in consideration of isotropy, a lattice shape in which a plurality of grooves (linear depressions) intersect, There is a spot shape in which a plurality of columnar or polygonal recesses are uniformly dispersed. In terms of the strength of the convex portions (distance portions between the concave portions), a specular shape by the circular concave portion is preferable. On the other hand, a lattice groove is preferable in the ease of processing, and the lattice shape is easy to be practically employed. The lattice shapes include orthogonal lattice, rhombus lattice, large basket pattern lattice, triangular lattice, and the like. In terms of the strength of the convex portion with respect to stress, a square orthogonal lattice (checkerboard scale) as shown in FIG. desirable.

Next, the shape of the cross section (section perpendicular | vertical to a brick surface) of an anchor recessed part is considered. FIG. 1: shows the embodiment which provided the grid | lattice-shaped groove | channel which consists of several linear groove | channel g of cross-sectional shape as a recessed part 3 for anchors in the pole brick 1, In this form, each groove | channel g The side of) is perpendicular to the brick surface and the groove width w is constant. Unlike this embodiment, when the side surface inclines so that the groove width becomes narrow toward the deep portion of the concave portion, tensile stress due to shrinkage of the metal film acts as a shear stress on the side surface to easily cause peeling. On the contrary, when the side surface is inclined so that the groove width becomes wider toward the deep portion of the concave portion, the stress applied to the side surface is concentrated at the core portion (the root portion of the convex portion) and the convex portion is easily broken. Therefore, in view of the stress action on the side surface, the form in which the cross section as shown in Fig. 1 constitutes the recessed portion 3 for the anchor with a rectangular groove g is preferable, and the stress is the side surface of the groove perpendicular to the brick surface. The stress component perpendicular to the side acts as an anchor effect.

Hereinafter, with reference to FIG. 2, the relationship between the grid | lattice-shaped groove | channel and metal film which are rectangular in cross-sectional shape is demonstrated in detail. 2 shows an example in which the metal coating 5 was formed by spraying a metal on the pole brick 1 of FIG.

In order to effectively obtain the anchor effect, a certain depth is required in the grooves constituting the anchoring recesses 3, but excessively deep grooves reduce the overall strength of the surface portion of the pole brick 1 and are difficult to machine. . Therefore, when a preferable range is calculated | required from these points, the depth of a groove | channel is preferably about 50-350 micrometers, More preferably, it becomes about 150-250 micrometers. This corresponds to 1 / 2-5 / 4 of the thickness of the preferable metal film 5 mentioned above, and when the ratio (d / m) is calculated | required as thickness of a metal film and making depth of a groove d, it is preferable d / m becomes 1 / 2-1, More preferably, it becomes 1 / 2-3 / 4.

On the other hand, the degree of dispersion of the stress generated between the metal film 5 and the pole brick 1 changes depending on the groove pitch (interval gap between the grooves p). It is necessary to make the pitch p small. In view of this, considering the stress durability of the metal film 5 and the strength of the pole brick 1, the groove pitch p is preferably about 2.5 mm or less, and more preferably about 1.5 mm or less. For the same reason, it is preferable that the groove width w is also narrow, and that the groove width w is also narrow in terms of maintaining the strength of the surface portion of the pole brick 1. However, when the groove width w is narrower than the particle size of the metal particles to be sprayed, the grooves cannot be filled by the spray particles, and therefore the groove width w is limited depending on the size of the spray particles. Usually, since the particle diameter of a sprayed particle is about 100 micrometers or more, the groove | channel width w also becomes about 100 micrometers or more, Preferably it is about 150 micrometers or more (depending on a spraying method, it can reduce to about 40 micrometers). In addition, in order to maintain the strength that the convex portion is not broken by resisting the stress, it is necessary to secure the convex portion width x (= difference between the groove intervals, the groove pitch p and the groove width w) according to the stress. Since the tensile stress applied from the metal film 5 is increased with the thickness m of the metal film 5 formed on the pole brick 1, the thicker the metal film is, the more the width required for the convex portion is increased. . From this point, the convex portion width x is preferably about four times or more of the thickness m of the metal film, and in view of reducing the groove pitch p, the preferred convex portion width x is And about 2.5 to 5 times the thickness (m) of the film. That is, x / m ratio is about 4-5. When the required convex part width (x) is determined based on the thickness (m) of the above-mentioned preferred metal film, the convex part width (x) is preferably about 700 µm to 2.2 mm, more preferably about 750 µm to 1.3 mm. do. As a result, preferable groove pitch p is about 800 micrometers-about 2.5 mm, and more preferable groove pitch p becomes about 1-1.5 mm. Therefore, considering the convex portion width x and the groove pitch p, the groove width w is preferably 300 μm or less, more preferably 250 μm or less.

As the stress applied to the side surface of the groove, the deeper the groove (larger side) causes the stress to be dispersed throughout the side surface, and the convex portion is less likely to break. Therefore, the smaller the ratio (p / d) of the groove pitch p to the depth d of the groove, the higher the dispersibility of the stress and the easier the peeling of the coating becomes. Based on the above-mentioned preferred groove pitch p and the depth d of the groove, the p / d value at which the stress is appropriately dispersed is preferably about 3 to 8.

In the above-described embodiment, the both sides of the grooves g constituting the anchoring recesses 3 are defined by one plane, respectively, and the cross section is formed in a rectangular shape. As in d), modifications are also possible in which each side of the groove is defined by a plurality of planes or curved surfaces. In these anchor recesses 3a to 3d, the two planes 11, 13, 21, 23 are formed so that the side surfaces of the grooves ga to gd slightly protrude or dent toward the recesses (Fig. 3 (a)). And (c)) or curved surfaces 15 and 25 (FIG. 3 (b) and (d)), the grooves (ga to gd) are groove widths (for the cores) from the surface of the pole bricks (1a to 1d). narrowed by the groove width w at w '). 3 (a) and 3 (b), the taper degree of the grooves (ga, gb) is large near the brick surface, and the flat surface 13 and the curved surface 15 of the core portion are perpendicular to the brick surface. In Figs. 3 (c) and 3 (d), the taper degree of grooves gb, gd is large at the core portion, and the plane 21 and the curved surface 25 near the brick surface are perpendicular to the brick surface. The form of FIG.3 (a) and FIG.3 (b) is preferable at the point which improves durability of a convex part. However, also in embodiment of FIG. 3, in order to prevent peeling by a shear stress, it is preferable that it is a deformation | transformation of the grade which can be substantially approximated to a rectangle, and therefore, the narrowing ratio of groove | ga g (ga-gd) (at the brick surface) It is preferable that the percentage of reduction of the groove width (w'-w) to the groove width w ') is about 90% or less, and the ratio of the grooves where the narrowing degree exceeds this is 40% of the entire groove constituting the anchor recess. It is preferable that it is less than (ratio computed based on the length of a groove | channel). The recessed part for anchor may be comprised by combining the groove | channel with a rectangular cross section of FIG. 1, and the narrowed groove | channel like FIG. In this case, 60% or more of the whole groove | channel which comprises the recessed part for anchors is preferable if it is the groove | channel g of a rectangular cross section or the groove | channel (ga-gd) whose narrowing rate is 90% or less.

When forming the spot-shaped recessed part as an anchor recessed part, when processing is considered, a cylindrical recessed part is practical, and also in this case, the dimension of a recessed part and the suitable range of arrangement | positioning are determined similarly to the above. That is, the depth of the recess is the depth of the groove described above, the diameter of the recess is the groove width described above, the spacing between the recesses is the spacing between the grooves described above, and the pitch of the recess is the groove pitch described above. Arrange as much as possible.

By forming the concave portion for anchoring as described above on the surface of the pole brick, a pole brick capable of stably fixing the metal sprayed coating is obtained. The groove can be formed mechanically using a grinding machine equipped with a grinding blade composed of a grindstone, a diamond blade, or the like. Or you may implement using a high energy beam, such as a laser, or high pressure water flow. When forming a spot-shaped recess as an anchor recess, grinding tools, such as a pin drill, may be used. If the surface of the pole brick is adjusted to a plane with high precision by cutting off by a grinding machine or the like before forming the anchor recess, it is preferable in that the metal-spray coating can be prevented from being peeled off due to unexpected unevenness.

Since the pole brick has the characteristic which does not exist in other bricks with few glass phases, and it is very strong and it is not easy to give an uneven | corrugated processing to the surface, it does not usually perform uneven | corrugated processing. However, through trial and error of some surface processing techniques, the uneven | corrugated processing method which has an anchor effect and the uneven | corrugated shape which did not lead to convex part destruction are found out and realization is possible. Specifically, the problem of peeling of the projection surface of the coating and the problem of breaking of the projection due to the stress of the coating are solved by trial and error.

Moreover, this invention is applied to the pole brick base material used for glass melting, etc., The base material is a simple shape, such as a rectangular parallelepiped, in many cases, Therefore, the surface which sprays is mostly flat. However, as the application range of the pole brick becomes wider, there is also a small demand for using the brick as a relatively complicated shape by machining the brick into a curved shape or the like depending on the use. In this case, the surface which should coat | cover metal with a thermal spray also inevitably becomes a three-dimensional shape which has a curved surface. Generally, hard and dense pole pole bricks are typical hardworking materials, and in order to process grooves with tightly controlled shapes and dimensions proposed by the present invention in the above-described three-dimensional shape, advanced processing techniques are required. The cost of this cannot be ignored.

When covering to the surface of a three-dimensional shape as mentioned above is requested | required, intermittent hole processing can be selected as a substitute of a groove | channel, and it is largely advantageous in the point of difficulty of processing and cost. It is preferable that the hole from which the effect of this invention is acquired is formed in the crossing position of orthogonal grid (checkerboard scale), or it is preferable to arrange | position at the position of a zigzag so that hole pitch distance may become the same. As for the distance of a hole pitch, about 0.7-2.5 mm is preferable, More preferably, it is about 1-1.6 mm. The hole diameter is preferably about 0.2 to 0.5 mm, more preferably about 0.3 to 0.4 mm. The depth of the hole is preferably about 0.05 to 0.35 mm, more preferably about 0.15 to 0.25 mm.

As above-mentioned, the electroforming brick which formed the recessed part for anchors inject | pours and sprays molten metal particle by the spraying method, and a metal sprayed coating is formed by cooling and solidifying a metal. The thermal spraying method includes a laser spraying method, a wire frame spraying method, a plasma spraying method, an arc spraying method, an oxyhydrogen spraying method, or the like. The metal particles to be injected are preferably fine and can be reduced to about 40 μm depending on the type of thermal spraying method. However, the metal particles to be injected by thermal spraying are generally about 50 to 150 μm. Since the temperature of the thermal sprayed metal particles is generally about 700 to 1500 ° C, when the electroplated brick is heated during the thermal spraying, the temperature difference between the thermal sprayed metal and the electroplated brick is reduced, and the adhesion between the thermal sprayed metal film and the thermal sprayed metal film is improved. Therefore, it is preferable, and after spraying in the state which heated the pole brick, it cools slowly to normal temperature. As for the heating temperature of a pole brick, about 200-500 degreeC is especially preferable about the temperature degree of a thermal spray metal, More preferably, you may be 300-400 degreeC. It is preferable that the temperature-fall rate at the time of slow cooling is as late as possible, Preferably it is 10 degrees C / min or less. Since the metal sprayed coating is a film formed by deposition of particles, it is distinguished by showing a granular deposition structure in cross section unlike a solidified film or the like due to application of molten metal or the like. In this structure, the density ratio is relatively low, and the stress due to expansion and contraction is alleviated as compared with a normal metal film.

As described above, once the electroplated brick is coated with the metal sprayed coating, the metal sprayed coating is firmly fixed to the surface of the brick, and the creep deformation and yielding ability of the metal are prevented unless the temperature change in practical use is not so severe. Peeling is avoided. The obtained metal film forming pole brick is excellent in durability under high temperature, and can be used not only for the fire-resistant and heat-resistant structural material for glass manufacturing facilities, but also for reaction catalyst walls for gases.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely with reference to an Example.

Example

According to the following operations, after the grooved bricks were subjected to groove processing, metal spraying was performed to prepare a sample of metal film-forming pole bricks, and the metal-sprayed coating state was observed during that time. Table 1 shows the form of the sample in Examples 1-3 and the thermal spraying result.

Example 1

(Sample Z1)

High zirconia pole brick (manufactured by Asahi Glass Co., Ltd .: X950, density 5.45 g / cm 2, silicon oxide 4.5%, ZrO ₂ content 95 mass% or more, compressive strength 400 kg / cm 2, bending strength 90 kg / cm 2, tensile strength 66.67 kg / Cm 2, thermal expansion coefficient 0.68, porosity 0.6 volume%, glass phase ratio 7 volume%) were cut into pieces of brick 50 mm long by 50 mm wide by 10 mm high, and one surface of 50 mm by 50 mm of the brick piece was cut into # 100. Grinding was performed using a transverse grinder equipped with a grindstone. A groove width (w): 0.2 mm, groove depth (d): 0.1 mm, groove pitch (p): 1 mm, convex part width (x): 0.8 mm using a processing machine equipped with a diamond blade on this grinding surface. The orthogonal lattice-shaped groove was formed.

The electroplated brick pieces were heated to 300 ° C. in an air atmosphere, and thermal spraying of platinum was started on the surface where the grooves were formed by using a wire-frame spraying method (flying spray particle diameter: about 100 μm, temperature about 100 ° C.), and the platinum coating After thermal spraying was continued until the film thickness became 300 micrometers, the brick piece was cooled slowly to normal temperature. In the thermal spraying, peeling of the thermal sprayed coating was observed when the film thickness was 200 µm. In addition, peeling of a thermal sprayed coating is the case where a part of coating is peeled from an old material, and is described as peeling.

(Sample Z2)

The orthogonal lattice shape of the groove was the same as the sample Z1 except that the groove width (w) was 0.2 mm, the groove depth (d) was 0.2 mm, the groove pitch (p) was 0.4 mm and the convex width (x) was 0.2 mm. The groove was formed in the grinding surface of the pole brick piece, and the thermal spraying of platinum was performed. As a result, peeling of the thermal sprayed coating was observed when the film thickness of the thermal sprayed coating became 100 micrometers.

(Sample Z3)

The orthogonal lattice shape of the groove was the same as the sample Z1 except that the groove width (w) was 0.2 mm, the groove depth (d) was 0.2 mm, the groove pitch (p) was 0.6 mm and the convex width (x) was 0.4 mm. The groove was formed in the grinding surface of the pole brick piece, and the thermal spraying of platinum was performed. As a result, peeling of the thermal sprayed coating was observed when the film thickness of the thermal sprayed coating became 100 micrometers.

(Sample Z4)

The orthogonal lattice shape of the groove was the same as the sample Z1 except that the groove width (w) was 0.2 mm, the groove depth (d) was 0.2 mm, the groove pitch (p) was 1 mm and the convex width (x) was 0.8 mm. The groove was formed in the grinding surface of the pole brick piece, and the thermal spraying of platinum was performed. Peeling of the thermal sprayed coating was not observed during the thermal spraying, and the thermal sprayed coating was in close contact with the pole brick pieces even after cooling. The film thickness of the thermal sprayed coating was 300 µm. Moreover, the durability of a film is also high and it is useful also as a heat resistant structure.

(Sample Z5)

The groove orthogonal lattice shape was the same as the sample Z1 except that the groove width (w) was 0.2 mm, the groove depth (d) was 0.2 mm, the groove pitch (p) was 1.4 mm and the convex width (x) was 1.2 mm. The groove was formed in the grinding surface of the pole brick piece, and the thermal spraying of platinum was performed. Peeling of the thermal sprayed coating was not observed during the thermal spraying, and the thermal sprayed coating was in close contact with the pole brick pieces even after cooling. The film thickness of the thermal sprayed coating was 300 µm. Moreover, the durability of a film is also high and it is useful also as a heat resistant structure.

(Sample Z6)

The orthogonal lattice shape of the groove was the same as the sample Z1 except that the groove width (w) was 0.3 mm, the groove depth (d) was 0.3 mm, the groove pitch (p) was 0.6 mm and the convex width (x) was 0.3 mm. The groove was formed in the grinding surface of the pole brick piece, and the thermal spraying of platinum was performed. As a result, peeling of the thermal sprayed coating was not observed during spraying, but peeling of the coating was observed at the time of slow cooling. The film thickness of the thermal sprayed coating was 300 µm.

(Sample Z7)

The orthogonal lattice shape of the groove was the same as the sample Z1 except that the groove width (w) was 0.3 mm, the groove depth (d) was 0.3 mm, the groove pitch (p) was 1.2 mm and the convex width (x) was 0.9 mm. The groove was formed in the grinding surface of the pole brick piece, and the thermal spraying of platinum was performed. Peeling of the thermal sprayed coating was not observed during the thermal spraying, and the thermal sprayed coating was in close contact with the pole brick pieces even after cooling. The film thickness of the thermal sprayed coating was 300 µm. Moreover, the durability of a film is also high and it is useful also as a heat resistant structure.

Example 2

(Sample A1)

Alumina pole brick (manufactured by Asahi Glass Co., Ltd .: MB-A, density 3.9 g / cm 2, silicon oxide 1%, Al ₂ O ₃ content 95 mass% or more, compressive strength 250 kg / cm 2, bending strength 83 kg / cm 2, tensile strength 41.67 kg / cm 2, thermal expansion coefficient of 0.7, porosity of 2.0% by volume, glass phase ratio of 1% by volume or less) were cut into 50 mm long x 50 mm wide x 10 mm high brick pieces, and the 50 mm x 50 mm one side of the brick piece. Was ground using a transverse grinder equipped with # 100 grindstone. A groove width (w): 0.2 mm, groove depth (d): 0.2 mm, groove pitch (p): 0.4 mm, convex part width (x): 0.2 mm using a processing machine equipped with a diamond blade on this grinding surface. The orthogonal lattice-shaped groove was formed.

The electroplated brick pieces were heated to 300 ° C. in an air atmosphere, and a thermal spraying of platinum was started on the surface where the grooves were formed (flying spray particle diameter: about 100 μm, temperature about 1000 ° C.), and the platinum coating After thermal spraying was continued until the film thickness became 300 micrometers, the brick piece was cooled slowly to normal temperature. In the thermal spraying, peeling of the thermal sprayed coating was observed when the film thickness was 100 µm.

(Sample A2)

The orthogonal lattice shape of the groove was the same as that of Sample A1 except that the groove width (w) was 0.2 mm, the groove depth (d) was 0.2 mm, the groove pitch (p) was 1.4 mm and the convex width (x) was 1.2 mm. The groove was formed in the grinding surface of the pole brick piece, and the thermal spraying of platinum was performed. Peeling of the thermal sprayed coating was not observed during the thermal spraying, and the thermal sprayed coating was in close contact with the pole brick pieces even after cooling. The film thickness of the thermal sprayed coating was 300 µm. The durability of a film is also high, and it is useful also as a heat resistant structure.

(Sample A3)

The orthogonal lattice shape of the groove is the same as that of Sample A1 except that the groove width (w) is 0.2 mm, the groove depth (d) is 0.2 mm, the groove pitch (p) is 5 mm and the convex width (x) is 4.8 mm. The groove was formed in the grinding surface of the pole brick piece, and the thermal spraying of platinum was performed. As a result, peeling of the thermal sprayed coating was not observed in the thermal spraying, but peeling of the coating was observed for each cell at the time of slow cooling. The film thickness of the thermal sprayed coating was 300 µm.

Example 3

(Sample Z8)

Except having changed the metal sprayed from platinum to Pt-10% Rh alloy, it carried out similarly to sample Z4, and sprayed on the electroplated brick piece which provided the groove in the grinding surface. Peeling of the thermal sprayed coating was not observed during the thermal spraying, and the thermal sprayed coating was in close contact with the pole brick pieces even after cooling. The film thickness of the thermal sprayed coating was 300 µm. Moreover, the durability of a film is also high and it is useful also as a heat resistant structure.

(Sample A4)

Except having changed the metal sprayed from platinum to Pt-10% Rh alloy, it carried out similarly to sample A2, and sprayed on the pole brick piece in which the groove was formed in the grinding surface. Peeling of the thermal sprayed coating was not observed during the thermal spraying, and the thermal sprayed coating was in close contact with the pole brick pieces even after cooling. The film thickness of the thermal sprayed coating was 300 µm. Moreover, the durability of the film is high and it is useful also as a heat resistant structure.

Example 4

Sample Z1 except for adopting a spot-shaped recess having a cylindrical recess having a diameter of 0.4 mm and a depth of 0.2 mm at an intersection position of an orthogonal lattice having a pitch of 1.4 mm as an anchor recess. In the same manner as that, an anchoring recess was formed on the grinding surface of the pole brick piece, and platinum was sprayed. Peeling of the thermal sprayed coating was not observed during the thermal spraying, and the thermal sprayed coating was in close contact with the pole brick pieces even after cooling.

BRIEF DESCRIPTION OF THE DRAWINGS It is a top view (a) which shows one Embodiment of the pole brick in this invention, and A-A line arrow sectional drawing of the pole brick of (a).

It is sectional drawing which shows one Embodiment of the metal film formation pole brick of this invention.

3: is sectional drawing (a)-(d) which shows another embodiment of the pole brick in this invention.

* Description of the sign *

1, 1a-1d: Poles 3, 3a-3d: Concave for anchor

5: metal film g, ga-gd: groove

11, 13, 21, 23: plane 15, 25: curved surface

d: depth of groove p: groove pitch

x: convex width w: groove width

Claims (13)

And a metal film formed to cover the surface of the electric pole brick so as to fill the anchor recess, and the metal film contains a platinum group metal, and the electric pole brick includes: A metal film-forming pole brick having a porosity of 5% by volume or less and a glass phase of 15% by mass or less. 2. The metal film-forming pole brick according to claim 1, wherein the metal film has a film thickness of 100 to 400 µm. The metal film-forming pole brick according to claim 1 or 2, wherein at least 60% of the recessed portion of the anchor is rectangular in cross-sectional shape. The metal according to any one of claims 1 to 3, wherein the anchor recess is composed of a plurality of regular grooves in parallel, and the spacing between the grooves of the plurality of grooves is 4 to 5 times the film thickness of the metal film. Encapsulation Formation Pole Brick. The metal film-forming pole brick according to any one of claims 1 to 4, wherein a depth of a groove of the anchor recess is 1/2 to 1 times the film thickness of the metal film. The metal film-forming pole brick according to any one of claims 1 to 5, wherein the metal film is a thermal sprayed coating composed of platinum or a platinum alloy. The metal film-forming pole brick according to any one of claims 1 to 6, which is used as a structural material for glass manufacturing equipment. The metal film-forming pole brick according to any one of claims 1 to 7, wherein a silicon oxide content of the pole brick is 10% by mass or less. A regular anchor recess is formed on the surface of the pole brick having a porosity of 5% by volume or less and a glass phase of 15% by mass or less, and a metal containing platinum group metal is sprayed on the pole brick to fill the anchor recess. A method of manufacturing a metal film-forming pole brick, wherein a metal film is formed to cover the surface of the pole brick. 10. The metal coating according to claim 9, wherein the anchor recess has a plurality of regular grooves in parallel, and the intervals of the plurality of grooves are 4 to 5 times the film thickness of the metal coating, and the cross-sectional shape of the grooves is rectangular. Method of manufacturing formed pole bricks. The method for producing a metal film-forming pole brick according to claim 9 or 10, wherein a depth of the anchor portion is 1/2 to 1 times the film thickness of the metal film. The said metal film is comprised from platinum or a platinum alloy, the film thickness of the said metal film is 100-400 micrometers, and the said pole brick has a silicon oxide content of 10 mass%. The manufacturing method of the following metal film formation pole brick. The method for producing a metal film-forming pole brick according to any one of claims 9 to 12, wherein the pole brick is heated to 300 to 500 ° C when the metal is sprayed.

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