WO2016063561A1

WO2016063561A1 - Coated metal substrate

Info

Publication number: WO2016063561A1
Application number: PCT/JP2015/064472
Authority: WO
Inventors: 友好中村; 孝則河合
Original assignee: イビデン株式会社
Priority date: 2014-10-24
Filing date: 2015-05-20
Publication date: 2016-04-28
Also published as: JP6581593B2; JPWO2016063561A1

Abstract

A coated metal substrate according to the present invention and having a ceramic coating layer comprising a ceramic starting material formed on a substrate comprising a metal, the coated metal substrate being characterized in that the interior of the ceramic coating layer has uniformly dispersed pores formed therein, the surface roughness (Ra) of the ceramic coating layer is 8μm or less, and the pores are directly surrounded by the ceramic coating layer.

Description

Coated metal substrate

The present invention relates to a coated metal substrate.

In vehicles such as automobiles equipped with an engine, a large amount of heat is generated in the engine part, but the generated heat is easily diffused to the surroundings through the engine member, and the generated heat is not necessarily fully utilized. It is.

Therefore, researches have been actively conducted to effectively use the heat generated in the engine and improve characteristics such as fuel efficiency. To reduce heat loss, the weight of the engine and its peripheral members have been reduced. Attempts have been made to insulate aluminum members used for the purpose.

Conventionally, as a method for achieving heat insulation of an aluminum member, an attempt has been made to form a heat insulating film on a substrate surface (for example, Patent Document 1).

JP 2012-072745 A International Publication No. 2012/093697 JP 2014-092035 A

In Patent Document 1, a porous layer is formed by anodization on the surface of an aluminum alloy base material, and a coating layer containing ZrO ₂ or the like having a lower thermal conductivity than the base material is provided on the porous layer. An insulation structure for aluminum products is disclosed.
However, since the coating layer described in Patent Document 1 is a thermal spray coating, the coating strength and the adhesion to the substrate are not sufficient, and there is a problem that the coating cracks or peels off. Patent Document 1 discloses that irregularities are also formed on the surface of the coating layer, reflecting the irregularities on the surface of the porous layer. When gas flows through the surface of the coating layer with irregularities, there is a problem that the gas flow is disturbed by the irregularities of the coating layer, and the heat insulation coefficient decreases due to an increase in heat transfer coefficient due to an increase in fluid resistance. there were.

Patent Document 2 discloses an exhaust pipe including a surface coating layer in which pores are unevenly distributed in the center portion in the thickness direction of the surface coating layer. According to Patent Document 2, if the pores are unevenly distributed in the central portion in the thickness direction of the surface coating layer, cracks generated in the vicinity of the surface are inhibited from progressing by the pores, and the surface coating layer may be completely destroyed. It is described that it can be prevented. However, in this method, since pores that can improve heat insulation exist only in the center portion of the surface coating layer, the heat insulation performance is applied in places where high heat insulation performance is required, such as engine members. There was a problem that was insufficient.

Patent Document 3 discloses an engine in which a heat insulation layer including a silicone resin, magnetic powder, a Si oxide obtained by oxidizing a part of the silicone resin, and hollow particles made of a nonmagnetic material is formed. A heat insulating structure for a combustion chamber member is disclosed. When the pores are formed of hollow particles as in Patent Document 3, a shell layer of the hollow particles exists at the interface between the pores and the Si-based oxide layer that is the ceramic coat layer. Therefore, there is a problem that cracks are likely to occur due to the difference in thermal expansion coefficient between the Si-based oxide layer, which is the ceramic coat layer, and the shell layer.

The inventors conducted extensive research to solve the above problems, and as a result, uniformly dispersed pores were formed in the ceramic coat layer, and the surface roughness (Ra) of the ceramic coat layer was suppressed to 8 μm or less. It has been found that heat insulation can be improved by constituting so that is directly surrounded by the ceramic coat layer, and the present invention has been conceived.

That is, the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a coated metal substrate on which a ceramic coat layer having excellent heat insulation properties is formed.

In order to achieve the above object, the coated metal substrate of the present invention is a coated metal substrate in which a ceramic coat layer made of a ceramic raw material is formed on a substrate made of metal, and the inside of the ceramic coat layer Are characterized in that uniformly dispersed pores are formed, the surface roughness (Ra) of the ceramic coat layer is 8 μm or less, and the pores are directly surrounded by the ceramic coat layer.

In the coated metal substrate of the present invention, pores that are uniformly dispersed are formed in the ceramic coating layer. Therefore, it becomes a ceramic coat layer excellent in heat insulation.
Furthermore, since the surface of the ceramic coat layer has a surface roughness (Ra) of 8 μm or less, the flow of gas flowing on the surface of the ceramic coat layer is hardly disturbed, and the apparent thermal conductivity can be lowered.
In addition, since the pores are directly surrounded by the ceramic coat layer, in other words, there is no shell layer made of hollow particles, so that the generation of cracks originating from the shell layer can be suppressed.
In addition, surface roughness (Ra) is arithmetic mean roughness based on JISB0601 (2001), for example, can be measured with a surface roughness measuring machine etc.

Whether or not the pores are uniformly dispersed can be confirmed by the following procedure.
First, the cross section of the ceramic coat layer is observed with a scanning electron microscope (hereinafter also referred to as SEM), the state of the pores in the cross section is photographed, and the number of pores having a pore diameter exceeding 0.1 μm is determined by the following procedure. Count.
The imaging magnification is changed as follows for each thickness (also referred to as film thickness) of the ceramic coat layer.
5 to 50 μm: 2000 times 50 to 100 μm: 1000 times 100 to 300 μm: 500 to 300 μm to less than 500 μm: 200 to 500 μm to less than 1000 μm: 150 to 1000 μm to less than 2000 μm Case: 100 times In addition, the SEM image is taken at five arbitrary locations of the ceramic coat layer which is a target for confirming the dispersion of pores. At this time, photographing is performed so that the entire area of the ceramic coat layer in the thickness direction is included in the SEM image. Subsequently, the photographed SEM image is divided into nine regions of 3 × 3 in the vertical direction, and the number of pores having a pore diameter of 0.1 μm or more present in each region is counted.
When 10 or more pores having a pore diameter of 0.1 μm or more can be confirmed in each region, that is, 10 or more pores having a pore diameter of 0.1 μm or more can be confirmed in all 9 regions × 5 locations = 45 regions. In this case, it is assumed that the pores existing in the ceramic coat layer are uniformly dispersed.
When the photographed SEM image is divided into nine regions, the ceramic coat layer is divided so that the thickness (film thickness) of the ceramic coat layer is divided into three equal parts. The direction perpendicular to the thickness direction is a predetermined region that is 1.5 times as long as the thickness direction of the divided ceramic coat layer.

That is, the coated metal substrate of the present invention is 2000 times, 50 μm or more and less than 100 μm when the thickness of the ceramic coat layer is 5 μm or more and less than 50 μm so that the entire region in the thickness direction of the ceramic coat layer is accommodated. In the case of 100 μm or more and less than 300 μm, 500 times, in the case of 300 μm or more and less than 500 μm, 200 times, in the case of 500 μm or more and less than 1000 μm, 150 times, in the case of 1000 μm or more and less than 2000 μm, 100 times A scanning electron microscope image of the cross section of the ceramic coat layer taken at a magnification of 5 mm is taken as the vertical length is the thickness of the ceramic coat layer, and the horizontal length is 1.5 times the thickness of the ceramic coat layer. Are randomly selected as 5 rectangular areas, and the rectangular areas are further divided into 9 areas each of 3 × 3 In case of a split to the total of 45 regions, in all areas of the 45, it can be said that the pore diameter or more pores 0.1μm is present more than 10 pieces.

In the coated metal substrate of the present invention, the metal is preferably aluminum or an aluminum alloy.
When the metal is aluminum or an aluminum alloy, it is lightweight, so that it is possible to reduce the weight of the engine and improve the fuel consumption rate.
Aluminum or an aluminum alloy can form an alumite layer by subjecting its surface to an alumite treatment or the like.

In the coated metal substrate of the present invention, an alumite layer is formed on the surface of a substrate made of aluminum or an aluminum alloy, and the ceramic coat layer is formed on the substrate on which the anodized layer is formed. It is preferable.
Since the alumite layer formed on the surface of the base material made of aluminum or an aluminum alloy is obtained by altering a part of the base material, the base material and the alumite layer are integrated. And since an alumite layer has many unevenness | corrugations on the surface, a contact area with a ceramic coat layer will increase. Furthermore, since the alumite layer is composed of an oxide, it can be chemically bonded to the atoms constituting the ceramic coat layer via oxygen, and the adhesive force between the substrate and the ceramic coat layer is increased. Therefore, the adhesiveness between the substrate and the ceramic coat layer can be improved.
Moreover, in the coated metal base material of the present invention, the ceramic coating material softened in the firing process spreads over the surface of the metal base material and enters the surface unevenness, thereby canceling the unevenness on the surface of the base material. Therefore, even when unevenness is formed on the surface of the metal substrate, the uneven shape is not reflected on the surface shape of the ceramic coat layer, and the unevenness is not formed on the surface of the ceramic coat layer. Therefore, the surface roughness of the surface of the ceramic coat layer can be reduced while maintaining the adhesive force of the ceramic coat layer.

In the coated metal substrate of the present invention, the softening point of the ceramic raw material is preferably 250 to 550 ° C.
If the softening point of the ceramic raw material is less than 250 ° C., the softening point is too low, so that the ceramic raw material is difficult to melt during firing, and it may be difficult to form a film having a uniform thickness. On the other hand, if the softening point of the ceramic raw material exceeds 550 ° C., the thermal decomposition of the surfactant may end before the ceramic raw material constituting the ceramic coating raw material softens. In such a case, the decomposition gas generated by the thermal decomposition of the surfactant diffuses into the firing atmosphere and cannot form pores.

In the coated metal substrate of the present invention, it is preferable that the ceramic coat layer further contains a crystalline inorganic material. By including a crystalline inorganic material in the ceramic coat layer, the mechanical strength, heat resistance, adhesiveness, heat insulation and the like of the ceramic coat layer can be improved.

In the coated metal substrate of the present invention, the crystalline inorganic material is composed of at least one selected from the group consisting of alumina, zirconia, titania, lanthania, samaria, silica, yttria, calcia, magnesia, ceria, and hafnia. It is preferable.
Since these crystalline inorganic materials are excellent in heat resistance, the heat resistance of the ceramic coat layer containing the crystalline inorganic material can be improved.

In the coated metal substrate of the present invention, the thickness of the ceramic coat layer is preferably 10 to 1000 μm.
When the thickness of the ceramic coat layer is less than 10 μm, the thickness of the ceramic coat layer is too thin, so that the coated metal substrate cannot exhibit sufficient heat insulation.
On the other hand, if the thickness of the ceramic coat layer exceeds 1000 μm, cracks may easily occur when a thermal shock or the like is applied to the ceramic coat layer.

FIG. 1A is a cross-sectional view schematically showing a cross section of a coated metal substrate of the present invention, and FIG. 1B is a partially enlarged cross-sectional view of a region indicated by a rectangle A in FIG. is there. FIG. 2A schematically shows a procedure for confirming whether pores in the ceramic coat layer are uniformly dispersed, and FIG. 2B shows a method of dividing an SEM image into nine regions. It is explanatory drawing which showed typically. FIG. 3 is an SEM image obtained by photographing a cross section of the coated metal substrate according to Example 1.

(Detailed description of the invention)
Hereinafter, the present invention will be specifically described. However, the present invention is not limited to the following contents, and can be appropriately modified and applied without departing from the scope of the present invention.

The coated metal substrate of the present invention is a coated metal substrate in which a ceramic coat layer made of a ceramic raw material is formed on a substrate made of metal, and the pores dispersed uniformly in the ceramic coat layer The surface roughness (Ra) of the ceramic coat layer is 8 μm or less, and the pores are directly surrounded by the ceramic coat layer.

FIG. 1A is a cross-sectional view schematically showing a cross section of a coated metal substrate of the present invention, and FIG. 1B is a partially enlarged cross-sectional view of a region indicated by a rectangle A in FIG. is there.
As shown in FIG. 1, in the coated metal base material 10 of the present invention, a ceramic coat layer 12 is formed on a base material 11 made of metal.
Inside the ceramic coat layer 12 are uniformly dispersed pores 13.
As shown in FIG. 1 (b), the pores 13 are directly surrounded by the ceramic coat layer 12. Furthermore, on the surface 12a of the ceramic coat layer, the surface roughness (Ra) is 8 μm or less.
In addition, the surface roughness (Ra) in this specification is a value measured based on JIS B 0601 (2001).

A method for confirming whether the pores are uniformly dispersed will be described with reference to FIGS. 2 (a) and 2 (b).
FIG. 2A schematically shows a procedure for confirming whether pores in the ceramic coat layer are uniformly dispersed, and FIG. 2B shows a method of dividing an SEM image into nine regions. It is explanatory drawing which showed typically.
First, the cross section of the ceramic coat layer for which the pore dispersion is to be confirmed is photographed by SEM.
At this time, an area indicated by a rectangle B shown in FIG. 2A is an area for capturing an SEM image. As shown in FIG. 2A, in the SEM image, a magnification in which the entire region of the ceramic coat layer 12 in the thickness direction of the ceramic coat layer 12 falls within the SEM image is selected.
The magnification of SEM varies depending on the thickness (film thickness) of the ceramic coating layer. When the thickness of the ceramic coating layer is 5 μm or more and less than 50 μm, it is 2000 times, when it is 50 μm or more and less than 100 μm, it is 1000 times, or 100 μm or more but less than 300 μm. Is 500 times, 200 times when 300 μm or more and less than 500 μm, 150 times when 500 μm or more and less than 1000 μm, and 100 times when 1000 μm or more and less than 2000 μm. 5 SEM images are taken at random for each ceramic coat layer. The description will be continued below assuming that FIG. 2A is one of SEM images (one of five) taken at random.
The photographed SEM image is divided into 9 blocks of 3 × 3 as shown in FIG.
In the SEM image shown in FIG. 2B, the double-headed arrow c is divided so that the longitudinal direction (the direction indicated by the double-headed arrow c in FIG. 2B) is divided into three equal parts. It is partitioned by double arrows c ₁ , c ₂ and c ₃ which are divided into three equal parts. When the thickness of the ceramic coat layer varies in the SEM image, the thickness of the ceramic coat layer at the portion where the thickness is the thickest is used as a reference.
Further, the length b in the horizontal direction (direction indicated by a double-headed arrow b in FIG. 2B) which is a direction perpendicular to the vertical direction is 1.5 times the thickness c of the ceramic coat layer, The double arrows b ₁ , b _2, and b ₃ that divide this into three are all 1.5 times longer than c ₁ , c ₂ , and c ₃ .
That is, the SEM image has a rectangular shape defined by (thickness of the ceramic coat layer) × (1.5 times the thickness of the ceramic coat layer) in the thickness direction (vertical direction) and the length direction ( It is divided into nine regions by dividing each of them in the horizontal direction.
Subsequently, the number of pores having a pore diameter of 0.1 μm or more present in each of the nine regions is counted. If the number of pores having a pore diameter of 0.1 μm or more is 10 or more in all 45 regions of 9 regions × 5 places, it is determined that the pores are uniformly dispersed in the ceramic coat layer.

In other words, the coated metal substrate of the present invention is 2000 times larger when the thickness of the ceramic coating layer is 5 μm or more and less than 50 μm so that the entire region in the thickness direction of the ceramic coating layer is accommodated, and 50 μm or more and less than 100 μm. 1000 times, 500 times if 100 μm or more and less than 300 μm, 200 times if 300 μm or more and less than 500 μm, 150 times if 500 μm or more and less than 1000 μm, 100 times if 1000 μm or more and less than 2000 μm In a scanning electron microscope (hereinafter also referred to as SEM) image of the cross section of the ceramic coat layer taken at a magnification, the vertical length is the thickness of the ceramic coat layer, and the horizontal length is 1 of the thickness of the ceramic coat layer. .Randomly select five rectangular areas to be multiplied by 5 times, and each of the rectangular areas is divided into 9 areas of 3 × 3 In the case of the equally divided to the total of 45 regions in all 45 areas, it can be said that the pore diameter or more pores 0.1μm is present more than 10 pieces.

When counting the number of pores having a pore diameter of 0.1 μm or more, if a plurality of pores are connected to form one pore, it is counted as one pore. Furthermore, pores that are not completely contained in the partitioned area are not counted. That is, for example, when the pores existing in the ceramic coat layer are all continuous pores, the number of pores is counted as one in total, so the number of pores in each region divided into nine is all 0.

The coated metal substrate of the present invention has excellent heat insulating performance because there are uniformly dispersed pores.

The ceramic coating layer constituting the coated metal substrate of the present invention has pores, but the pores are directly surrounded by the ceramic coating layer.
Examples of the case where the pores are not directly surrounded by the ceramic coat layer include a case where the pores are formed of a structure different from the ceramic coat layer, for example, hollow particles. In such a case, the pores are surrounded by the ceramic coat layer via the hollow particles (also referred to as a shell layer). When the ceramic coat layer and the shell layer are different materials, cracks may occur in the ceramic coat layer due to the difference in thermal expansion coefficient.
In the ceramic coat layer constituting the coated metal substrate of the present invention, since the pores are directly surrounded by the ceramic coat layer and there is no shell layer, the above problem does not occur.

The thermal conductivity at room temperature of the ceramic coating layer constituting the coated metal substrate of the present invention is preferably 0.1 to 3 W / m · K.
If the thermal conductivity is less than 0.1 W / m · K, the porosity required to achieve the above thermal conductivity is increased, so that the mechanical strength of the formed ceramic coat layer may be excessively lowered. is there. On the other hand, if the thermal conductivity exceeds 3 W / m · K, there is a problem that a sufficient heat insulating effect cannot be obtained. In order to obtain a desired heat insulation effect, it is necessary to increase the thickness of the ceramic coat layer. Therefore, when applying the coated metal substrate of the present invention to an engine member or the like, it is difficult to secure a space in the design. There is a problem. The thermal conductivity is measured based on JIS R 1611 (2010) using a laser flash device (thermal constant measuring device: NETZSCH LFA457 Microflash).

The average pore diameter of the pores formed in the ceramic coat layer is not particularly limited, but is preferably 0.1 to 80 μm, preferably 0.5 to 50 μm, and 1 to 50 μm. Is more preferable.
When the average pore diameter is less than 0.1 μm, the heat insulating effect obtained by the pores is small, and a sufficient heat insulating effect may not be obtained. On the other hand, when the average pore diameter exceeds 80 μm, the pore size is too large, and the mechanical strength of the ceramic coat layer may be lowered.
The average pore diameter of the pores can be obtained using an image similar to the SEM image used for determining whether or not the pores described above are uniformly dispersed. Specifically, the average pore diameter can be obtained by measuring the pore diameter of all the pores present in the nine divided areas and obtaining the average value. When the shape of the pores is not circular, the diameter of the pores is the diameter corresponding to the projected area circle (Haywood diameter).

The porosity of the ceramic coat layer constituting the coated metal substrate of the present invention is preferably 5 to 75%, more preferably 10 to 60%, and even more preferably 20 to 45%.
When the porosity of the ceramic coat layer is less than 5%, the heat insulating performance of the ceramic coat layer may not be sufficient. On the other hand, when the porosity of the ceramic coat layer exceeds 75%, the porosity is too high, the mechanical strength of the ceramic coat layer is lowered, and cracks are likely to occur.
The porosity of the ceramic coat layer can be obtained using an image similar to the SEM image used for determining whether or not the above-described pores are uniformly dispersed. Specifically, the total value of the area occupied by all the pores existing in the nine divided areas is obtained and divided by the total area of the nine areas, and this value is measured at five locations. The average value of the five locations is taken as the porosity of the ceramic coat layer.

The surface of the ceramic coat layer (the surface not in contact with the substrate) has a surface roughness (Ra) of 8 μm or less, preferably 4 μm or less, and more preferably 2 μm or less.
The lower limit of the surface roughness (Ra) is not particularly limited, but is preferably 1 μm from the viewpoint of product yield.
When the surface roughness (Ra) of the ceramic coat layer exceeds 8 μm, the flow of fluid flowing on the surface of the ceramic coat layer tends to be turbulent, and the heat transfer coefficient increases, leading to energy loss.

Next, each member which comprises the coated metal base material of this invention is demonstrated one by one.
First, the base material constituting the coated metal base material of the present invention will be described.
Examples of the base material made of metal include stainless steel, heat resistant steel (SUH), aluminum, aluminum alloy, iron, inconel, hastelloy, and invar. Moreover, various cast products (for example, cast iron, cast steel, carbon steel, etc.) etc. are mentioned.
Specific examples of the heat resistant steel (SUH) include martensitic heat resistant steel (SUH3, SUH11, etc.), austenitic heat resistant steel (SUH35, etc.), ferritic heat resistant steel (SUH446, etc.) and the like. Further, Ni-based heat-resistant alloys such as Inconel (NCF751 etc.) are also included.
Aluminum alloys include pure aluminum (1000s), Al-Cu alloys (2000s), Al-Mn alloys (3000s), Al-Si alloys (4000s), Al-Mg alloys ( 5000 series), Al-Mg-Si based alloys (6000 series), Al-Zn-Mg based alloys (7000 series), and the like. The composition of the alloy is not particularly limited.

The shape of the substrate is not particularly limited, and for example, the shape can be arbitrarily set according to the shape of a member used as a gas flow member, etc., but at least in the portion where the gas flows, A ceramic coat layer is preferably formed. Specific examples of the gas distribution member include engine members such as an intake port, an exhaust port, an engine valve, and a piston. The substrate may be a plate-like body such as a flat plate, a curved plate, a bent plate, or a cone such as an umbrella type or a mushroom type.

The surface of the substrate is preferably subjected to a roughening treatment. This is because the surface area is increased by the roughening treatment, and the adhesion between the substrate and the ceramic coat layer is increased.
The surface roughness (Ra) of the roughened substrate is preferably 0.05 to 10 μm.
When the surface roughness (Ra) is less than 0.05 μm, an increase in the surface area of the substrate does not contribute much to an increase in adhesion. On the other hand, when the surface roughness (Ra) exceeds 10 μm, air is likely to intervene between the ceramic coat layer formed on the substrate surface and the substrate surface, and the adhesion with the ceramic coat layer is reduced. .

Next, the alumite layer that may be formed on the substrate surface will be described.
The method for forming the alumite layer on the base material is not particularly limited, and a conventionally known method can be used. For example, the base material is used as an anode and an electric current is supplied in an electrolytic bath. A method of forming an alumite layer by [alumite treatment (also referred to as anodizing treatment)] can be applied.
When alumite treatment is performed on a part of the base material, it is preferable to protect by masking tape or the like on a portion where the alumite treatment is not performed.

The thickness of the alumite layer is preferably 0.2 to 100 μm.
If the thickness of the alumite layer is less than 0.2 μm, the thickness of the alumite layer is too thin, and the effect of improving the adhesion with the ceramic coat layer may be hardly obtained. On the other hand, if the thickness of the alumite layer exceeds 100 μm, it takes too much time to form the alumite layer, which is uneconomical. The thickness of the alumite layer is more preferably 10 to 50 μm.
In addition, the thickness of an alumite layer can be measured by observing the cross section of a coat metal base material using SEM etc.

An alumite layer is a layer of a composite oxide of aluminum oxide or aluminum oxide and another metal oxide formed by oxidation of a metal substrate made of aluminum or an aluminum alloy. The base material and the alumite layer are in close contact with each other because they are chemically bonded via oxygen.

As the current waveform during electrolysis, direct current, alternating current, AC / DC superimposition, AC / DC combined use, incomplete rectification waveform, pulse waveform, rectangular wave, and the like can be used.
Moreover, as an electrolysis method, a constant current, a low voltage, a constant power method, a high-speed alumite method applying continuous, intermittent, or current recovery can be used.

Next, the ceramic coat layer will be described.
The ceramic coat layer is made of a ceramic raw material, and examples of the ceramic raw material include amorphous inorganic materials.
The amorphous inorganic material is preferably made of glass, and more preferably made of low softening point glass having a softening point of 250 to 550 ° C.
Examples of the low softening point glass having a softening point of 250 to 550 ° C. include SiO ₂ —TiO ₂ glass, SiO ₂ —PbO glass, SiO ₂ —PbO—B ₂ O ₃ glass, and B ₂ O ₃ —PbO glass. Al ₂ O ₃ —SiO ₂ —B ₂ O ₃ —PbO glass, Na ₂ O—P ₂ O ₅ —SiO ₂ glass, and the like.
The softening point is measured using, for example, a glass automatic softening point / strain point measuring device (SSPM-31) manufactured by Opt Corporation, based on the method specified in JIS R 3103-1 (2001). be able to.

The ceramic coat layer may further contain a crystalline inorganic material in addition to the ceramic raw material described above.
The crystalline inorganic material is preferably made of at least one selected from the group consisting of alumina, zirconia, titania, lanthania, samaria, silica, yttria, calcia, magnesia, ceria, and hafnia.

The thickness of the ceramic coat layer is preferably 10 to 1000 μm, more preferably 10 to 600 μm, and even more preferably 10 to 200 μm.
If the thickness of the ceramic coat layer is less than 10 μm, the thickness of the ceramic coat layer is too thin, so that the coated metal substrate cannot exhibit sufficient heat insulation. On the other hand, if the thickness of the ceramic coat layer exceeds 1000 μm, cracks may easily occur when a thermal shock or the like is applied to the ceramic coat layer.

Next, a method for producing the coated metal substrate of the present invention will be described.
The coated metal substrate of the present invention includes, for example, a substrate preparation step for preparing a substrate made of metal, and a ceramic coat layer formed by applying a ceramic coat material made of a ceramic material and a surfactant on the substrate. It can be produced by a coating layer forming step for forming a coating layer for forming and a firing step in which the substrate on which the coating layer is formed is fired at a predetermined temperature to form a ceramic coat layer.

Hereinafter, the above-described substrate preparation step, coating layer forming step, and firing step will be described.

(A) Substrate preparation step In the substrate preparation step, a substrate made of metal is prepared.

Since the shape, material, and the like of the base material are the same as those described in the description of the coated metal base material of the present invention, the description thereof is omitted here.

First, in the base material preparation step, it is preferable to perform a cleaning process to remove impurities on the surface of the base material.
The cleaning treatment is not particularly limited, and a conventionally known cleaning treatment method can be used. Specifically, for example, a method of performing ultrasonic cleaning in an alcohol solvent can be used.

When it is desired to further improve the adhesion between the substrate and the ceramic coat layer, a roughening treatment may be applied to the portion where the ceramic coat layer is formed. Examples of the roughening treatment include sand blast treatment, etching treatment, high temperature oxidation treatment, and alkali treatment. These may be used alone or in combination of two or more. You may perform a washing process after this roughening process.
In addition, it is preferable to perform a roughening process ahead of the coating layer formation process mentioned later.

When the substrate is a substrate made of aluminum or an aluminum alloy, the substrate surface is preferably subjected to an alumite treatment.
By applying the alumite treatment, an alumite layer can be formed on the surface of the substrate, and the adhesion between the substrate and the ceramic coat layer can be further improved.
When alumite treatment is performed on a part of the substrate, it is preferable to protect it by attaching a masking tape or the like to a portion where the alumite treatment is not performed.
In addition, it is preferable to perform an alumite process before the coating layer formation process mentioned later.

As the electrolytic bath used for the alumite treatment, an alkaline bath or a non-aqueous bath such as formamide and boric acid can be used in addition to the acidic bath. Acid baths include sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfosalicylic acid, pyrophosphoric acid, sulfamic acid, phosphomolybdic acid, boric acid, malonic acid, succinic acid, maleic acid, citric acid, tartaric acid, phthalic acid, itacone An aqueous solution in which one or two or more acids, malic acid, glycolic acid and the like are dissolved can be used.
Moreover, as an alkaline bath, the aqueous solution which melt | dissolved 1 type, or 2 or more types of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium phosphate, ammonia water etc. can be used.
By the alumite treatment, an alumite layer having a thickness of 0.2 to 100 μm is formed on the surface of the substrate.

(B) Coating layer forming step (b-1) Ceramic coating material preparation step Subsequently, a ceramic coating material for forming a coating layer is prepared.
A ceramic coating material is obtained by mixing the ceramic material and the surfactant.
The surfactant that is mixed with the ceramic raw material to constitute the ceramic coating raw material may be a liquid or a solid.

Since the ceramic raw material is the same as that described in the description of the coated metal substrate of the present invention, the description thereof is omitted here.

The ceramic coating raw material can be obtained, for example, by mixing a ceramic raw material, a surfactant, and water and wet-mixing with a ball mill or the like. The order and combination of mixing the three components are not particularly limited. For example, the ceramic raw material and water may be mixed first, and a surfactant may be further added. May be added, or the ceramic raw material, surfactant and water may be mixed at once.
The surfactant is a general term for substances having a hydrophilic group and a hydrophobic group in the molecule, and the kind thereof is not particularly limited, and may be a liquid or a solid.

The surfactant contained in the ceramic coat raw material undergoes thermal decomposition in the subsequent firing step to form pores. That is, the surfactant functions as a pore forming agent.

The mixing ratio of the ceramic raw material and water is not particularly limited, but about 100 parts by weight of water is preferable with respect to 100 parts by weight of the ceramic raw material. This is because when the ceramic raw material and water are mixed in such a weight ratio, a viscosity suitable for application to a metal substrate is likely to be obtained. Moreover, you may mix | blend dispersion media, such as an organic solvent, and an organic binder with the said ceramic coat raw material as needed.

As the dispersion medium, for example, water or an organic solvent such as methanol, ethanol, or acetone can be used. The content of the dispersion medium in the ceramic coating raw material is not particularly limited. For example, the dispersion medium is preferably 50 to 150 parts by weight with respect to 100 parts by weight of the ceramic raw material. This is because, by blending the dispersion medium in such a ratio, the viscosity of the ceramic coat raw material becomes a viscosity suitable for application to the substrate.
Examples of the organic binder include polyvinyl alcohol, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, and the like. These may be used alone or in combination of two or more. Further, a dispersion medium and an organic binder may be used in combination.

The content of the surfactant in the ceramic coating raw material is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight in terms of solid content, based on the total amount of the ceramic coating raw material. Preferably, it is 0.5 to 3% by weight.
When the content of the surfactant is less than 0.1% by weight, a sufficient amount of pores may not be formed in the ceramic coat layer. On the other hand, when the content of the surfactant exceeds 10% by weight, the amount of the surfactant to be added is too large, and a large amount of pores may be formed and connected to each other. Such pores do not become pores uniformly dispersed in the ceramic coat layer, and there is a possibility that the heat insulation performance and the mechanical strength are lowered.

The surfactant is preferably a water-soluble surfactant.
When the surfactant is water-soluble, it is excellent in self-dispersibility in the softened ceramic raw material, and it becomes easy to form uniform pores. Therefore, a ceramic coat layer having high heat insulation performance can be obtained. Further, the type of the surfactant is not particularly limited, and any anionic, cationic or nonionic surfactant may be used, but self-dispersibility and formation of uniform pores in the ceramic raw material. From the viewpoint, it is more preferable to use an anionic surfactant.
Examples of the anionic surfactant include polycarboxylic acid and / or salt thereof, naphthalene sulfonate formalin condensate and / or salt thereof, polyacrylic acid and / or salt thereof, polymethacrylic acid and / or salt thereof, polyvinyl Examples thereof include sulfonic acid and / or a salt thereof.
The water-soluble surfactant is one having an HLB value of 8.0 or more in the Griffin method.

The thermal decomposition temperature of the surfactant is preferably 200 to 600 ° C.
When the thermal decomposition temperature of the surfactant is within the above range, pores uniformly dispersed in the ceramic coat layer are easily formed.
If the thermal decomposition temperature is lower than 200 ° C., the thermal decomposition of the surfactant may be completed before the ceramic raw material constituting the ceramic coating raw material is softened in the initial stage of the firing process. In such a case, the decomposition gas generated by the thermal decomposition of the surfactant diffuses into the firing atmosphere and cannot form pores. On the other hand, it is technically difficult to set the thermal decomposition temperature to a value exceeding 600 ° C.
The thermal decomposition temperature of the surfactant is a temperature at which the weight of the surfactant is decreased by 5% by weight as measured by thermogravimetric analysis (TGA).

If necessary, a crystalline inorganic material may be further added to the ceramic coat raw material.
When the crystalline inorganic material is added to the ceramic coating raw material, the timing of adding the crystalline inorganic material is not particularly limited. For example, before mixing the ceramic raw material, the surfactant, and water, the ceramic raw material and the crystalline material are mixed. You may have the process of mixing an inorganic material.
Since the crystalline inorganic material is the same as that described in the description of the coated metal substrate of the present invention, the description thereof is omitted here.
In addition, when adding a crystalline inorganic material further as a ceramic coat raw material, you may have the process of mixing a ceramic raw material and a crystalline inorganic material, before mixing a ceramic raw material, surfactant, and water mentioned above. .

(B-2) Coating step Next, as a coating step, a coating layer for forming a ceramic coating layer is formed by coating a ceramic coating material for forming a ceramic coating layer on a substrate.

The thickness of the coating layer is not particularly limited, but is preferably 10 to 1000 μm, and is preferably thick enough to form a ceramic coat layer having a thickness of 10 to 200 μm.
When the thickness of the coating layer is less than 10 μm, the thickness of the formed ceramic coating layer is too thin, and the coated metal substrate may not be able to exhibit sufficient heat insulation.
On the other hand, when the thickness of the coating layer exceeds 1000 μm, the thickness of the formed ceramic coat layer becomes too thick, and cracks may easily occur when a thermal shock is applied to the ceramic coat layer.

Examples of the method for forming the coating layer on the substrate include spray coating, electrostatic coating, inkjet, transfer using a stamp or roller, brush coating, and the like.

(C) Firing step Next, as a firing step, the substrate on which the coating layer is formed is fired at 300 to 600 ° C. to form a ceramic coat layer on the surface of the substrate.
The firing temperature is preferably equal to or higher than the softening point of the amorphous inorganic material. By setting the firing temperature to a temperature equal to or higher than the softening point of the amorphous inorganic material, the applied amorphous inorganic material is softened and melted, and the formed ceramic coat layer and the substrate are firmly adhered.
At this time, the surfactant contained in the ceramic coat raw material is dispersed in the softened ceramic raw material, and pores are formed by causing thermal decomposition.
Since the surfactant has self-dispersibility, it can be widely dispersed in the softened ceramic raw material to form uniformly dispersed pores in the ceramic coat layer. Furthermore, since the pores formed by the decomposition of the surfactant are directly surrounded by the ceramic coat layer, the generation of foreign matters can be suppressed, and the deterioration of heat insulation performance and the generation of cracks can be suppressed.
Further, when pores are exposed on the surface of the ceramic coat layer during firing, the ceramic raw material forming the ceramic coat layer is softened, so that the exposed portions of the pores can be closed quickly. Therefore, pores are not exposed on the surface of the fired ceramic coat layer, and a ceramic coat layer with high flatness (low surface roughness) can be obtained.
When the alumite layer is formed on the substrate surface, the ceramic coat layer and the alumite layer are in close contact with each other, and the ceramic coat layer penetrates into the irregularities such as cracks formed in the alumite layer, It adheres more firmly to the base material and alumite layer.

The effects of the coated metal substrate of the present invention are listed below.
(1) In the coated metal substrate of the present invention, pores are uniformly dispersed in the ceramic coat layer formed on the substrate. Therefore, it is excellent in heat insulation performance and thermal shock resistance.

(2) Since the pores are directly surrounded by the ceramic coat layer in the coated metal substrate of the present invention, it is difficult for foreign matter to enter the pores, and the pores can be prevented from being broken from the inside. Therefore, it is possible to suppress the deterioration of the heat insulating performance of the coated metal substrate and the occurrence of cracks.

(3) Since the surface roughness (Ra) of the ceramic coat layer is 8 μm or less in the coated metal substrate of the present invention, the flow of fluid flowing on the surface of the coated metal substrate is hardly disturbed, and the thermal conductivity Can be kept low.

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

(Example 1)
(A) Substrate preparation step A plate (150 mm × 70 mm × 0.5 mmt) made of aluminum (A1050) is prepared as a substrate, and ultrasonic cleaning is performed in an alcohol solvent, followed by sand blasting. The surface (both sides) of the material was roughened. The sand blasting process was performed for 60 minutes using Al ₂ O ₃ abrasive grains. Thereby, the surface roughness (Ra) measured based on JIS B 0601 (2001) on the surface of the substrate was 1.0 μm.

(B) Coating layer forming step (b-1) Ceramic coat raw material preparing step SiO ₂ —TiO ₂ glass (softening point 400 ° C.) was prepared as a powder of an amorphous inorganic material.
Methylcellulose was prepared as an organic binder.
A polycarboxylic acid type surfactant was prepared as the surfactant.
In the preparation of the raw material mixture, 2 parts by weight of a surfactant is added to 100 parts by weight of the amorphous inorganic material powder, 100 parts by weight of water is further added, and a slurry is prepared by wet mixing with a ball mill. The raw material was obtained.

(B-2) Coating process A ceramic coating material was coated on the surface of a flat substrate by spray coating.
The coating time was adjusted so that the fired ceramic coating layer had a thickness of 330 μm, and the coating was dried in a dryer at 100 ° C. for 60 minutes.

(C) Firing Step After the above step, a ceramic coat layer was formed by heating in a heating furnace at 520 ° C. for 10 minutes in the air to obtain a coated metal substrate according to Example 1. Thereafter, the surface of the coated metal substrate was cut vertically, and the cross section thereof was photographed by SEM. The obtained photograph is shown in FIG. Note that the chipping of the ceramic coat layer seen in the upper left part of FIG. 3 is missing when the ceramic coat layer is cut in order to take an SEM image.

(Example 2)
(C) A coated metal substrate according to Example 2 was obtained in the same manner as in Example 1 except that heating was performed at 560 ° C. for 60 minutes in the firing step.

(Comparative Example 1)
(C) In the firing step, a coated metal substrate according to Comparative Example 1 was obtained in the same manner as in Example 1 except that heating was performed at 610 ° C. for 10 minutes.

(Evaluation of properties of coated metal substrate)
About the coated metal base material manufactured by each Example and the comparative example, the characteristic was evaluated in the following procedures.

(Verification of pore dispersibility and measurement of film thickness)
The surface of the coated metal substrate produced in each of the examples and comparative examples was cut vertically, and five sections were randomly selected and photographed by SEM. Whether each of the obtained SEM images is divided into nine regions by the method described above, and the pores are uniformly dispersed by counting the number of pores having a pore diameter of 0.1 μm or more in each region. It was confirmed. The results are shown in Table 1. The case where the pores are uniformly dispersed is indicated by ◯, and the case where the pores are not uniformly dispersed is indicated by ×.
Furthermore, the thickness of the ceramic coat layer was measured at 10 locations randomly selected from the five SEM images, and this average value was taken as the thickness (film thickness) of the ceramic coat layer. The results are shown in Table 1.

(Measurement of porosity)
Using the same SEM image used for confirming the dispersibility of the pores, the ratio of the pores shown in the ceramic coat layer was determined. The average value of the ratio of the pores in the five SEM images was determined as the porosity. The results are shown in Table 1.

(Measurement of pore diameter)
Using the same SEM image used to confirm the dispersibility of the pores, measure the size of all pores (pore size) by visual observation, and measure the average pore size by averaging the obtained numerical values. did. The results are shown in Table 1.

(Measurement of surface roughness)
For the coated metal substrates produced in the examples and comparative examples, the surface roughness Ra of the ceramic coat layer was measured using a surface roughness measuring machine (manufactured by Tokyo Seimitsu Co., Ltd., Handy Surf E-35B). The results are shown in Table 1.

(Measurement of thermal conductivity)
(B-1) In each example and comparative example, the ceramic coat raw material prepared in the ceramic coat raw material preparation step is applied on an aluminum plate placed on a horizontal surface and fired under the same conditions as in each example and comparative example. Thus, test pieces for measuring thermal conductivity according to Example 1, Example 2, and Comparative Example 1 were prepared. The film thickness of the test piece for measuring thermal conductivity was 330 μm for the test piece according to Example 1, and 700 μm for the test piece according to Example 2 and the test piece according to Comparative Example 1. About this test piece, it measured based on JISR1611 (2010) using the laser flash apparatus (thermal constant measuring apparatus: NETZSCH LFA457 Microflash), and measured the heat conductivity of the thickness direction of the ceramic coat layer. The results are shown in Table 1. However, the test piece according to Comparative Example 1 was brittle and cracked when installed in the laser flash device, and the thermal conductivity could not be measured.

From the above results, it was found that the coated metal substrate of the present invention was excellent in heat insulating properties because the pores were uniformly dispersed in the ceramic coat layer.

DESCRIPTION OF SYMBOLS 10 Coated metal base material 11 Base material 12 Ceramic coat layer 12a Surface of ceramic coat layer 13 Pore

Claims

A coated metal substrate in which a ceramic coat layer made of a ceramic raw material is formed on a metal substrate,
In the ceramic coat layer, uniformly dispersed pores are formed, and the surface roughness (Ra) of the ceramic coat layer is 8 μm or less,
The coated metal base material, wherein the pores are directly surrounded by the ceramic coat layer.
The coated metal substrate according to claim 1, wherein the metal is aluminum or an aluminum alloy.
An alumite layer is formed on the surface of the substrate,
The coated metal substrate according to claim 2, wherein the ceramic coat layer is formed on the substrate on which the alumite layer is formed.
The coated metal substrate according to any one of claims 1 to 3, wherein a softening point of the ceramic raw material is 250 to 550 ° C.
The coated metal substrate according to any one of claims 1 to 4, wherein the ceramic coat layer further contains a crystalline inorganic material.
6. The coated metal group according to claim 5, wherein the crystalline inorganic material is at least one selected from the group consisting of alumina, zirconia, titania, lanthania, samaria, silica, yttria, calcia, magnesia, ceria, and hafnia. Wood.
The coated metal substrate according to any one of claims 1 to 6, wherein the ceramic coat layer has a thickness of 10 to 1000 袖 m.
When the thickness of the ceramic coat layer is 5 μm or more and less than 50 μm, it is 2000 times when the thickness of the ceramic coat layer is 5 μm or more and less than 100 μm, and when the thickness is 50 μm or more and less than 100 μm, it is 1000 times, or 100 μm or more and less than 300 μm. Of the ceramic coating layer photographed at a magnification of 500 times, 200 times when 300 μm or more and less than 500 μm, 150 times when 500 μm or more and less than 1000 μm, and 100 times when 1000 μm or more and less than 2000 μm. Scanning electron microscope images in the cross section are randomly selected as five rectangular areas with the vertical length being the thickness of the ceramic coat layer and the horizontal length being 1.5 times the thickness of the ceramic coat layer. In addition, when the rectangular area is equally divided into 9 areas each of 3 × 3 in the vertical direction, for a total of 45 areas,
The coated metal substrate according to any one of claims 1 to 7, wherein all of the 45 regions have 10 or more pores having a pore diameter of 0.1 µm or more.