CN110958994A

CN110958994A - Ceramic coating with functional micro-nano structure on surface and preparation method thereof

Info

Publication number: CN110958994A
Application number: CN201880000793.3A
Authority: CN
Inventors: 徐少林; 徐康; 卢勇光; 徐光明; 袁丹丹
Original assignee: Southwest University of Science and Technology
Current assignee: Southwest University of Science and Technology; Southern University of Science and Technology
Priority date: 2018-07-10
Filing date: 2018-07-10
Publication date: 2020-04-03
Also published as: WO2020010524A1

Abstract

A preparation method of a ceramic coating comprises the following steps: providing an alkyl resin solution; the alkyl resin solution contains an alkyl resin; providing a substrate, depositing an alkyl resin solution on the substrate; providing a template, wherein a first micro-nano structure is arranged on the surface of the template; contacting one surface of the template provided with the first micro-nano structure with one surface of the substrate deposited with an alkyl resin solution, and carrying out imprinting treatment; separating the substrate from the template, and then carrying out pyrolysis treatment to obtain a ceramic coating with a second micro-nano structure on the surface; the first micro-nano structure and the second micro-nano structure are complementary in space. A ceramic coating is also disclosed.

Description

Ceramic coating with functional micro-nano structure on surface and preparation method thereof

Technical Field

The invention belongs to the technical field of micro-nano processing, and particularly relates to a ceramic coating with a functional micro-nano structure on the surface and a preparation method thereof.

Background

In the technical field of micro-nano processing and manufacturing, the minimum size resolution of a laboratory process can reach 10nm, and the micro-nano surface structure processing and manufacturing in industry is widely applied.

The existing micro-nano processing technology has the following defects: firstly, the traditional micro-nano manufacturing process cannot efficiently prepare a high-quality micro-nano structure on the surface of a ceramic material at low cost, and the micro-nano structure prepared on the surface of other materials by the traditional process has poor limit performances such as high-temperature mechanical properties, wear resistance, corrosion resistance and the like, so that the micro-nano structure cannot work in a limit environment, such as but not limited to an engine cylinder with high-temperature and high-frequency reciprocating motion, a micro-channel system in a strong corrosion environment and the like. Secondly, a series of functionalities can be obtained by designing and preparing the micro-nano structure on the surface of the ceramic material, for example, the wear resistance of the ceramic bearing in a lubricating state can be obviously improved by the surface micro-texture, and the friction coefficient of the ceramic bearing can be reduced.

Nanoimprint can be used for preparing high-quality surface micro-nano structures with high efficiency and low cost, and has already received wide attention of researchers; among the materials known to us, ceramics are widely studied and used in many fields because of their remarkable properties of high temperature resistance, wear resistance and corrosion resistance. In the research results at home and abroad, the patent 'a method for patterning the surface of a functional ceramic material' (application number: 201610685050.7) shows that the method is adopted to add metal oxide nano-particles into the traditional photoresist, and a ten-micron-sized oxide ceramic surface structure is obtained through traditional imprinting and high-temperature sintering, so the appearance of the results is poor. At present, no corresponding report that the ceramic coating with the good-appearance micro-nano structure can be prepared on the surface of various substrates with high efficiency and low cost is found.

Technical problem

The invention aims to overcome the defects in the prior art, and provides a ceramic coating and a preparation method thereof, so as to solve the technical problem that the ceramic coating with a micro-nano structure cannot be prepared efficiently at low cost in the prior art.

Technical solution

In order to achieve the purpose, the invention adopts the following technical scheme:

in one aspect, the present invention provides a method for preparing a ceramic coating, comprising the steps of:

providing an alkyl resin solution; the alkyl resin solution contains an alkyl resin;

providing a substrate, depositing the alkyl resin solution on the substrate;

providing a template, wherein a first micro-nano structure is arranged on the surface of the template; contacting one surface of the template provided with the first micro-nano structure with one surface of the substrate deposited with the alkyl resin solution, and carrying out imprinting treatment;

separating the substrate from the template, and then carrying out pyrolysis treatment to obtain a ceramic coating with a second micro-nano structure on the surface;

the first micro-nano structure and the second micro-nano structure are complementary in space.

In another aspect, the present invention also provides a ceramic coating, which is prepared by the above preparation method of the present invention.

Advantageous effects

The preparation method of the ceramic coating provided by the invention is based on a precursor derivation method and a micro-nano imprinting process, and is used for preparing the ceramic coating with high performance and a micro-nano structure on the surface. The preparation method has the advantages of simple process, low cost and high efficiency, and has the conditions of mass production and large-area production, and the finally obtained ceramic coating has better mechanical property and potential of being used under various limit conditions, such as high-temperature creep resistance, high-temperature hardness, abrasion resistance and corrosion resistance.

The ceramic coating provided by the invention is provided with a micro-nano structure on the surface and is prepared by the preparation method provided by the invention. The ceramic coating combines the performance of the ceramic material and the performance of the micro-nano structure, so that the ceramic coating prepared by taking the alkyl resin as the raw material has better mechanical performance and has the potential of being used under various limit conditions (such as high-temperature creep resistance, high-temperature hardness, abrasion resistance, corrosion resistance and the like).

Drawings

FIG. 1 is a diagram showing a process for preparing a ceramic coating according to example 1 of the present invention;

FIG. 2 is an AFM image of a ceramic coating obtained in example 1 of the present invention;

FIG. 3 is a Fourier infrared spectrum of the ceramic coating obtained in example 1 of the present invention;

FIG. 4 is a graph of nano-indentation mechanical test results of the ceramic coating obtained in example 1 of the present invention;

FIG. 5 is a diagram showing a process for preparing a ceramic coating obtained in example 2 of the present invention;

FIG. 6 is an SEM photograph of a ceramic coating obtained in example 2 of the present invention;

FIG. 7 is a graph of the nano-indentation mechanical test results of the ceramic coating obtained in example 2 of the present invention.

Modes for carrying out the invention

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The embodiment of the invention provides a preparation method of a ceramic coating on one hand, which comprises the following steps:

s01: providing an alkyl resin solution; the alkyl resin solution contains an alkyl resin;

s02: providing a substrate, depositing the alkyl resin solution on the substrate;

s03: providing a template, wherein a first micro-nano structure is arranged on the surface of the template; contacting one surface of the template provided with the first micro-nano structure with one surface of the substrate deposited with the alkyl resin solution, and carrying out imprinting treatment;

s04: separating the substrate from the template, and then carrying out pyrolysis treatment to obtain a ceramic coating with a second micro-nano structure on the surface;

The preparation method of the ceramic coating provided by the embodiment of the invention is based on a precursor derivation method and a micro-nano imprinting process, and is used for preparing the ceramic coating with high performance and a micro-nano structure on the surface. The preparation method has the advantages of simple process, low cost and high efficiency, and has the conditions of mass production and large-area production, and the finally obtained ceramic coating has better mechanical property and potential of being used under various limit conditions, such as high-temperature creep resistance, high-temperature hardness, abrasion resistance and corrosion resistance.

The alkyl resin in the alkyl resin solution of the embodiment of the invention has certain sensitivity to light or heat, is a resin containing alkyl and is liquid at normal temperature, and can be converted into a compact ceramic material through chemical and physical changes under certain conditions. As a preferred embodiment, the alkyl resin is thermally cured, specifically, the alkyl resin solution containing the alkyl resin is deposited on the substrate and subjected to high-temperature imprinting treatment (preferably at 140-; according to another embodiment, the alkyl resin is subjected to photocuring, specifically, an alkyl resin solution containing the alkyl resin and a photoinitiator is deposited on a substrate to be subjected to imprinting treatment, then, under the photoinitiator, the photocrosslinking reaction is promoted to be cured, and the micro-nano structure is replicated and then, the micro-nano structure is pyrolyzed to obtain the ceramic coating. Further preferably, the alkyl resin includes at least one of silane, polysilazane, polysiloxane, polysilazane, and polysilaborane.

Specifically, in the above step S01 of the embodiment of the present invention, the alkyl resin solution further contains a photoinitiator for promoting a photo-crosslinking reaction, and after the step of imprint processing of step S03, a step of photo-curing processing is further included. And carrying out photocuring treatment on the substrate and the template which are subjected to the imprinting treatment together to finish the photocuring process.

The photoinitiator is selected corresponding to the alkyl resin, and the alkyl resin is subjected to photo-crosslinking reaction under the initiation of the photoinitiator in the process of being subjected to photo-curing treatment, so that the alkyl resin solution is cured into a film. The photoinitiator is generally selected from photoinitiator types with faster crosslinking and curing speed, and includes but is not limited to at least one of Irgacure-651 (benzoin diethyl ether), Irgacure-184 (1-hydroxycyclohexyl phenyl ketone), Irgacure-1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone), and Irgacure 819 (phenyl phosphine oxide). The alkyl resin includes, but is not limited to, at least one of silane, polysilazane, polysiloxane, polysilazane, and methyl-vinyl polysilazane is preferred in the embodiments of the present invention. The mass ratio of the photoinitiator to the alkyl resin is (3-6): 100. the photoinitiator and the alkyl resin are mixed in the mass ratio range, and the curing speed is high.

Further, the process of the photo-curing treatment includes ultraviolet irradiation. Specifically, the substrate after the hot embossing treatment and the template may be placed together under an ultraviolet lamp for irradiation. The ultraviolet lamp wavelength includes, but is not limited to, 405nm and 365nm, the power and the lumen have no influence on the light curing speed, and the preferable irradiation time range is 3-10 seconds, and in the time range, the alkyl resin in the alkyl resin solution can better perform a crosslinking curing reaction to complete the light curing step of forming the film by the alkyl resin solution.

Furthermore, the alkyl resin solution also contains a modifier for improving the crosslinking reaction density. The modifier can improve the photocuring efficiency, thereby improving the curing density, further improving the compactness and strength of the coating, inhibiting side reaction and improving the stability of the alkyl resin solution, namely under the condition of simultaneously containing alkyl resin, photoinitiator and modifier, the comprehensive effect of photocuring crosslinking of the alkyl resin is better. Preferably, the modifier comprises at least one of pentaerythritol triacrylate PETA, methacrylate, ethyl acrylate, pentaerythritol tetrakis (3-mercaptopropionate). Preferably, the mass ratio of the modifier to the alkyl resin is (6-12): 100, i.e. the mass ratio of the modifier to the photoinitiator may be 2: 1. the modifier has the best effect of inhibiting side reactions within the mass ratio range.

Further, in the step S02, the material of the substrate includes any one of a metal material, a ceramic material, and a semiconductor material. Namely, the ceramic coating can be directly prepared on the surface of the ceramic material and also can be prepared on a substrate made of other materials. The alkyl resin solution may be deposited on the substrate in a variety of ways, including but not limited to spin coating, pulling, or dipping. If a spin coating process is used, the spin coating conditions may be 500rpm for 6s and then 2500rpm for 10s, so that the alkyl resin solution can be uniformly spin-coated on the substrate.

Further, in the step S03, the template material includes, but is not limited to, any one of PDMS (polydimethylsiloxane) and photoresist; the photoresist comprises SU-8 photoresist, mr-UVCur06, mr-UVCur21 and the like. The template is made of soft material and is very suitable for imprinting treatment. The surface of the template is provided with a first micro-nano structure, and graph transcription can be completed under certain temperature, humidity and pressure conditions. The conditions for pattern transfer are adjusted according to the viscosity of the alkyl resin solution, etc., and preferably, the pressure of the imprint treatment is 0.8 to 1.2 MPa. Under the pressure condition, the alkyl resin solution can be better filled into the micro-nano structure of the template, so that the second micro-nano structure on the surface of the final ceramic coating is more complete, in a specific embodiment, for example, the template graph can be better copied by stamping for 20-30s under the low pressure of 0.5-0.7MPa and then stamping for 20-30min under the high pressure of 0.8-1.2MPa, and the copying effect is optimal. More preferably, the temperature of the imprinting process is 140-160 ℃. Under the temperature condition, the alkyl resin solution can only contain alkyl resin, and the alkyl resin can be directly solidified through thermal crosslinking reaction, for example, hot stamping can be carried out for 20-30s at 140-160 ℃ under the low pressure of 0.5-0.7MPa, and then stamping can be carried out for 20-30min under the high pressure of 0.8-1.2 MPa.

Further, in order to better deposit the alkyl resin solution on the substrate, the method further comprises the step of sequentially performing a first cleaning process and a first drying process on the substrate before the step of depositing the alkyl resin solution on the substrate. Wherein the first cleaning treatment comprises soaking the substrate in absolute ethyl alcohol for 20-40min (the temperature can be preferably 20-40 ℃), and the conditions for performing the first drying treatment after the substrate surface cleaning are finished comprise: the temperature is 80-100 deg.C, and the time is 3-5 min. More preferably, the drying may be performed in a clean air environment. Under the conditions of the above-described first cleaning process and first drying process, a cleaner substrate can be obtained, so that the alkyl resin solution can be better deposited on the substrate.

Meanwhile, in order to better copy the micro-nano structure, before the steps of contacting the template with the substrate and carrying out hot embossing treatment, the method also comprises the step of sequentially carrying out second cleaning treatment and second drying treatment on the template. Wherein the second cleaning process comprises: soaking the template in a mixed solution containing anhydrous ethanol and a surfactant for 20-40min (the temperature can be preferably 20-40 ℃); the surfactant is selected from at least one of ethoxylated sodium alkyl sulfate and dodecylbenzene sulfonic acid. The surfactant can remove impurities on the template, so that the template is cleaned more thoroughly, and the subsequent process is facilitated. More preferably, the mass ratio of the absolute ethyl alcohol to the surfactant is 10: (1-2) in the above range, the surfactant is most effective. After the substrate surface is cleaned, the conditions for performing the first drying treatment include: the temperature is 25-30 deg.C, and the time is 3-5 min. More preferably, the drying may be performed in a clean air environment. Under the conditions of the second cleaning treatment and the second drying treatment, a purer template can be obtained, and the micro-nano structure can be better copied.

Further, in step S04, after the substrate is separated from the template by demolding, an alkyl resin coating (i.e., a preformed ceramic coating that is not converted) with a second micro-nano structure remains on the substrate; and (3) carrying out separation pyrolysis treatment on the alkyl resin coating, and decomposing and volatilizing solvents, redundant molecules and the like in the alkyl resin coating so as to finish the conversion from precursors to ceramics and form a mature ceramic coating. Preferably, the temperature of the pyrolysis treatment is 900-1500 ℃, and the time is 1-2 h. More preferably, the pyrolysis treatment comprises: heating to 900-. Under the preferred pyrolysis treatment conditions, the alkyl resin coating can be pyrolyzed better, so that the solvent and the redundant molecules in the alkyl resin coating can be completely decomposed and volatilized to form a complete ceramic coating.

Further, the pyrolysis treatment may be performed in a pure gas environment, such as argon, nitrogen, ammonia, and the like. Namely, after the substrate and the template are demolded and separated, the substrate is placed in the gas environment for pyrolysis treatment, and the pyrolysis effect is better.

In another aspect, the embodiments of the present invention further provide a ceramic coating, which is prepared by the preparation method described in the embodiments of the present invention.

The ceramic coating provided by the embodiment of the invention is prepared by the preparation method provided by the embodiment of the invention. The ceramic coating provided by the embodiment combines the performance of the ceramic material and the performance of the micro-nano structure, so that the ceramic coating prepared by taking alkyl resin as a raw material has better mechanical performance and has the potential of being used under various limit conditions (such as high-temperature creep resistance, high-temperature hardness, abrasion resistance, corrosion resistance and the like).

The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.

Example 1

As shown in fig. 1, a method for preparing a ceramic coating with a micro-nano structure on the surface comprises the following specific steps:

step 1: preparing an alkyl resin solution coating on a substrate, and preparing a uniform alkyl resin solution containing alkyl resin (methyl-vinyl polysilazane), a photoinitiator and a modifier; spin-coating an alkyl resin solution on a monocrystalline silicon wafer substrate under the following spin-coating conditions: 500rpm for 6s, then 1500rpm for 10s (see FIGS. 1a, 1 b);

step 2: copying a micro-nano structure, namely covering a soft PDMS template on a substrate which is spin-coated with a base resin solution, wherein the soft PDMS template is provided with a micron-scale columnar array structure which is in a hexagonal arrangement column shape, one surface provided with the micron-scale columnar array structure is contacted with the substrate, and then completing graph transcription by keeping the low pressure of 0.7MPa for 30s and the high pressure of 1.05MPa for 30min (see figure 1 c);

and step 3: photocuring, namely performing illumination treatment on the substrate and the template subjected to the imprinting treatment under the condition of illumination for 20s under the ultraviolet light with the wavelength of 405nm to perform crosslinking reaction to finish the photocuring process; (see FIG. 1 d)

And 4, step 4: demolding, releasing the template from the substrate, and leaving the cured alkyl resin on the substrate (see fig. 1 e);

and 5: high temperature pyrolysis, placing the substrate in a tubular furnace protected by nitrogen, heating to 1000 deg.C at a heating rate of 5 deg.C/min, and maintaining at 1000 deg.C for 1 hr (as shown in FIG. 1d, in the process, the alkyl resin, methyl-vinyl polysilazane, is pyrolyzed to produce ceramic Si_xC_yN_z _；The product contains trace amounts of O, x: y: z is 1: 0.800: 1.202), cooling to room temperature at a cooling rate of 5 ℃/min; a ceramic coating with a micro-nano structure is obtained (see figure 1 f).

Check final sample effect: the result of AFM (atomic force microscope) scanning and shooting is shown in FIG. 2, the magnification is 4000 times, a clear porous structure can be seen, and the one-dimensional shrinkage rate is about 20%. The results of Fourier infrared spectroscopy of the ceramic coating are shown in FIG. 3. The nano-indentation mechanical test result graph of the ceramic coating is shown in fig. 4.

We also explored the chemical reactions that occur in step 5 pyrolysis. In the temperature range of 400-; in the range of 600 ℃ and 800 ℃, the main reaction is a free radical reaction; at a temperature above 800 ℃, a cross-linking hydrosilation reaction occurs. The reaction equation is as follows:

at the temperature of 400-600 ℃,

coupling dehydrogenation reaction:

2≡Si-H → 2≡Si-Si≡+H₂↑；≡Si-H+H-N= →≡Si-N=+H₂↑；

transamination: = SiH-NH → = Si = N- + NH₃↑；

At the temperature of 400-600 ℃,

free radical reaction: CH (CH)₃·+X-H →CH₄× + X (X is Si, C, N);

at the temperature of over 800 ℃, the temperature of the mixture is controlled,

cross-linking hydrosilation reaction, 2 ≡ Si-CH₂·→≡Si-CH₂-Si≡。

In order to compare the mechanical properties of the ceramic coating prepared in this example with those of the ceramic coatings prepared in the prior art, a nano-indentation hardness test was performed on the samples. The test result shows that the Vickers hardness of the ceramic coating with the micro-nano structure can reach 9 GPa.

Example 2

As shown in fig. 5, a method for preparing a ceramic coating with a micro-nano structure on the surface comprises the following specific steps:

step 1: preparing a pure alkyl resin coating on a substrate, wherein an alkyl resin solution only contains methyl-vinyl polysilazane, and spin-coating the alkyl resin solution on a monocrystalline silicon wafer substrate under the spin-coating conditions that: 500rpm for 6s, then 1500rpm for 10s (see FIG. 5 a);

step 2: copying a micro-nano structure, covering a soft PDMS template on a substrate which is spin-coated with alkyl resin, wherein the soft PDMS template is provided with a micron-scale columnar array structure which is in a hexagonal arrangement column shape, contacting one surface provided with the micron-scale columnar array structure with the substrate, and then completing pattern transfer and crosslinking curing under the heating condition of 150 ℃ at low pressure of 0.8 MPa for 30s and high pressure of 1.25MPa for 30min (see figure 5 b);

and step 3: demolding, releasing the template from the substrate, leaving the cured alkyl resin on the substrate (see fig. 5 c);

and 4, step 4: high-temperature pyrolysis, namely putting the substrate into a tubular furnace protected by nitrogen, heating to 1000 ℃ at the heating rate of 5 ℃/min, keeping the temperature at 1000 ℃ for 1 hour (as shown in figure 5 d), and cooling to room temperature at the cooling rate of 5 ℃/min; and obtaining the ceramic coating with the micro-nano structure.

Check final sample effect: scanning and shooting are carried out by adopting SEM (scanning electron microscope) in an amplifying way, the SEM detection result is shown in figure 6, the amplifying factor is 4000 times, a clear porous structure can be seen, and the one-dimensional shrinkage rate is about 17%. The nano-indentation mechanical test result graph of the ceramic coating is shown in fig. 7.

In order to compare the mechanical properties of the ceramic coating prepared in this example with those of the ceramic coatings prepared in the prior art, a nano-indentation hardness test was performed on the samples. The test result shows that the Vickers hardness of the ceramic coating with the micro-nano structure reaches 9.4 GPa.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims

A preparation method of a ceramic coating is characterized by comprising the following steps:

providing an alkyl resin solution; the alkyl resin solution contains an alkyl resin;

providing a substrate, depositing the alkyl resin solution on the substrate;

providing a template, wherein a first micro-nano structure is arranged on the surface of the template; contacting one surface of the template provided with the first micro-nano structure with one surface of the substrate deposited with the alkyl resin solution, and carrying out imprinting treatment;

separating the substrate from the template, and then carrying out pyrolysis treatment to obtain a ceramic coating with a second micro-nano structure on the surface;

the first micro-nano structure and the second micro-nano structure are complementary in space.
The method according to claim 1, wherein the alkyl resin solution further contains a photoinitiator for promoting a photo-initiated crosslinking reaction, and further comprises a step of photocuring treatment after the step of imprint treatment.
The production method according to claim 2, wherein the mass ratio of the photoinitiator to the alkyl resin is (3-6): 100, respectively; and/or

The photoinitiator comprises at least one of benzoin diethyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and phenyl phosphine oxide.
The method of claim 2, wherein the photocuring process comprises ultraviolet light irradiation.
The method according to claim 2, wherein the alkyl resin solution further contains a modifier for increasing the crosslinking reaction density.
The production method according to claim 5, wherein the mass ratio of the modifier to the alkyl resin is (6-12): 100, respectively; and/or

The modifier comprises at least one of pentaerythritol triacrylate, methacrylate, ethyl acrylate, and pentaerythritol tetrakis (3-mercaptopropionate).
The production method according to claim 1, wherein the pressure of the imprint treatment is 0.5 to 1.2 MPa; and/or

The temperature of the stamping treatment is 140-160 ℃; and/or

The temperature of the pyrolysis treatment is 900-1500 ℃, and the time is 1-2 h.
The method of claim 7, wherein the pyrolysis treatment comprises: heating to 900-.
The production method according to any one of claims 1 to 8, further comprising, prior to the step of depositing the alkyl resin solution on the substrate, subjecting the substrate to a first cleaning treatment and a first drying treatment in this order; and/or

Before the steps of contacting the template with the substrate and carrying out hot embossing treatment, the method also comprises the step of sequentially carrying out second cleaning treatment and second drying treatment on the template.
The method of claim 9, wherein the first cleaning process comprises: soaking the substrate with absolute ethyl alcohol for 20-40 min; and/or

The conditions of the first drying treatment include: the temperature is 80-100 deg.C, and the time is 3-5 min.
The method of claim 9, wherein the second cleaning process comprises: soaking the template for 20-40min by using a mixed solution containing anhydrous ethanol and a surfactant; and/or

The conditions of the second drying treatment include: the temperature is 25-30 deg.C, and the time is 3-5 min.
The method according to claim 11, wherein the mass ratio of the absolute ethyl alcohol to the surfactant is 10: (1-2); and/or

The surfactant includes at least one of ethoxylated sodium alkyl sulfate and dodecylbenzene sulfonic acid.
The method of any one of claims 1-8, wherein the alkyl resin comprises at least one of a silane, a polysilazane, a polysiloxane, a polysilazane, and a polysilaborane.
The production method according to any one of claims 1 to 8, wherein a material of the substrate includes any one of a metallic material, a ceramic material, and a semiconductor material; and/or

The template material includes any one of polydimethylsiloxane and photoresist.
A ceramic coating produced by the production method according to any one of claims 1 to 14.