JP6603503B2 - Structure manufacturing method and structure - Google Patents

Description

The present invention relates to a structure manufacturing method and a structure.

Attempts have been made in the past to provide a base material made of metal or the like with a ceramic coat made of various ceramic raw materials according to the application, and to give the base material predetermined performance and function.

For example, in Patent Document 1, in an electrically heated catalyst, an insulating surface between the exhaust pipe and the electric heating catalyst is provided by providing a ceramic coat mainly composed of glass on the inner surface of the exhaust pipe as a base material. The technology to be secured is described.

In Patent Document 2, a ceramic coating mainly composed of glass is provided on an exhaust system component that is a base material to ensure heat insulation, and heat is externally applied during operation of an engine using the exhaust system component. Techniques for suppressing release are described.

JP 2012-154318 A International Publication No. 2014/034395

In Patent Documents 1 and 2, a ceramic coating layer is formed by applying and baking a ceramic raw material on a base material. Thus, when baking a ceramic raw material to a base material, a ceramic raw material shrink | contracts, a part of base material covered with the ceramic raw material may be exposed, or the edge part of a ceramic coat layer may become thin. That is, a so-called “sink” may occur in the ceramic coat layer. This is a phenomenon that occurs because the expansion coefficient of the base material and the expansion coefficient of the ceramic raw material do not match. In particular, when a ceramic material is applied thickly, sink marks are likely to occur.
When such sink marks occur, the ceramic coat layer is not formed on a part of the base material that was planned to be covered with the ceramic coat layer, and a part of the base material is exposed. There are cases where the end portion becomes thin and a sufficient thickness cannot be secured. Due to this, there has been a problem that the insulating property and the heat insulating property are lowered.

The present invention has been made to solve the above problems, and an object of the present invention is to produce a structure in which a ceramic coat layer having a sufficient thickness is formed on a predetermined portion of a metal substrate. And a structure manufactured by the manufacturing method.

That is, the structure manufacturing method of the present invention includes a coating planned region determining step for determining a coating planned region on a part of the surface of a base material made of metal, and a boundary between the planned coating region outside the planned coating region. A first glass material application step for applying the first glass material in a strip shape so as to contact with the first glass material; and the first glass material so as to cover at least a part of the upper region of the first coating material region and the first glass material. A second glass material application step of applying the second glass material so as to continue from at least a part of the upper surface of the material to the coating-scheduled region, and the first glass material and the second glass material on the surface of the substrate. And a ceramic coating layer forming step of forming a ceramic coating layer, wherein the second glass material has a softening point higher than that of the first glass material.

In the first glass material application step of the structure manufacturing method of the present invention, the first glass material is applied in a strip shape outside the planned coating region so as to be in contact with the boundary of the planned coating region.
As will be described later, in the structure manufacturing method of the present invention, it is possible to suppress the occurrence of sink marks in the ceramic coat layer by applying the first glass material. Therefore, it becomes easy to control the position of the end portion of the ceramic coat layer. Therefore, the area to be covered with the ceramic coat layer can be firmly covered with the ceramic coat layer by applying the first glass material in a strip shape outside the planned coat area so as to be in contact with the boundary of the coat planned area. .

In the second glass material application step of the structure manufacturing method of the present invention, the covering region and at least a part of the upper surface of the first glass material are covered, and the upper surface of the first glass material is covered. The second glass material is applied so as to continue from at least a part to the planned coating region. The second glass material has a higher softening point than the first glass material.
When the second glass material is applied after the first glass material is applied as described above, it is possible to prevent sink marks from occurring in the ceramic coat layer for the following reason.
First, the principle of “sinking” will be described.
When the glass material is applied to the base material and then heated and baked on the base material, the glass material is softened. When the glass material is softened, the glass material tends to aggregate due to surface tension. This aggregating force is one of the causes of sink marks.
Next, the principle that can prevent the occurrence of sink marks in the method for producing a structure according to the present invention will be described.
In the structure manufacturing method of the present invention, since the softening point of the second glass material is higher than that of the first glass material, the first glass material and the second glass material are applied to the surface of the substrate in the ceramic coat layer forming step. When baking, the first glass material is first softened. Even if the first glass material is softened, the first glass material is sandwiched between the base material and the second glass material, so that aggregation of the first glass material is suppressed. That is, since the force with which the second glass material and the base material sandwich the first glass material is stronger than the force with which the first glass material tends to aggregate, the first glass material is less likely to aggregate.
Thereafter, as the heating is performed, the first glass material is further softened, the adhesion between the first glass material and the surface of the base material is improved, and the first glass material is baked onto the surface of the base material.
Thereafter, when the heating proceeds, the second glass material starts to soften. When the second glass material starts to soften, it tends to agglomerate due to surface tension. At this time, the first glass material has already been softened, and the adhesion between the second glass material and the first glass material becomes high. Yes. Therefore, the first glass material functions as a paste material, and aggregation of the second glass material is suppressed.
That is, since the force with which the first glass material and the second glass material are in close contact with each other is stronger than the force with which the second glass material attempts to aggregate, the second glass material is less likely to aggregate.
As a result, it is possible to suppress the occurrence of sink marks in the ceramic coat layer.

In the structure manufacturing method of the present invention, in the second glass material application step, the second glass material may be applied so as to cover only a part of the upper surface of the first glass material. Further, in the structure manufacturing method of the present invention, in the second glass material application step, the second glass material is covered so that the entire upper surface of the first glass material is covered and the end surface of the first glass material is exposed. Material may be applied. Furthermore, in the manufacturing method of the structure of the present invention, in the second glass material application step, the second glass material so as to cover all of the upper surface of the first glass material and the end surface of the first glass material. May be applied.
That is, in the structure manufacturing method of the present invention, if the second glass material is applied so that the planned coating region and at least a part of the upper surface of the first glass material are continuous, the other part of the first glass material. The second glass material may be applied in any manner.

In the structure manufacturing method of the present invention, the softening point of the first glass material is desirably 300 to 700 ° C.
When the first glass material has a softening point of 300 to 700 ° C., when the first glass material and the second glass material are baked on the substrate in order to form the ceramic coat layer in the production of the structure of the present invention, The first glass material and the second glass material are heated and softened and mixed. Therefore, the interface between the first glass material and the second glass material is unlikely to occur, and the function of the first glass material for bringing the second glass material and the base material into close contact with each other is suitably exhibited.
When the softening point of the first glass material is less than 300 ° C., the difference from the softening point of the second glass material becomes too large, the foaming of the first glass material becomes remarkable, the adhesion with the base material is lowered, and peeling occurs. There are concerns. The foaming of the first glass material includes the foaming of pores formed by the pore former and the foaming of pores formed naturally.
When the softening point of the first glass material exceeds 700 ° C., it is technically difficult to produce a second glass material having a higher softening point. Furthermore, in order to soften the 2nd glass material, it is necessary to make 2nd glass material high temperature, and it becomes easy to damage a base material with the heat. Furthermore, the crystallization of the first glass material is promoted and the strength of the ceramic coat layer is lowered.

In the manufacturing method of the structure of the present invention, the softening point of the second glass material is preferably 550 to 800 ° C.
When the softening point of the second glass material is 550 to 800 ° C., the second glass material is softened and melted by heating at a temperature exceeding the softening point, so that the ceramic coat layer can be easily formed.

In the structure manufacturing method of the present invention, the first glass material preferably contains water and / or an organic binder.
If the first glass material contains water and / or an organic binder, the first glass material will have a viscosity. When these have viscosity, it will become easy to apply | coat to the surface of a base material, and will also become easy to control the application quantity.
On the other hand, when the 1st glass material containing water and / or an organic binder is baked on a base material in a ceramic coat layer formation process, water and / or an organic binder will disappear by evaporation and decomposition. For this reason, the degree of firing shrinkage of the first glass material is increased, and sink marks are likely to occur in the ceramic coat layer.
However, in the structure manufacturing method of the present invention, it is possible to prevent sink marks from occurring in the ceramic coat layer based on the above principle. Therefore, even if the degree of firing shrinkage of the first glass material is increased, the coating area can be reliably covered with the ceramic coat layer.

In the structure manufacturing method of the present invention, the first glass material preferably contains an organic solvent.
When the first glass material contains an organic solvent, the surface tension tends to decrease. As a result, when the first glass material is applied to the surface of the base material, the first glass material is easily adapted to the surface of the base material and is easily applied. On the other hand, when the 1st glass material containing an organic solvent is baked on a base material in a ceramic coat layer formation process, an organic solvent will be evaporated and decomposed and will disappear. For this reason, the degree of firing shrinkage of the first glass material is increased, and sink marks are likely to occur in the ceramic coat layer.
However, in the structure manufacturing method of the present invention, it is possible to prevent sink marks from occurring in the ceramic coat layer based on the above principle. Therefore, even if the degree of firing shrinkage of the first glass material is increased, the coating area can be reliably covered with the ceramic coat layer.

In the structure manufacturing method of the present invention, the second glass material preferably contains water and / or an organic binder.
If the second glass material contains water and / or an organic binder, the second glass material will have a viscosity. When these have viscosity, it will become easy to apply | coat to the surface of a base material, and will also become easy to control the application quantity.
On the other hand, when the second glass material containing water and / or an organic binder is baked on the substrate in the ceramic coat layer forming step, the water and / or the organic binder disappears by evaporation or decomposition. For this reason, the degree of firing shrinkage of the second glass material increases, and sink marks are likely to occur in the ceramic coat layer.
However, in the structure manufacturing method of the present invention, it is possible to prevent sink marks from occurring in the ceramic coat layer based on the above principle. Therefore, even if the degree of firing shrinkage of the second glass material is increased, the planned coating region can be reliably covered with the ceramic coat layer.

In the structure manufacturing method of the present invention, the second glass material preferably contains an organic solvent.
When the second glass material contains an organic solvent, the surface tension tends to decrease. As a result, when the second glass material is applied to the surface of the base material, the second glass material is easily adapted to the surface of the base material and is easily applied. Furthermore, when apply | coating 2nd glass material to 1st glass material, 2nd glass material becomes easy to become familiar with 1st glass material, and becomes easy to apply | coat. On the other hand, when the second glass material containing the organic solvent is baked on the substrate in the ceramic coat layer forming step, the organic solvent is evaporated and decomposed and disappears. For this reason, the degree of firing shrinkage of the second glass material increases, and sink marks are likely to occur in the ceramic coat layer.
However, in the structure manufacturing method of the present invention, it is possible to prevent sink marks from occurring in the ceramic coat layer based on the above principle. Therefore, even if the degree of firing shrinkage of the second glass material is increased, the planned coating region can be reliably covered with the ceramic coat layer.

In the structure manufacturing method of the present invention, the width of the first glass material applied in the first glass material application step is preferably 2 to 60 mm.
When the width of the first glass material is less than 2 mm, the contact area between the first glass material and the second glass material becomes small. Therefore, the range in which the first glass material works as a paste is narrowed. As a result, it is difficult to prevent the occurrence of sink marks.
When the width of the first glass material exceeds 60 mm, the first glass material is applied to a range where the second ceramic material contracts or more when the ceramic coat layer is formed on the substrate. Therefore, it is not economical to apply the first glass material in a range exceeding the above range.

The structure of the present invention is a structure comprising a base material and a ceramic coat layer formed on the surface of the base material. The ceramic coat layer includes a first glass material and the first glass material. Is made of a second glass material having a high softening point, the area of the surface of the base material where the ceramic coat layer is formed is smaller than the entire area of the surface of the base material, The first glass material is formed on the peripheral edge of the ceramic coat layer so as to be in a strip shape and in direct contact with the surface of the base material, and is inside the portion where the first glass material is formed. The second glass material covers at least a part of the surface of the base material and the upper surface of the first glass material, and covers the surface of the base material inside the portion where the first glass material is formed. With the second glass material Characterized in that it continuously with the second glass material covering at least a portion of the top surface of the first glass material.

In the structure of the present invention, the area of the surface of the substrate where the ceramic coat layer is formed is smaller than the entire area of the surface of the substrate.
That is, the surface of the substrate has a portion where the ceramic coat layer is formed and a portion where it is not formed.

Moreover, in the structure of this invention, the 1st glass material is formed in the peripheral part of a ceramic coat layer so that it may contact | connect the strip | belt shape and the surface of the said base material directly. And the 2nd glass material has covered the surface of the base material inside the part in which the 1st glass material is formed, and at least one part of the upper surface of the 1st glass material. Further, the second glass material has a higher softening point than the first glass material.
When manufacturing the structure of the present invention, a coating area to be covered with the ceramic coat layer is determined on the surface of the substrate, and the first glass material is in contact with the boundary of the coating area on the outside of the coating area. Is applied in a strip shape. Thereafter, the second glass material is covered so as to cover at least a part of the upper surface of the coating target region and the first glass material and to continue from at least a part of the upper surface of the first glass material to the coating target region. Apply. Thereafter, the first glass material and the second glass material are baked onto the surface of the substrate.
At this time, since the second glass material has a higher softening point than the first glass material, when the first glass material and the second glass material are baked on the surface of the substrate, the first glass material is first softened. Even if the first glass material is softened, the first glass material is sandwiched between the base material and the second glass material, so that aggregation of the first glass material is suppressed.
Thereafter, as the heating is performed, the first glass material is further softened, the adhesion between the first glass material and the surface of the base material is improved, and the first glass material is baked onto the surface of the base material.
Thereafter, when the heating proceeds, the second glass material starts to soften. When the second glass material starts to soften, it tends to agglomerate due to surface tension. At this time, the first glass material has already been softened, and the adhesion between the second glass material and the first glass material becomes high. Yes. Therefore, the first glass material functions as a paste material, and aggregation of the second glass material is suppressed.
That is, since the force with which the first glass material and the second glass material are in close contact with each other is stronger than the force with which the second glass material attempts to aggregate, the second glass material is less likely to aggregate.
As a result, it is possible to suppress the occurrence of sink marks in the ceramic coat layer.

In the structure of the present invention, only a part of the upper surface of the first glass material may be covered with the second glass material. Moreover, in the structure of this invention, all the upper surfaces of the said 1st glass material may be covered with the said 2nd glass material, and the end surface of the said 1st glass material may be exposed. Moreover, in the structure of this invention, all the upper surfaces of the said 1st glass material and the end surface of the said 1st glass material may be covered with the said 2nd glass material.
That is, in the structure of the present invention, the second glass material covers at least a part of the surface of the base material inside the portion where the first glass material is formed and the upper surface of the first glass material, If the second glass material covering the surface of the base material inside the portion where the glass material is formed and the second glass material covering at least a part of the upper surface of the first glass material are continuous, the first glass material The other portions may be covered with the second glass material in any way.

In the structure of the present invention, the softening point of the first glass material is desirably 300 to 700 ° C.
When the structure of the present invention is produced when the softening point of the first glass material is 300 to 700 ° C., the first glass material and the second glass material are baked on the base material to form the ceramic coat layer. The first glass material and the second glass material are heated to soften and mix. Therefore, the interface between the first glass material and the second glass material is unlikely to occur, and the function of the first glass material for bringing the second glass material and the base material into close contact with each other is suitably exhibited.
If the softening point of the first glass material is less than 300 ° C., the difference from the softening point of the second glass material becomes too large. Therefore, when the structure of the present invention is manufactured, the foaming of the first glass material is remarkable. There is a concern that the adhesion with the base material will be reduced and peel off.
When the softening point of the first glass material exceeds 700 ° C., it is technically difficult to produce a second glass material having a higher softening point. Furthermore, when manufacturing the structure of this invention, in order to soften a 2nd glass material, it is necessary to make 2nd glass material high temperature, and it becomes easy to damage a base material with the heat.

In the structure of the present invention, the softening point of the second glass material is preferably 550 to 800 ° C.
When the softening point of the second glass material is 550 to 800 ° C., the second glass material is softened and melted by heating at a temperature exceeding the softening point, so that the ceramic coat layer can be easily formed.

In the structure of the present invention, the peripheral edge portion of the ceramic coat layer is in a range from the end of the ceramic coat layer toward the inside by a distance of 40 times the average thickness of the ceramic coat layer.

In the structure of the present invention, the average thickness of the ceramic coat layer is desirably 50 to 1500 μm.
When the average thickness of the ceramic coat layer is less than 50 μm, it is difficult to obtain the effect that the substrate is covered with the ceramic coat layer.
If the average thickness of the ceramic coat layer exceeds 1500 μm, the thermal stress generated by the difference in thermal expansion between the ceramic coat layer and the substrate becomes large, and therefore the ceramic coat layer is easily damaged.

In the structure of the present invention, it is desirable that the substrate is made of at least one selected from stainless steel, steel, iron, copper, aluminum, inconel, hastelloy, and invar.
Since stainless steel, steel, iron, copper, aluminum, inconel, hastelloy, and invar are easy to process, the base material can be easily processed according to the application.

The structure of the present invention may be used as an exhaust pipe.

FIGS. 1A to 1C are perspective views schematically showing an example of sink marks produced when a ceramic coat layer is formed on the surface of a base material made of metal by a general method. FIG. 2 is a perspective view schematically showing an example of a covering-scheduled region determining step in the structure manufacturing method of the present invention. Drawing 3 is a mimetic diagram showing typically an example of the 1st glass material application process in the manufacturing method of the structure of the present invention. FIG. 4 is a schematic view schematically showing an example of a second glass material application step in the method for manufacturing a structure of the present invention. FIG. 5 is a schematic view schematically showing an example of a ceramic coat layer forming step in the structure manufacturing method of the present invention. FIGS. 6A to 6D are schematic views schematically showing an example of a ceramic coat layer forming step over time in the structure manufacturing method of the present invention. FIG. 7 is a plan view schematically showing another example of the first glass material application step in the method for manufacturing a structure of the present invention. 8A to 8C are cross-sectional views schematically showing an example of the application range of the second glass material in the second glass material application step in the structure manufacturing method of the present invention. FIG. 9 is a perspective view schematically showing an example of the structure of the present invention. FIG. 10 is a perspective view schematically showing an example when the structure of the present invention is used as an exhaust pipe. FIG. 11 is a perspective view schematically showing an example when the structure of the present invention is used as an exhaust pipe. FIG. 12 is a perspective view schematically showing an example when the structure of the present invention is used as an exhaust pipe. Fig.13 (a) is a perspective view which shows typically an example at the time of using the structure of this invention as a casing. FIG.13 (b) is the sectional view on the AA line of Fig.13 (a). Fig.14 (a) is a perspective view which shows typically an example at the time of using the structure of this invention as a casing. FIG. 14B is a cross-sectional view taken along the line BB in FIG. Fig.15 (a) is a perspective view which shows typically an example at the time of using the structure of this invention as a casing. FIG.15 (b) is CC sectional view taken on the line of Fig.15 (a). FIG. 16 is a top view photograph of the structure according to Example 1. FIG. 17 is a top view photograph of the structure according to Example 2. 18 is a top view photograph of the structure according to Example 3. FIG. FIG. 19 is a top view photograph of the structure according to Comparative Example 1.

(Detailed description of the invention)
Details will be described below.

Before explaining the method for producing a structure according to the present invention, sink marks generated when a ceramic coat layer is formed on the surface of a base material made of metal by a general method will be explained.

FIGS. 1A to 1C are perspective views schematically showing an example of sink marks produced when a ceramic coat layer is formed on the surface of a base material made of metal by a general method.

In general, when a ceramic coat layer is formed on the surface of a substrate made of metal, first, as shown in FIG. 1A, the surface 511 of the substrate 510 is covered with the ceramic coat layer. A planned covering region 520 (a range indicated by hatching in FIG. 1A) is determined.

And as shown in FIG.1 (b), the ceramic raw material 530 is apply | coated to the coating plan area | region 520. FIG. The ceramic raw material 530 applied to the substrate 510 is dried, heated, and baked onto the surface 511 of the substrate 510 to form a ceramic coat layer 550 (see FIG. 1C).
During the drying and heating, the ceramic raw material 530 is melted. However, when the ceramic raw material 530 is melted, the ceramic raw material 530 at the end portion moves to gather in the center due to surface tension. In addition, since the volatile components in the ceramic raw material 530 are also volatilized during drying and heating, the ceramic raw material 530 contracts.

As a result, as shown in FIG. 1C, sink marks are generated in the ceramic coat layer 550, and the end portion of the planned coating region 520 is not covered with the ceramic coat layer 550, or is exposed. May become thinner.
That is, when the ceramic raw material 530 is melted and baked and fired and contracted, it causes sinking in the ceramic coat layer 550.
In addition, it is conceivable that the ceramic raw material 530 is applied in advance beyond the range of the planned coating region 520 in anticipation of the occurrence of sink marks in the ceramic coat layer 550, but the degree of sinking is determined when the ceramic raw material 530 is prepared. Therefore, it is difficult to accurately cover the surface 511 of the substrate 510 with the ceramic coat layer 550 without waste.

On the other hand, in the structure manufacturing method of the present invention, it is possible to suppress the occurrence of sink marks in the ceramic coat layer. The principle will be described.

The manufacturing method of the structure of the present invention includes a coating planned area determining step for determining a coating planned area on a part of the surface of a base material made of metal, and a boundary of the planned coating area outside the planned coating area. A first glass material application step for applying the first glass material in a strip shape, a coating-scheduled region, and at least part of the upper surface of the first glass material so as to cover at least a part of the upper surface of the first glass material; A second glass material application step for applying the second glass material so as to continue from a part to the coating area, and a ceramic for baking the first glass material and the second glass material on the surface of the substrate to form a ceramic coating layer Coating layer forming step.

In the covering area determination step in the structure manufacturing method of the present invention, first, a base material made of metal is prepared, and a covering area to be covered with a ceramic coat layer is determined on a part of the surface of the base material. To do. In addition, the area of the area to be coated is smaller than the entire area of the surface of the base material.

In the present specification, the “base material made of metal” is not limited to a base material made only of metal, but also includes a base material containing an element other than a metal for improving strength and heat resistance.

In the first glass material application step in the structure manufacturing method of the present invention, the first glass material is applied in a strip shape outside the planned coating region so as to be in contact with the boundary of the planned coating region.

In the second glass material application step in the structure manufacturing method of the present invention, at least a part of the upper surface of the first glass material and a region to be covered and at least a part of the upper surface of the first glass material are covered. 2nd glass material is apply | coated so that it may continue to a coating plan area | region.

In the first glass material application step and the second glass material application step in the structure manufacturing method of the present invention, the second glass material has a higher softening point than the first glass material.
By doing in this way, it can suppress that a sink mark arises in a ceramic coat layer in the ceramic coat layer formation process mentioned below.

In the ceramic coat layer forming step in the structure manufacturing method of the present invention, the first glass material and the second glass material are baked on the surface of the substrate to form a ceramic coat layer.
When baking the first glass material and the second glass material on the surface of the base material, heat is applied to the first glass material and the second glass material.
In the structure manufacturing method of the present invention, since the softening point of the second glass material is higher than that of the first glass material, the first glass material and the second glass material are applied to the surface of the substrate in the ceramic coat layer forming step. When baking, the first glass material is first softened.
Even if the first glass material is softened, since the first glass material is sandwiched and pressed between the base material and the second glass material, aggregation of the first glass material is suppressed. That is, the second glass material and the base material have a stronger force to press the first glass material than the force that the first glass material tends to agglomerate, so that the first glass material is less likely to agglomerate.
Thereafter, as the heating is performed, the first glass material is further softened, the adhesion between the first glass material and the surface of the base material is improved, and the first glass material is baked onto the surface of the base material.
Thereafter, when the heating proceeds, the second glass material starts to soften. When the second glass material starts to soften, it tends to agglomerate due to surface tension. At this time, the first glass material has already been softened, and the adhesion between the second glass material and the first glass material becomes high. Yes. Therefore, the first glass material functions as a paste material, and aggregation of the second glass material is suppressed.
That is, since the force with which the first glass material and the second glass material are in close contact with each other is stronger than the force with which the second glass material attempts to aggregate, the second glass material is less likely to aggregate.
In the structure manufacturing method of the present invention, it is possible to suppress the occurrence of sink marks in the ceramic coat layer based on such a principle.

An example of the series of steps will be described below with reference to the drawings.

FIG. 2 is a perspective view schematically showing an example of a covering-scheduled region determining step in the structure manufacturing method of the present invention.
First, in the covering plan area | region determination process in the manufacturing method of the structure of this invention, as shown in FIG. 2, first, the base material 10 which consists of metals is prepared, and it is a covering plan on a part of surface 11 of the base material 10. A region 20 (indicated by hatching in FIG. 2) is determined. In FIG. 2, reference numeral 20 a indicates the boundary of the planned covering region 20. Note that the area of the planned covering region 20 is smaller than the entire area of the surface 11 of the substrate 10.

Drawing 3 is a mimetic diagram showing typically an example of the 1st glass material application process in the manufacturing method of the structure of the present invention.
In the first glass material application step after the above-described covering area determination step, as shown in FIG. 3, the first glass material 30 is strip-shaped so as to be in contact with the boundary 20 a of the covering area on the outside of the covering area 20. Apply to.

FIG. 4 is a schematic view schematically showing an example of a second glass material application step in the method for manufacturing a structure of the present invention.
After the first glass material application step, in the second glass material application step, as shown in FIG. 4, the first region of the coating and the first glass material so as to cover at least a part of the upper surface and the first glass material application step are covered. The second glass material 40 is applied so as to continue from at least a part of the upper surface of the glass material 30 to the coating target region 20.
In the structure manufacturing method of the present invention, the second glass material 40 has a higher softening point than the first glass material 30.

FIG. 5 is a schematic view schematically showing an example of a ceramic coat layer forming step in the structure manufacturing method of the present invention.
After the second glass material application step, in the ceramic coat layer forming step, the first glass material 30 and the second glass material 40 are baked on the surface 11 of the substrate 10 to form the ceramic coat layer 50, as shown in FIG. To do.
By forming the ceramic coat layer in this way, it is possible to suppress the occurrence of sink marks in the ceramic coat layer.

The ceramic coat layer forming step in the structure production method of the present invention will be described in more detail.
FIGS. 6A to 6D are schematic views schematically showing an example of a ceramic coat layer forming step over time in the structure manufacturing method of the present invention.
As shown in FIG. 6A, after the first glass material 30 and the second glass material 40 are applied to the surface 11 of the base material 10, the first glass material 30 and the second glass material 40 are baked to heat them. Is added.
Since the second glass material 40 has a higher softening point than the first glass material 30, when the first glass material 30 and the second glass material 40 are baked on the surface 11 of the base material 10 in the ceramic coat layer forming step. First, as shown in FIG. 6B, the first glass material 30 is softened.
Even if the first glass material 30 is softened, since the first glass material 30 is sandwiched and pressed between the base material 10 and the second glass material 40, aggregation of the first glass material 30 is suppressed. . That is, the second glass material 40 and the base material 10 have a stronger force to press the first glass material 30 than the force that the first glass material 30 tends to agglomerate.
Then, as shown in FIG.6 (c), the 1st glass material 30 further softens as it heats, the adhesiveness of the 1st glass material 30 and the surface 11 of the base material 10 improves, and the 1st glass The material 30 will be baked onto the surface 11 of the substrate 10.
Thereafter, when the heating proceeds, the second glass material 40 starts to soften as shown in FIG. When the second glass material 40 starts to soften, it tends to aggregate due to surface tension. At this time, the first glass material 30 is already softened, and the adhesion between the second glass material 40 and the first glass material 30 is increased. Is high. Therefore, the 1st glass material 30 works as a paste material, and aggregation of the 2nd glass material 40 is suppressed.
That is, since the force with which the first glass material 30 and the second glass material 40 are in close contact with each other is stronger than the force with which the second glass material 40 is to aggregate, the second glass material 40 is less likely to aggregate.
In the structure manufacturing method of the present invention, it is possible to suppress the occurrence of sink marks in the ceramic coat layer based on such a principle.

Hereinafter, desirable aspects and the like of each step in the method for producing a structure according to the present invention will be described in more detail.

<Scheduled area determination process>
In the covering area determination step in the structure manufacturing method of the present invention, first, a base material made of metal is prepared.
Although it does not specifically limit as a base material, It is desirable to consist of at least 1 type selected from stainless steel, steel, iron, copper, aluminum, Inconel, Hastelloy, and Invar. Since stainless steel, steel, iron, copper, aluminum, inconel, hastelloy, and invar are easy to process, the base material can be easily processed according to the application.

In the method for producing a structure of the present invention, the shape of the substrate is not particularly limited, and may be a planar substrate or a curved substrate.
Further, it may be a base material having a three-dimensional shape such as a prismatic shape such as a triangular prism, a quadrangular prism, a hexagonal prism, an octagonal prism, a cylindrical shape, or a spherical shape.

Next, an area to be covered that is to be covered with the ceramic coat layer is determined.

In the covering scheduled region determining step in the structure manufacturing method of the present invention, the boundary of the covering planned region may be linear or curved.

In the covering scheduled region determining step in the structure manufacturing method of the present invention, a roughened surface may be formed in the covering planned region.
As described above, in the ceramic coat layer forming step, the first glass material and the second glass material tend to soften and aggregate. When the roughened surface is formed in the coating planned region, the adhesion between the surface of the base material and the ceramic coat layer can be improved in the structure manufactured through the subsequent steps.
The surface roughness of the roughened surface to form a coating region where is not particularly limited, Ra = 0.05 to 4.0 _m, it is desirable that Rz JIS = 1.5~20μm.

In this specification, “Ra” means arithmetic average roughness determined in accordance with JIS B 0601 (2001).
Further, in this specification, “Rz _JIS ” means ten-point average roughness determined in accordance with JIS B 0601 (2001).
These can be measured by using Handy Surf E-35B manufactured by Tokyo Seimitsu Co., Ltd., with a measurement distance of 10 mm.

<First glass material application process>
In the first glass material application step in the structure manufacturing method of the present invention, the first glass material is applied in a strip shape so as to be in contact with the boundary of the planned coating region outside the planned coating region.

In the first glass material coating step in the structure manufacturing method of the present invention, the coating method is not particularly limited, and brushing, sputtering, spraying, powder coating, electrostatic coating, pressure bonding, dipping, thermal transfer, spin coating, lining Etc. can be used.

In the first glass material application step in the structure manufacturing method of the present invention, the first glass material may be formed continuously or may be applied intermittently.

More specifically, the continuous application of the first glass material means the application of the first glass material as shown in FIG. 3, and the intermittent application of the first glass material means the following FIG. The first glass material is applied as shown in FIG.

FIG. 7 is a plan view schematically showing another example of the first glass material application step in the method for manufacturing a structure of the present invention.
In this step, the first glass material may be intermittently formed on the surface 11 of the substrate 10 as shown in FIG.
In the present specification, “application of the first glass material in a strip shape” includes continuous application as shown in FIG. 3 and intermittent application as shown in FIG. 7.

In the manufacturing method of the structure of the present invention, it is desirable to apply the first glass material continuously.
When the first glass material is continuously applied, the first glass material and the second glass material are always in contact with each other in the ceramic coat layer forming step described later. Therefore, it becomes easy to prevent the occurrence of sink marks.

In the method for producing a structure according to the present invention, the width of the first glass material is not particularly limited, but it is desirable that the first glass material is applied so as to be 2 to 60 mm.
When the width of the first glass material is less than 2 mm, the contact area between the first glass material and the second glass material becomes small. Therefore, the range in which the first glass material works as a paste is narrowed. As a result, it is difficult to prevent the occurrence of sink marks.
When the width of the first glass material exceeds 60 mm, the first glass material is applied in a range that the second ceramic material contracts or more when the ceramic coat layer is formed on the substrate. Therefore, it is not economical to apply the first glass material in a range exceeding the above range.

In the structure manufacturing method of the present invention, the softening point of the first glass material is not particularly limited, but is preferably 300 to 700 ° C, and more preferably 400 to 690 ° C.
When the first glass material has a softening point of 300 to 700 ° C., when the first glass material and the second glass material are baked on the substrate in order to form the ceramic coat layer in the production of the structure of the present invention, The first glass material and the second glass material are heated and softened and mixed. Therefore, the interface between the first glass material and the second glass material is unlikely to occur, and the function of the first glass material for bringing the second glass material and the base material into close contact with each other is suitably exhibited.
If the softening point of the first glass material is less than 300 ° C., the difference from the softening point of the second glass material becomes too large, and foaming of the first glass material becomes remarkable when forming the ceramic coat layer. There is concern that the adhesive strength with the material is reduced and the material peels off. The foaming of the first glass material includes the foaming of pores formed by the pore former and the foaming of pores formed naturally.
When the softening point of the first glass material exceeds 700 ° C., it is technically difficult to produce a second glass material having a higher softening point. Furthermore, in order to soften the 2nd glass material, it is necessary to heat considerably, and it becomes easy to damage a base material with the heat.

The softening point of the first glass material can be measured by the following method.
First, put the solid component of the first glass material into a differential thermal balance (manufactured by Rigaku, “TG-DTA” model number TG8120) so as to be an appropriate amount, and raise the temperature to 950 ° C. at a setting of 10 ° C./min in the atmosphere. A DTA curve is obtained at a sampling period of 1 second.
The fourth inflection point of the obtained DTA curve is taken as the softening point.

In the structure manufacturing method of the present invention, the constituent material of the first glass material is not particularly limited, and silica glass, boric acid glass, phosphoric acid glass and the like can be used. Among these, silica glass is desirable.

In the method for manufacturing a structure of the present invention, the first glass material preferably contains water and / or an organic binder. If the first glass material contains water and / or an organic binder, the first glass material will have a viscosity. The first glass material having viscosity is easily applied to the surface of the substrate, and the amount of application is easily controlled.
The organic binder is not particularly limited, and examples thereof include polyvinyl alcohol, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and the like.
These may be used alone or in combination of two or more.

Moreover, it is desirable that the first glass material contains an organic solvent. When the first glass material contains an organic solvent, the surface tension tends to decrease. As a result, when the first glass material is applied to the surface of the base material, the second glass material is easily adapted to the surface of the base material and is easily applied.
Although it does not specifically limit as an organic solvent, Methanol, ethanol, etc. are mention | raise | lifted.
These may be used alone or in combination of two or more.

The first glass material may contain water and an organic solvent, may contain an organic binder and an organic solvent, or may contain water, an organic binder and an organic solvent.
The total weight of water, the organic binder, and the organic solvent with respect to the weight of the first glass material is preferably 5 to 80%.

<Second glass material application process>
In the second glass material application step in the structure manufacturing method of the present invention, the second glass material is applied so as to cover at least a part of the area to be covered and the upper surface of the first glass material.

In the second glass material coating step in the structure manufacturing method of the present invention, the coating method is not particularly limited, and brushing, sputtering, spraying, powder coating, electrostatic coating, pressure bonding, dipping, thermal transfer, spin coating, lining Etc. can be used.

In the structure manufacturing method of the present invention, the range in which the second glass material is applied will be described.
The 1st glass material apply | coated by the 1st glass material application | coating process has an upper surface and an end surface.
In the present specification, the “end surface of the first glass material” means an end surface of the first glass material located in a direction toward the outside of the coating target region.

In the second glass material application step in the structure manufacturing method of the present invention, the second glass material may be applied so as to cover only a part of the upper surface of the first glass material.
In the second glass material application step, the second glass material may be applied so as to cover the entire upper surface of the first glass material and expose the end face of the first glass material.
In the second glass material application step, the second glass material may be applied so as to cover the entire upper surface of the first glass material and the end surface of the first glass material.
That is, as long as at least a part of the upper surface of the coating region and the first glass material is applied, the second glass material is applied to other parts of the first glass material. May be.

The range in which the second glass material is applied will be described in detail with reference to the drawings.
8A to 8C are cross-sectional views schematically showing an example of the application range of the second glass material in the second glass material application step in the structure manufacturing method of the present invention.
8A to 8C, the first glass material 30 has an upper surface 30a and an end surface 30b.

As shown to Fig.8 (a), you may apply | coat the 2nd glass material 40 so that only a part of upper surface 30a of the 1st glass material 30 may be covered in a 2nd glass material application | coating process.
As shown in FIG. 8A, in the second glass material application step, the second glass material 40 is covered so as to cover the entire upper surface 30a of the first glass material 30 and expose the end face 30b of the first glass material 30. May be applied.
As shown in FIG. 8A, in the second glass material application step, the second glass material 40 is applied so as to cover the entire upper surface 30a of the first glass material 30 and the end face 30b of the first glass material. May be.

In the method for producing a structure of the present invention, the softening point of the second glass material is not particularly limited as long as it is higher than the softening point of the first glass material, but is preferably 550 to 800 ° C., preferably 650 to 790. Is more desirable.
When the softening point of the second glass material is 550 to 800 ° C., the second glass material is softened and melted by heating at a temperature exceeding the softening point, so that the ceramic coat layer can be easily formed.

The softening point of the second glass material can be measured by the following method.
First, put the solid component of the second glass material in a differential thermal balance (manufactured by Rigaku, “TG-DTA” model number TG8120) so as to be an appropriate amount, and raise the temperature to 950 ° C. at a setting of 10 ° C./min in the air atmosphere. A DTA curve is obtained at a sampling period of 1 second.
The fourth inflection point of the obtained DTA curve is taken as the softening point.

In the structure manufacturing method of the present invention, the constituent material of the second glass material is not particularly limited, and is desirably selected in accordance with the performance to be imparted to the ceramic coat layer formed in the ceramic coat layer forming step.

For example, when heat insulating performance is imparted to the ceramic coat layer, the constituent material of the second glass material is at least one of barium glass, boron glass, strontium glass, alumina silicate glass, soda zinc glass, and soda barium glass. It is desirable to include. In these, it is desirable to contain barium glass.
When these materials are used, it is possible to form a ceramic coat layer having low thermal conductivity and heat resistance and durability.

In the method for producing a structure of the present invention, a pore-forming material may be added to the second glass material when heat insulating performance is imparted to the ceramic coat layer.
When the second glass material includes a pore former, the pore former is decomposed and pores are formed in the ceramic coat layer in the ceramic coat layer forming step.
When pores are present in the ceramic coat layer, heat is not easily transmitted through the pores, so that the heat insulation of the ceramic coat layer is improved.

The pore former is not particularly limited, and balloons that are fine hollow spheres composed of oxide ceramics, spherical acrylic particles, carbon such as graphite, carbonates, foaming agents, and the like can be used. Moreover, it is desirable that the formed ceramic coat layer has high heat insulation performance, and for that purpose, it is more desirable that pores having a small diameter are uniformly dispersed.
From such a viewpoint, the pore former is preferably carbon, carbonate, or a foaming agent. Examples of the carbonate and the foaming agent include CaCO ₃ , BaCO ₃ , NaHCO ₃ , Na ₂ CO ₃ , (NH ₄ ) ₂ CO _{3 and the} like.
Further, among these, carbon such as graphite is preferable.

In the method for producing a structure according to the present invention, when the insulating performance is imparted to the ceramic coat layer, it is desirable to include at least one of alumina and mullite as a constituent material of the second glass material. Among these, it is desirable to contain alumina.
When these materials are used, it is possible to form a ceramic coat layer having high insulation properties and heat resistance and durability.

In the structure manufacturing method of the present invention, it is desirable that the second glass material contains water and / or an organic binder. If the second glass material contains water and / or an organic binder, the second glass material will have a viscosity. The second glass material having viscosity is easily applied to the surface of the substrate, and the amount of application is easily controlled.
The organic binder is not particularly limited, and examples thereof include polyvinyl alcohol, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and the like.
These may be used alone or in combination of two or more.

The second glass material preferably contains an organic solvent. When the second glass material contains an organic solvent, the surface tension tends to decrease. As a result, when the second glass material is applied to the surface of the base material, the second glass material is easily adapted to the surface of the base material and is easily applied. Furthermore, when apply | coating 2nd glass material to 1st glass material, 2nd glass material becomes easy to become familiar with 1st glass material, and becomes easy to apply | coat.
On the other hand, when the 2nd glass material containing these substances is baked on a base material in a ceramic coat layer formation process, these substances will disappear by evaporation and decomposition. For this reason, the degree of firing shrinkage of the second glass material increases, and sink marks are likely to occur in the ceramic coat layer.
However, in the structure manufacturing method of the present invention, it is possible to prevent sink marks from occurring in the ceramic coat layer based on the above principle. Therefore, even if the degree of firing shrinkage of the second glass material is increased, the planned coating region can be reliably covered with the ceramic coat layer.
Although it does not specifically limit as an organic solvent, Methanol, ethanol, etc. are mention | raise | lifted.
These may be used alone or in combination of two or more.

The second glass material may contain water and an organic solvent, may contain an organic binder and an organic solvent, or may contain water, an organic binder and an organic solvent.
The total weight of water, the organic binder and the organic solvent with respect to the weight of the second glass material is preferably 5 to 80%.

<Ceramic coat layer formation process>
In the ceramic coat layer forming step in the structure manufacturing method of the present invention, the first glass material and the second glass material are baked on the surface of the substrate. Before this, the first glass material and the second glass material are baked. May be dried.

In the method for producing a structure of the present invention, the conditions for drying the first glass material and the second glass material are not particularly limited, and water and organic binder contained in the first glass material and the second glass material. It is desirable to adjust appropriately according to the type and amount of the organic solvent.
For example, as a drying condition when the total weight of water, the organic binder, and the organic solvent is 5 to 80% with respect to the weight of the first glass material and the second glass material, the drying temperature is 70 to 120 ° C. and the drying time. Is preferably 20 to 60 minutes.

In the structure manufacturing method of the present invention, the first glass material and the second glass material are baked on the surface of the substrate.
The conditions for baking the first glass material and the second glass material are not particularly limited as long as the temperature is higher than the softening point of the second glass material, but the baking temperature is 310 to 910 ° C. and the baking time is 10 to 60 minutes. It is desirable that

A structure can be manufactured through the above steps. Moreover, the structure manufactured in this way is also the structure of the present invention.

The structure of the present invention will be described.

The structure of the present invention is a structure comprising a base material made of a metal and a ceramic coat layer formed on the surface of the base material.

In the structure of the present invention, the area of the surface of the substrate where the ceramic coat layer is formed is smaller than the entire area of the surface of the substrate.
That is, the surface of the substrate has a portion where the ceramic coat layer is formed and a portion where it is not formed.

The ceramic coat layer of the structure of the present invention is composed of a first glass material and a second glass material having a higher softening point than the first glass material.
The first glass material is formed on the peripheral edge portion of the ceramic coat layer so as to be in a strip shape and in direct contact with the surface of the substrate, and is a base inside the portion where the first glass material is formed. A second glass material covering the surface of the substrate and at least a part of the upper surface of the first glass material with the second glass material, and covering the surface of the base material inside the portion where the first glass material is formed; The second glass material covering at least a part of the upper surface of the one glass material is continuous.

In the structure of the present invention, as described in the method for manufacturing the structure of the present invention, the use of the first glass material and the second glass material can suppress the occurrence of sink marks in the ceramic coat layer. it can.
In addition, since the 1st glass material and the 2nd glass material in the structure of this invention have already demonstrated in the manufacturing method of the structure of the said invention, description here is abbreviate | omitted.

In the structure of the present invention, the softening point of the first glass material or the softening point of the second glass material contained in the ceramic coat layer can be measured by the following method.
First, a differential thermal balance (manufactured by Rigaku, “TG-DTA”) is used so that the first glass material or the second glass material contained in the ceramic coat layer is scraped into a powder form, and the powdered ceramic coat layer is scraped to an appropriate amount. TG8120), the temperature is raised to 950 ° C. at a setting of 10 ° C./min in an air atmosphere, and a DTA curve is obtained at a sampling period of 1 second.
The fourth inflection point of the obtained DTA curve is taken as the softening point.

The peripheral edge portion of the ceramic coat layer of the structure of the present invention is, for example, a range inward from the end portion of the ceramic coat layer by a distance 40 times the average thickness of the ceramic coat layer.
In addition, that the 1st glass material is formed in the peripheral part of a ceramic coat layer means that at least one part of the 1st glass material is located in the peripheral part.

Details will be described below.
An example of the structure of the present invention is the structure shown in FIG.
FIG. 9 is a perspective view schematically showing an example of the structure of the present invention.
As shown in FIG. 9, the structure 100 which is an example of the structure of this invention is a structure which consists of the base material 10 which consists of metals, and the ceramic coat layer 50 formed in the surface 11 of the base material 10. As shown in FIG. .

The area of the surface 11 of the substrate 10 where the ceramic coat layer 50 is formed is smaller than the entire area of the surface 11 of the substrate 10.
That is, the surface 11 of the substrate 10 includes a portion where the ceramic coat layer 50 is formed and a portion where the ceramic coat layer 50 is not formed.

The ceramic coat layer 50 includes the first glass material 30 and the second glass material 40 having a softening point higher than that of the first glass material 30.

As shown in FIG. 9, the first glass material 30 is formed in a strip shape and in direct contact with the surface 11 of the substrate 10 on the peripheral edge 55 of the ceramic coat layer 50.

Further, the second glass material 40 covers the surface 11 of the base material 10 inside the portion where the first glass material 30 is formed and a part of the upper surface of the first glass material 30, and the first glass material 30. The second glass material 40 that covers the surface 11 of the base material 10 inside the portion where is formed, and the second glass material 40 that covers at least a part of the upper surface of the first glass material 30 are continuous.

In the structure of the present invention, the average thickness of the ceramic coat layer is preferably 50 to 1500 μm.
When the average thickness of the ceramic coat layer is less than 50 μm, it is difficult to obtain the effect that the substrate is covered with the ceramic coat layer.
If the average thickness of the ceramic coat layer exceeds 1500 μm, the thermal stress generated by the difference in thermal expansion between the ceramic coat layer and the substrate becomes large, so that the ceramic coat layer is easily damaged.

In the structure of the present invention, it is desirable that the base material be at least one selected from stainless steel, steel, iron, copper, aluminum, inconel, hastelloy, and invar.
Since stainless steel, aluminum, steel, iron, copper, inconel, hastelloy, and invar are easy to process, the base material can be easily processed according to the application.

The use of the structure of the present invention will be described.
The structure of the present invention includes, for example, an exhaust pipe, a casing that houses an exhaust gas treatment body in an exhaust gas purification device, an engine head (including an intake port and an exhaust port), a cylinder, a piston, a turbo housing, a heat exchanger, an EGR pipe, It can be used for engine valve applications.

The case where the structure of the present invention is used for an exhaust pipe will be described.
When the structure of the present invention is used as an exhaust pipe, the exhaust pipe may include a base material having an exhaust gas inlet and an exhaust gas outlet, and a ceramic coat layer formed on the surface of the base material. Good.
Further, the ceramic coat layer is composed of a first glass material and a second glass material, and the first glass material is formed in a band shape on the peripheral edge of the ceramic coat layer on the inlet side, and on the surface of the base material It may be formed so as to be in direct contact with.
Furthermore, the second glass material covers at least a part of the surface of the base material inside the portion where the first glass material is formed and the upper surface of the first glass material, and the first glass material is formed. The 2nd glass material which covers the surface of the base material inside a part, and the 2nd glass material may continue at least one part of the upper surface of a 1st glass material.

When the structure of the present invention is used as an exhaust pipe, the ceramic coat layer may be formed on the inner surface of the substrate, may be formed on the outer surface of the substrate, and the inner surface of the substrate and You may form in both the outer surfaces of a base material.
The inner surface of the substrate means the surface of the substrate on the flow path side through which the exhaust gas passes.
The outer surface of the substrate means the surface of the substrate opposite to the flow path side through which the exhaust gas passes.

When the structure of the present invention is used as an exhaust pipe, the ceramic coat layer is preferably made of barium glass. When the ceramic coat layer is barium glass, the heat insulation of the exhaust pipe is improved.

A case where exhaust gas passes through the exhaust pipe using the structure of the present invention as an exhaust pipe will be described.
The exhaust gas flows from the inlet of the exhaust pipe and is exhausted from the outlet of the exhaust pipe.
When the exhaust gas reaches the inlet of the exhaust pipe, the exhaust gas has a sufficiently high temperature. Further, when passing through the exhaust pipe, heat is released from the exhaust gas, and the temperature of the exhaust gas tends to decrease. However, when the ceramic coat layer is formed on the exhaust pipe as described above, the heat insulation of the exhaust pipe is increased, and the temperature of the exhaust gas can be prevented from being lowered. The exhaust gas is purified by the exhaust gas treatment body installed in the exhaust gas purification device installed downstream, but if the exhaust gas temperature does not decrease and is sufficiently high, the exhaust gas quickly adjusts the temperature of the exhaust gas treatment body. The exhaust gas treatment body can be suitably exerted the exhaust gas purification function of the exhaust gas treating body. That is, exhaust gas purification efficiency is improved.

Furthermore, when manufacturing such an exhaust pipe, after apply | coating 1st glass material to the surface of a base material, 2nd glass material is apply | coated so that at least one part of the upper surface of 1st glass material may be covered. . Therefore, the position of the end portion of the ceramic coat layer can be controlled.
Therefore, the part of the base material to be covered with the ceramic coat layer can be reliably covered.
Moreover, desired heat insulation performance and insulation performance can be ensured by forming the ceramic coat layer.

The exhaust pipe will be described in further detail. For example, the exhaust pipe shown in FIGS.
FIGS. 10-12 is a perspective view which shows typically an example at the time of using the structure of this invention as an exhaust pipe.

In Figure 10, the exhaust pipe 200, the exhaust gas inlet 201, a substrate 210 having an outlet 202 of the exhaust gas, a ceramic coating layer 250 ₁ is formed on the inner surface 211 ₁ of the substrate 210.
The ceramic coat layer 250 ₁ is composed of a first glass material 230 ₁ and a second glass material 240 _1, and the first glass material 230 ₁ is formed on the peripheral edge 255 ₁ of the ceramic coat layer 250 ₁ on the inlet side. , the belt, and are formed so as to be in direct contact with the inner surface 211 ₁ of the substrate 210.
Further, the inner surface 211 ₁ of the inner substrate 210 than the portion where the first glass material 230 ₁ is formed, and a first upper surface of the glass material 230 ₁ second glass material 240 ₁ covers the inner surface 211 ₁ and the second glass material 240 ₁ covering and the upper surface of the first glass material 230 ₁ and the second glass material 240 ₁ are continuous.
ing.

In Figure 11, the exhaust pipe 200, the exhaust gas inlet 201, a substrate 210 having an outlet 202 of the exhaust gas, a ceramic coating layer 250 ₂ formed on the outer surface 211 _{and second} substrate 210.
Ceramic coating layer 250 ₂ includes a first glass material 230 _2, has become a second glass material 240 ₂ which, the first glass material 230 _2, the peripheral portion 255 ₂ of the ceramic coating layer 250 _{and second} inlet-side , the belt, and are formed so as to be in direct contact with the outer surface 211 _{and second} substrate 210.
Furthermore, the outer surface 211 _{and second} inner substrate 210 than the portion where the first glass material 230 ₂ are formed, and a first upper surface of the glass material 230 ₂ second glass material 240 ₂ covers the outer surface 211 ₂ and the second glass material 240 ₂ covering a first upper surface of the glass material 230 ₂ and the second glass material 240 ₂ are continuous.

In Figure 12, the exhaust pipe 200, the exhaust gas inlet 201, a substrate 210 having an outlet 202 of the exhaust gas, are formed on the outer surface 211 _{and second} inner surfaces 211 ₁ and the base 210 of the substrate 210 a ceramic coating layer 250 ₁ and a ceramic coating layer 250 ₂ are.
The ceramic coat layer 250 ₁ is composed of a first glass material 230 ₁ and a second glass material 240 _1, and the first glass material 230 ₁ is formed on the peripheral edge 255 ₁ of the ceramic coat layer 250 ₁ on the inlet side. , the belt, and are formed so as to be in direct contact with the inner surface 211 ₁ of the substrate 210.
Further, the inner surface 211 ₁ of the inner substrate 210 than the portion where the first glass material 230 ₁ is formed, and a first upper surface of the glass material 230 ₁ second glass material 240 ₁ covers the inner surface 211 ₁ and the second glass material 240 ₁ covering and the upper surface of the first glass material 230 ₁ and the second glass material 240 ₁ are continuous.
Ceramic coating layer 250 ₂ includes a first glass material 230 _2, has become a second glass material 240 ₂ which, the first glass material 230 _2, the peripheral portion 255 ₂ of the ceramic coating layer 250 _{and second} inlet-side , the belt, and are formed so as to be in direct contact with the outer surface 211 _{and second} substrate 210.
Furthermore, the outer surface 211 _{and second} inner substrate 210 than the portion where the first glass material 230 ₂ are formed, and a first upper surface of the glass material 230 ₂ second glass material 240 ₂ covers the outer surface 211 ₂ and the second glass material 240 ₂ covering a first upper surface of the glass material 230 ₂ and the second glass material 240 ₂ are continuous.

The case where the structure of this invention is used for the casing which accommodates the exhaust-gas-treatment body in an exhaust gas purification apparatus is demonstrated.
In the exhaust gas purification apparatus using the structure of the present invention, the casing includes a base material, and the base material includes an exhaust gas inlet, an inlet-side inlet cone portion, an exhaust gas outlet, and an outlet cone. Has a part.
A ceramic coat layer is formed in the inlet cone portion. The ceramic coat layer is composed of a first glass material and a second glass material. The first glass material is a ceramic coat layer on the inlet side. May be formed in a belt-like shape and in direct contact with the surface of the substrate.
In addition, a ceramic coat layer is formed in the outlet cone portion, and the ceramic coat layer is composed of a first glass material and a second glass material, and the first glass material is a ceramic on the inlet side. You may form in the peripheral part of a coating layer so that it may contact | connect the strip | belt shape and the surface of a base material directly.

When the structure of the present invention is used for a casing that accommodates an exhaust gas treatment body in an exhaust gas purification apparatus, the ceramic coat layer may be formed on the inner surface of the base material of each cone part, and the base material of each cone part It may be formed on the outer surface.
The inner surface of the substrate means the surface of the substrate on the flow path side through which the exhaust gas passes.
The outer surface of the substrate means the surface of the substrate opposite to the flow path side through which the exhaust gas passes.

When the structure of the present invention is used in a casing that houses an exhaust gas treating body in an exhaust gas purification apparatus, the ceramic coat layer is preferably made of barium glass. When the ceramic coat layer is made of barium glass, in addition to improving the heat insulation of the exhaust pipe, the adhesion is also improved.

The internal structure of the casing when the structure of the present invention is used for a casing for housing an exhaust gas treating body in an exhaust gas purification apparatus will be described.
The casing contains an exhaust gas treating body around which a holding sealing material is wound.
The exhaust gas treating body is preferably in the form of a honeycomb, and preferably carries a catalyst for purifying the exhaust gas.
The exhaust gas flows in from the inlet and passes through the exhaust gas treating body. However, since the exhaust gas treating body carries a catalyst, the exhaust gas is purified by the catalytic action.

The holding sealing material is used for the purpose of protecting the exhaust gas treatment body from the external impact, the purpose of preventing the exhaust gas treatment body from falling out of the casing, and the purpose of improving heat insulation and preventing the temperature of the exhaust gas from decreasing. Yes.

In the case where the structure of the present invention is used for a casing for accommodating an exhaust gas treatment body in an exhaust gas purification apparatus, an effect when the ceramic coat layer is formed on the inner surface and / or the outer surface of the base material of the cone portion explain.
When the exhaust gas reaches the inlet of the casing, the exhaust gas has a sufficiently high temperature. Further, when passing through the casing, heat is released from the exhaust gas, and the temperature of the exhaust gas tends to decrease. However, when the exhaust gas passes through the casing, if a ceramic coat layer is formed on the inner surface and / or the outer surface of the cone part, these have high heat insulating properties. It is possible to prevent the temperature from decreasing. Exhaust gas is purified by the exhaust gas purifier, but if the temperature of the exhaust gas does not decrease and is sufficiently high, the exhaust gas quickly raises the temperature of the exhaust gas treater, which is suitable for the exhaust gas purifier function. Can be demonstrated. That is, exhaust gas purification efficiency is improved.
Moreover, in such a casing, since the ceramic coat layer is also formed in the outlet cone portion, the temperature of the exhaust gas is maintained even after the exhaust gas passes through the exhaust gas treating body.

When the structure of the present invention is used in a casing that houses an exhaust gas treating body in an exhaust gas purifying apparatus, the following effects are obtained when the ceramic coat layer is formed on the inner surface of the base material of the cone portion.
When the temperature of the exhaust gas decreases when the exhaust gas passes through the exhaust gas purification device, the condensed water of the exhaust gas is likely to be generated, and the flow path of the exhaust gas is easily corroded. However, when such a casing is used, the temperature of the exhaust gas is unlikely to decrease, so that it is possible to prevent the exhaust gas agglomerated water from being generated, and to prevent corrosion of the flow path.

In the case where the structure of the present invention is used for a casing for accommodating an exhaust gas treating body in an exhaust gas purification apparatus, when the casing is manufactured, the first glass material is applied to the surface of the base material, and then the first glass material is applied. A second glass material is applied so as to cover at least a part of the upper surface of the substrate. Therefore, the position of the end portion of the ceramic coat layer can be controlled.
Therefore, the part of the base material to be covered with the ceramic coat layer can be reliably covered.
Moreover, desired heat insulation performance and insulation performance can be ensured by forming the ceramic coat layer.

The exhaust gas purification device will be described in further detail. For example, the exhaust gas purification device as shown in FIGS. 13 (a) and 13 (b), FIGS. 14 (a) and 14 (b) and FIGS. 15 (a) and 15 (b) below. Can be given.

Fig.13 (a) is a perspective view which shows typically an example at the time of using the structure of this invention as a casing. FIG.13 (b) is the sectional view on the AA line of Fig.13 (a).
As shown in FIGS. 13A and 13B, the casing 300 includes a base material 310. The casing 300 accommodates an exhaust gas treatment body 360 around which a holding sealing material 370 is wound.
The substrate 310 includes an exhaust gas inlet 301, an inlet cone portion 303 on the inlet 301 side, an exhaust gas outlet 302, and an outlet cone portion 304.
A ceramic coating layer 351a ₁ is formed on the inner surface 311a ₁ of the base material 310 of the inlet cone portion 303 on the inlet 301 side. The ceramic coating layer 351a ₁ includes the first glass material 330a ₁ and the second glass material 330a ₁ . It is made of glass material 340a ₁ Metropolitan. The first glass material 330 a ₁ is formed in a strip shape and directly in contact with the inner surface 311 a _{1 of the} substrate 310 on the peripheral edge portion 355 a ₁ of the ceramic coat layer 350 a ₁ on the inflow port 301 side.
A ceramic coat layer 351b ₁ is formed on the inner surface 311b ₁ of the base 310 of the outlet cone portion 304 on the inlet 301 side. The ceramic coat layer 351b ₁ includes the first glass material 330b ₁ and the second glass material 330b ₁ . It is made of glass material 340b ₁ Metropolitan. The first glass material 330b ₁ is formed on the peripheral edge portion 355b ₁ of the ceramic coat layer 350b ₁ on the inflow port 301 side so as to be in contact with the inner surface 311b _{1 of the} substrate 310 in a strip shape.

Fig.14 (a) is a perspective view which shows typically an example at the time of using the structure of this invention as a casing. FIG. 14B is a cross-sectional view taken along the line BB in FIG.
As shown in FIGS. 14A and 14B, the casing 300 includes a base material 310. The casing 300 accommodates an exhaust gas treatment body 360 around which a holding sealing material 370 is wound.
The substrate 310 includes an exhaust gas inlet 301, an inlet cone portion 303 on the inlet 301 side, an exhaust gas outlet 302, and an outlet cone portion 304.
A ceramic coating layer 351a ₂ is formed on the inlet 301 side of the outer surface 311a ₂ of the base material 310 of the inlet cone portion 303. The ceramic coating layer 351a ₂ includes the first glass material 330a ₂ and the second glass material 330a ₂ . It is made of glass material 340a ₂ Metropolitan. The first glass material 330a ₂ is formed in a strip shape and in direct contact with the outer surface 311a _{2 of the} substrate 310 at the peripheral edge portion 355a ₂ of the ceramic coat layer 350a ₂ on the inlet 301 side.
A ceramic coat layer 351b ₂ is formed on the outer surface 311b ₂ of the base material 310 of the outlet cone portion 304 on the inlet 301 side. The ceramic coat layer 351b ₂ includes the first glass material 330b ₂ and the second glass material 330b ₂ . It is made of glass material 340b ₂ Metropolitan. The first glass material 330b ₂ is formed on the peripheral edge portion 355b ₂ of the ceramic coat layer 350b ₂ on the inflow port 301 side so as to be in direct contact with the outer surface 311b ₂ of the base material 310.

Fig.15 (a) is a perspective view which shows typically an example at the time of using the structure of this invention as a casing. FIG.15 (b) is CC sectional view taken on the line of Fig.15 (a).
As shown in FIGS. 15A and 15B, the casing 300 includes a base material 310. The casing 300 accommodates an exhaust gas treatment body 360 around which a holding sealing material 370 is wound.
The substrate 310 includes an exhaust gas inlet 301, an inlet cone portion 303 on the inlet 301 side, an exhaust gas outlet 302, and an outlet cone portion 304.
A ceramic coating layer 351a ₁ is formed on the inner surface 311a ₁ of the base material 310 of the inlet cone portion 303 on the inlet 301 side. The ceramic coating layer 351a ₁ includes the first glass material 330a ₁ and the second glass material 330a ₁ . It is made of glass material 340a ₁ Metropolitan. The first glass material 330 a ₁ is formed in a strip shape and directly in contact with the inner surface 311 a _{1 of the} substrate 310 on the peripheral edge portion 355 a ₁ of the ceramic coat layer 350 a ₁ on the inflow port 301 side.
A ceramic coat layer 351b ₁ is formed on the inner surface 311b ₁ of the base 310 of the outlet cone portion 304 on the inlet 301 side. The ceramic coat layer 351b ₁ includes the first glass material 330b ₁ and the second glass material 330b ₁ . It is made of glass material 340b ₁ Metropolitan. The first glass material 330b ₁ is formed on the peripheral edge portion 355b ₁ of the ceramic coat layer 350b ₁ on the inflow port 301 side so as to be in contact with the inner surface 311b _{1 of the} substrate 310 in a strip shape.
A ceramic coating layer 351a ₂ is formed on the inlet 301 side of the outer surface 311a ₂ of the base material 310 of the inlet cone portion 303. The ceramic coating layer 351a ₂ includes the first glass material 330a ₂ and the second glass material 330a ₂ . It is made of glass material 340a ₂ Metropolitan. The first glass material 330a ₂ is formed in a strip shape and in direct contact with the outer surface 311a _{2 of the} substrate 310 at the peripheral edge portion 355a ₂ of the ceramic coat layer 350a ₂ on the inlet 301 side.
A ceramic coat layer 351b ₂ is formed on the outer surface 311b ₂ of the base material 310 of the outlet cone portion 304 on the inlet 301 side. The ceramic coat layer 351b ₂ includes the first glass material 330b ₂ and the second glass material 330b ₂ . It is made of glass material 340b ₂ Metropolitan. The first glass material 330b ₂ is formed on the peripheral edge portion 355b ₂ of the ceramic coat layer 350b ₂ on the inflow port 301 side so as to be in direct contact with the outer surface 311b ₂ of the base material 310.

Hereinafter, effects of the method for producing the structure of the present invention will be described.
(1) In the structure manufacturing method of the present invention, in the first glass material application step, the first glass material is applied in a strip shape so as to be in contact with the boundary of the region to be coated on the outside of the region to be coated. In the material application step, the second region is formed so as to cover at least a part of the upper surface of the first glass material and the region to be covered and at least a part of the upper surface of the first glass material to the region to be covered. Apply glass material. The second glass material has a higher softening point than the first glass material.
Since the second glass material has a higher softening point than the first glass material, when the first glass material and the second glass material are baked on the surface of the substrate in the ceramic coat layer forming step, first, the first glass material is Soften. Even if the first glass material is softened, since the first glass material is sandwiched and pressed between the base material and the second glass material, aggregation of the first glass material is suppressed. That is, the second glass material and the base material have a stronger force to press the first glass material than the force that the first glass material tends to agglomerate, so that the first glass material is less likely to agglomerate.
Thereafter, as the heating is performed, the first glass material is further softened, the adhesion between the first glass material and the surface of the base material is improved, and the first glass material is baked onto the surface of the base material.
Thereafter, when the heating proceeds, the second glass material starts to soften. When the second glass material starts to soften, it tends to agglomerate due to surface tension. At this time, the first glass material has already been softened, and the adhesion between the second glass material and the first glass material becomes high. Yes. Therefore, the first glass material functions as a paste material, and aggregation of the second glass material is suppressed.
That is, since the force with which the first glass material and the second glass material are in close contact with each other is stronger than the force with which the second glass material attempts to aggregate, the second glass material is less likely to aggregate.
As a result, it is possible to suppress the occurrence of sink marks in the ceramic coat layer.

(Example)
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1
(1) Covering area determination step (1-1) Preparation of base material First, a flat base material (vertical × horizontal × height = 40 mm × 40 mm × 1.5 mm) made of a stainless steel material (SUS430) was prepared. .

(1-2) Determination of Covering Planned Region Next, in the lateral direction of the flat plate, a region from the right end of the flat plate to 19.5 mm was set as the planned coating region.

(2) 1st glass material application | coating process Next, the silica type glass (softening point: 680 degreeC) which is a 1st glass material was apply | coated to the outer side of a coating plan area | region so that the boundary of a coating plan area | region may be touched.
The applied first glass material had a thickness of 5 μm and a width of 5 mm.

(3) Second glass material application step Next, silica-based glass (softening point: 780 ° C.), which is the second glass material, is covered so as to cover only a part of the upper surface of the coating target region and the first glass material. Applied.
The applied second glass material had a thickness of 250 μm.

(4) Ceramic coat layer forming step (4-1) Drying of the first glass material and the second glass material Next, the base material coated with the first glass material and the second glass material is placed at 70 ° C. for 20 minutes. Dried under conditions.

(4-2) Firing of the first glass material and the second glass material Next, the base material coated with the first glass material and the second glass material is fired under the conditions of 900 ° C. for 60 minutes, and the ceramic coat layer Formed.

The structure according to Example 1 was manufactured through the above steps. In the structure according to Example 1, the average thickness of the ceramic coat layer was 250 μm.
The manufactured structure is shown in FIG. FIG. 16 is a top view photograph of the structure according to Example 1. In FIG. 16, the range indicated by the arrow indicates the planned covering area.
As shown in FIG. 16, in the structure according to Example 1, all of the planned coating region was covered with the ceramic coat layer.

(Example 2)
In the “(3) second glass material application step” of the first embodiment, the second glass material is used so as to cover all of the region to be coated and the upper surface of the first glass material and expose the end surface of the first glass material. A structure according to Example 2 was manufactured in the same manner as in Example 1 except that a certain silica-based glass (softening point: 780 ° C.) was applied.
The manufactured structure is shown in FIG. FIG. 17 is a top view photograph of the structure according to Example 2. In FIG. 17, the range indicated by the arrow indicates the planned covering area.
As shown in FIG. 17, in the structure according to Example 2, the entire covered region was covered with the ceramic coat layer.

(Example 3)
In “(1-2) Determining the area to be coated” in Example 1, in the lateral direction of the flat plate, the area from the right end of the flat plate to 15.5 mm was set as the area to be covered, and “ In the (3) second glass material application step, silica-based glass (softening point: softening point: so as to cover the coating region, the entire upper surface of the first glass material, and the end surface of the first glass material. A structure according to Example 3 was manufactured in the same manner as in Example 1 except that 780 ° C. was applied.
The manufactured structure is shown in FIG. 18 is a top view photograph of the structure according to Example 3. FIG. In FIG. 18, a range indicated by an arrow indicates a planned covering area.
As shown in FIG. 18, in the structure according to Example 3, the entire coating area was covered with the ceramic coat layer.

(Comparative Example 1)
In the “(3) Second glass material application step” of Example 1, the same procedure as in Example 1 except that silica-based glass (softening point: 780 ° C.), which is the second glass material, was applied only to the coating area. A structure according to Comparative Example 1 was manufactured.
The manufactured structure is shown in FIG. FIG. 19 is a top view photograph of the structure according to Comparative Example 1. In FIG. 19, a range indicated by an arrow indicates a planned covering area.
As shown in FIG. 19, in the structure according to Comparative Example 1, sink marks were generated in the ceramic coat layer, and there was a portion where the ceramic coat layer was not formed in the planned coating region.

As described above, after the first glass material is applied, the second glass material is applied so as to cover at least a part of the region to be covered and the upper surface of the first glass material. It was shown that the occurrence can be suppressed.

10, 210, 310 Base material ₁₁ , 211 ₁ , 211 ₂ , 311a ₁ , 311a ₂ , 311b ₁ , 311b ₂ Surface 20 of the base material Planned coating region 20a Boundaries 30, 230 ₁ , 230 ₂ , 330a _{1 of the} planned coating region , 330a ₂ , 330b ₁ , 330b ₂ First glass material 30a Upper surface 30b of the first glass material End surface 40, 240 ₁ , 240 ₂ , 340a ₁ , 340a ₂ , 340b ₁ , 340b _{2 of} the first glass material 2nd glass material _{50,250 1, 250 2, 350a 1} , 350a 2, 350b 1, 350b 2 ceramic coating layer _{51,251 1, 251 2, 351a 1} , 351a 2, 351b 1, end of 351b ₂ ceramic coating layer 55,255 ₁ , 255 ₂ , 355 a ₁ , 355 a ₂ , 355 _{b 1} , 3 55b ₂ Peripheral part 100 of ceramic coat layer Structure 200 Exhaust pipe 201, 301 Inlet 202, 302 Outlet 300 Casing 303 Inlet cone part 304 Outlet cone part 360 Exhaust gas treatment body 370 Holding sealing material

Claims (18)

A coating planned area determining step for determining a coating planned area on a part of the surface of the base material made of metal;
A first glass material application step of applying a first glass material in a strip shape so as to be in contact with a boundary of the planned coating region outside the planned coating region;
The second glass so as to cover at least a part of the upper surface of the first coated glass region and the upper surface of the first glass material and to continue from at least a part of the upper surface of the first glass material to the predetermined coated region. A second glass material application step of applying the material;
A ceramic coat layer forming step of baking the first glass material and the second glass material on the surface of the substrate to form a ceramic coat layer;
The second glass material has a softening point higher than that of the first glass material. The method for manufacturing a structure according to claim 1, wherein in the second glass material application step, the second glass material is applied so as to cover only a part of the upper surface of the first glass material. 2. The structure according to claim 1, wherein in the second glass material application step, the second glass material is applied so as to cover the entire upper surface of the first glass material and expose an end surface of the first glass material. Manufacturing method. 2. The structure according to claim 1, wherein in the second glass material application step, the second glass material is applied so as to cover all of the upper surface of the first glass material and an end surface of the first glass material. Production method. The method for manufacturing a structure according to any one of claims 1 to 4, wherein a softening point of the first glass material is 300 to 700 ° C. The method for manufacturing a structure according to any one of claims 1 to 5, wherein a softening point of the second glass material is 550 to 800 ° C. The said 1st glass material is a manufacturing method of the structure in any one of Claims 1-6 containing water and / or an organic binder. The said 1st glass material is a manufacturing method of the structure in any one of Claims 1-7 containing an organic solvent. The said 2nd glass material is a manufacturing method of the structure in any one of Claims 1-8 containing water and / or an organic binder. The said 2nd glass material is a manufacturing method of the structure in any one of Claims 1-9 containing an organic solvent. The method for manufacturing a structure according to any one of claims 1 to 10, wherein a width of the first glass material applied in the first glass material application step is 2 to 60 mm. A structure comprising a base material made of metal and a ceramic coat layer formed on the surface of the base material,
The ceramic coat layer is composed of a first glass material and a second glass material having a higher softening point than the first glass material,
Of the surface of the substrate, the area of the portion where the ceramic coat layer is formed is smaller than the entire area of the surface of the substrate,
The first glass material is formed on the peripheral edge of the ceramic coat layer so as to be in a strip shape and in direct contact with the surface of the base material,
The second glass material covers at least a part of the surface of the base material inside the portion where the first glass material is formed and the upper surface of the first glass material,
The second glass material covering the surface of the base material inside the portion where the first glass material is formed and the second glass material covering at least a part of the upper surface of the first glass material are continuous. A structure characterized by The structure according to claim 12, wherein the softening point of the first glass material is 300 to 700 ° C. The structure according to claim 12 or 13, wherein a softening point of the second glass material is 550 to 800 ° C. The structure according to any one of claims 12 to 14, wherein a peripheral edge portion of the ceramic coat layer is a range that is directed inward from an end portion of the ceramic coat layer by a distance 40 times the average thickness of the ceramic coat layer. . The structure according to any one of claims 12 to 15, wherein an average thickness of the ceramic coat layer is 50 to 1500 µm. The structure according to any one of claims 12 to 16, wherein the substrate is made of at least one selected from stainless steel, steel, iron, copper, aluminum, inconel, hastelloy, and invar. The structure according to any one of claims 12 to 17, which is used as an exhaust pipe.