JP2010120010A - Method for forming inorganic coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming an inorganic coating film excellent in durability regardless of dispensing with wax or polymer processing. <P>SOLUTION: Raw water (a) is brought into contact with particles 14 comprising a ceramic material, which comprises an ore selected from one or more kinds of quartz porphyry, tourmaline and granite porphyry capable of eluting a silicon component and an aluminum component upon the contact with water and contains 50-80 wt.% of silicone 10-50 wt.% of aluminum, 1.0-10 wt.% of titanium and 1.0-9.0 wt.% of iron as chemical components, or particles each of which has a surface layer containing the ceramic material as a surface layer component, an exciting current is applied to the raw water (a) to elute the charged chemical components to thereby obtain charged water (b), this charged water (b) is subsequently introduced into and passed through an electromagnetic field to produce an induced current, the charged water (b) subjected to magnetic field treatment is next ejected on the surface of a work 33 or the work 33 is immersed in and brought into contact with the charged water (b) to form the inorganic coating film based on the oxide composed of the eluted components on the surface of the work 33. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to the surface of components such as iron, aluminum, synthetic resin, glass, rubber, ceramics, and the like used for jewelry such as glasses, accessories, etc. in addition to automobiles, railway vehicles, ships, aircraft, home appliances, etc. The present invention relates to a method for forming an inorganic coating for protecting a painted surface.

  Conventionally, dust, dust, insects, and the like are likely to adhere to the surfaces of the constituent members used outdoors such as automobiles, railway vehicles, ships, and airplanes, and always have to be cleaned. Although the surface of these devices is usually coated and protected with a surface coating such as wax or polymer processing, it has been pointed out that these materials are organic products and become environmental pollution sources.

  In addition, these protective coatings are easily affected by weathering due to ultraviolet rays, etc., and have weaknesses such as fading and gloss deterioration of the coating and deterioration in appearance and function, and further, the protective coating itself is soft and easily damaged. Appearance protection was not enough. For this reason, it is necessary to frequently repeat the wax and polymer processing, and there is a problem that material costs and man-hours are required. Furthermore, daily goods such as eyeglasses, jewelry, and mirrors have a problem that the surface is easily cloudy and it is difficult to remove the attached oil and fat.

In order to cope with such a problem, a method of forming a silica borate film by an electrodeposition action by a charge generated by tourmaline has been proposed (see Patent Document 1). However, the protective coating obtained by this method has not been sufficient in terms of coating durability.
Furthermore, the inventor of the present application has proposed a novel inorganic film forming method and an apparatus thereof (hereinafter referred to as a prior invention) as shown in Patent Document 2. Based on this technology, we have made improvements so that inorganic coatings can be obtained stably with high quality, and have developed to further enhance the functions.

Japanese Patent Laid-Open No. 2000-192086 Japanese Patent No. 3948671

  The present invention has been made to solve the above-described problems, and realizes an inorganic coating having excellent durability and low cost for protecting the surface of an outdoor member such as an automobile, a railway vehicle, a ship, and an aircraft. In addition to having the same advantages as the prior invention that can eliminate the need for conventional wax and polymer processing, contribute to pollution control and environmental conservation, and furthermore, a high-quality inorganic coating can be stably obtained. It provides an inorganic film formation method that can improve the surface properties such as brightness and gloss performance and anti-fogging properties of coatings, and improve safety against natural ecosystems such as sterilization of charged water. is there.

  And this invention is based on the said prior invention, and paid its attention to the specific elution chemical component in a film formation liquid for the solution of the subject, Specifically, the raw material used as the basis of the elution component This is based on the finding that when the chemical composition has a specific value, a high-value film function can be obtained stably.

  The above-mentioned problems are caused by the use of one or more selected ores selected from quartz porphyry, tourmaline, and barley stone that can elute silicon and aluminum components in contact with water. Ceramic particles containing 50 to 80% silicon (mass%, the same applies hereinafter), aluminum 10 to 50%, titanium 1.0 to 10%, iron 1.0 to 9.0%, or the ceramic material as surface layer components The raw water is brought into contact with the particles having the surface layer, and the chemical component charged with this raw water is eluted together with the excitation current to form charged water, and then the charged water is introduced into and passed through the electromagnetic field to induce an induced current. After being generated, the charged water subjected to the magnetic field treatment is sprayed on the surface of the work or the work is immersed in the charged water and brought into contact with the work surface to form an inorganic coating mainly composed of the oxide of the eluted component on the work surface. form An inorganic film forming method of the present invention which is characterized in that, can be solved.

  In addition, the chemical composition (mass%) in this invention is shown by the value at the time of setting content of the structural element which excluded oxygen among the structural elements as 100%. In the following description, the same applies except when it is explicitly described as an oxide.

  And, in order to modify the coating function of the present invention, the ceramic material can be embodied in a form containing 0.01 to 0.5% of silver, and further, the silver is galena, pyroxenite, And / or can be preferably embodied in a form that is refined and extracted from horned silver ore.

The inorganic film forming method of the present invention is configured as described above, and the inorganic film obtained from the treated water obtained therefrom is based on the following characteristic principle.
The inorganic coating obtained by the present invention is a SiO ₂ —Al ₂ O ₃ —TiO ₂ -based ore composed of particles of the ceramic material or an elution component of particles having a surface layer made of the ceramic material. It is a film, has iron oxide (collectively referred to as FeO) as a subcomponent, and silver oxide can also be added. Furthermore, magnesium oxide (MgO), calcium oxide (CaO), etc. may be included as an accompanying component. These coatings have the characteristics of ultra-thin type plating at the nanometer level, and also have the characteristics of electrochemical reaction plating.

Thus, according to the inorganic film forming method of the present invention, when the obtained inorganic film is SiO ₂ —Al ₂ O ₃ —TiO ₂ , FeO film, the conventional wax is realized with low cost and excellent durability. In addition to eliminating the need for polymer processing, the photocatalytic function that decomposes and removes contaminants, and useful surface modification such as high gloss, hydrophilicity, and antifogging properties can be expected. Furthermore, a coating film containing silver oxide (AgO) is given more sterilization properties and is more preferable for the ecosystem. Thus, the present invention has an extremely large practical value as an inorganic film forming apparatus that has solved the conventional problems.

The typical block diagram of the main apparatuses for demonstrating this invention. The graph which shows the relationship between an injection pressure and a film thickness. The graph which shows the relationship between processing time and film thickness. The graph which shows the reflectance of a process surface. The graph which shows the friction coefficient of a process surface. The graph which shows the surface hardness of a process surface. The graph which shows the photoelectron analysis (ESCA) result of a process surface. The graph which shows the decomposability | degradability of a process surface. The graph which shows the effect of magnetic field processing. The graph which shows the relationship between the iron content of charge water, and the iron content of a ceramic material. The graph which shows the change of the glossiness in outdoor exposure. The graph which shows the relationship between Si amount, Al amount, and glossiness. The graph which shows the change of the contact angle before and behind ultrasonication. The graph which shows the relationship between ultrasonic irradiation and active oxygen.

Next, an embodiment according to the inorganic film forming method of the present invention will be described with reference to FIGS. 1 to 8 and FIGS.
First, FIG. 1 shows the principle of an inorganic coating film forming apparatus used in the present invention. The basic configuration is a charged water generating tank 1 that generates charged water, a magnetic field processing tank 2 that magnetically processes the charged water, and a workpiece. It is comprised at least from the film formation tank 3 which makes the surface contact magnetic-field-treated water and forms an inorganic film, and this point is the same as that of a prior invention.

(Charged water generation tank)
This charged water generation tank 1 is provided with a raw water supply port 11 for introducing raw water a such as tap water and well water, and a charged water outlet 12 for taking out treated water b, and is in contact with the water at least. Innumerable particles made of ceramic material that elutes silicon, aluminum, titanium, and iron components as eluting components (hereinafter, these particles and particles having surface layers made of these ceramic materials as a surface layer component are simply referred to as ceramic particles. 14), and the ceramic particle loading unit 13 is loaded.

The ceramic particles 14 are suitably spherical particles having a particle diameter of 3 to 10 mm made of a SiO ₂ —Al ₂ O ₃ —TiO ₂ ceramic material having the following chemical composition, but increase the generation efficiency of charged water described later. More preferably, it is composed of a ceramic material containing 50% or more of one or more selected ores selected from quartz porphyry, tourmaline, and barleystone. This ceramic material has a chemical composition (as oxide) of 50 to 80% silicon (mass%, the same applies hereinafter), aluminum 10 to 50%, titanium 1.0 to 10%, iron 1.0 to 9.0. % Is important, and if it is out of these ranges, a preferred inorganic film cannot be formed.

Quartz porphyry, tourmaline, and barleystone are natural ores, and there are many types of them.
First, quartz porphyry has a mineral composition similar to granite, which is a volcanic rock. It mainly contains quartz and feldspar, and contains 10% of minor components such as biotite. An example of the chemical composition is SiO ₂ : 77%, Al _2. O ₃ : 13% NaKO: 8%, other TiO ₂ , Fe ₂ O ₃ , MgO, etc. 1% or less.
Further, tourmaline (tourmaline) has a general chemical formula of (Ca / Na) (Mg / Fe ²⁺ / Fe ³⁺ / Al / Li) ₃ Al ₆ (BO ₃ ) ₃ (Si ₆ O ₁₈ ) (OH, F) _{In the} case where the specific component in (Mg / Fe ²⁺ / Fe ³⁺ / Al / Li) is the main component, for example, when “Mg” is the main component, Mainly called “iron tourmaline”.
Barley stone is weathered granite, and examples of its chemical composition are SiO ₂ : 66%, Al ₂ O ₃ : 16% NaKO: 6%, other Fe ₂ O ₃ : 2%, CaO: 3%, MgO: 1% or the like.

The ceramic material and ceramic particles of the present invention can be produced by the following procedure.
An ore selected from quartz porphyry, tourmaline, and barley stone is pulverized to a particle size of 0.1 mm or less to obtain an ore pulverized product. Granulate into an appropriate three-dimensional shape such as shape. The granulated product is dried and then sintered in a heating furnace. The degree of sintering is such that it is not damaged by handling such as loading into the charged water generation tank 1, but it is more preferable to use a porous material that maintains a water absorption of 5% or more.

  The ceramic particles may be composed only of ores selected from quartz porphyry, tourmaline, and barleystone, but suitable ore forming aids (clays), extenders (silica sand, chamotte, etc.) ), A sintered binder (feldspar, glass powder, etc.) may be added. In that case, it is important that the selected ore occupies 50% or more in order to ensure the effects of the present invention. And as a chemical composition (as oxide) of these ceramic particles, silicon 50 to 80% (mass%, the same applies hereinafter), aluminum 10 to 50%, titanium 1.0 to 10%, iron 1.0 to 9.0% It is important to include

  In addition, when the said chemical composition cannot be comprised from the ore selected from the said quartz porphyry, tourmaline, and barleystone, it is necessary to add separately about the component which is insufficient. Usually, 1.0 to 10% titanium and 1.0 to 9.0% iron are not sufficiently obtained from the selected ore, so the form of titanium oxide or iron oxide before or after grinding the ore. The desired chemical composition can be obtained by adding and mixing the required amount.

Furthermore, a preferred method for adding titanium and iron components will be described.
If the porous ore granulated particles before sintering or after firing are impregnated with an aqueous solution of soluble titanium or soluble iron, for example, an aqueous solution of an appropriate concentration such as titanium nitrate or iron nitrate, and heated and decomposed, Fine titanium and iron oxides can be exposed and dispersed in the pores from the surface toward the central portion. According to this method, almost all of the added amount is dispersed in a state where it can be contacted with water, so that it is easier to elute compared with the case of simply mixing titanium oxide or iron oxide, and the coating performance based on each component. It is possible to contribute effectively to the reforming.

  In order to obtain ceramic particles having a predetermined chemical composition according to the present invention, ceramic particles sintered in advance by changing the content of a specific element of the chemical composition, for example, silicon, aluminum, titanium, iron, etc. They may be prepared in various types, and may be combined and mixed so as to have a predetermined chemical composition. Table 1 shows ceramic particles 1 to 3 which are examples having such a composition for mixing. According to such a method, the chemical composition of ceramic particles for practical use can be easily set within a desired range.

  The ceramic particles of the present invention may be embodied as particles having a surface layer composed of a ceramic material having a specific chemical composition as described above, that is, particles having a plurality of layer structures in which the surface layer and the core have different components. Good. In this case, since the eluted component is supplied from the surface layer portion, there is an advantage that the raw material cost can be reduced. Needless to say, the surface layer portion is required to contain 50% or more of the selected ore and have the chemical composition.

  In the present invention, it is preferable that silver is contained in at least the surface portion of the ceramic particles in order to improve the coating performance and to provide sterilization performance. In this case, if the silver content is less than 0.1%, the effect is dilute, and if it exceeds 0.5%, the effect does not improve for the content. % Is sufficient.

  The silver component may be pulverized by mixing metallic silver with the selected ore. However, as in the case of titanium and iron described above, silver is added to the granulated particles before sintering or after firing. When impregnated with an aqueous solution of salt, for example, silver nitrate, silver chloride, silver acetate or the like, and heated and decomposed, the fine silver oxide is exposed and dispersed in the pores from the surface of the ceramic particles to the core. It is preferable to hold it. Thus, since the dispersed silver is not covered with other components, all the added amount can be eluted, so that it contributes to the improvement of the film performance with a relatively small silver content. Can do.

Further, this method has an advantage that the silver content can be easily adjusted. The silver content is proportional to the amount of silver salt aqueous solution impregnated in the target ceramic particles, and is also proportional to the concentration of silver salt aqueous solution, so by controlling the concentration of silver salt aqueous solution or the amount of impregnation The silver content of the ceramic particles can be adjusted.
In addition, it is preferable that the silver is refined and extracted from galena, bright silver ore, and / or square silver ore.

  These ceramic particles are loaded in the ceramic particle loading unit 13 so that the raw water a fed from the raw water supply port 11 can pass while contacting the ceramic particles 14. For example, it is preferable that the ceramic particles 14 flow and be agitated by the water stream of the raw water a, and the ceramic particles 14 and the raw water a are in sufficient contact with each other. In this case, the ceramic particles 14 are loaded in a flowable manner. Good.

  In the charged water generation tank 1, when the raw water a comes into contact with the ceramic particles 14 containing the ore component described above, the water is instantaneously discharged into the water, and together with the excitation current, at least silicon, aluminum, titanium and iron are eluted from the ceramic particles 14. Charged water b in which the components are eluted and activated in a charged state is obtained. This excitation current is obtained semipermanently from the ceramic particles 14 and is the main starting force for forming the inorganic coating obtained by the present invention.

(Magnetic field treatment tank)
Next, the magnetic field treatment tank 2 includes a charged water inlet 21 through which the charged water b obtained in the charged water generation tank 1 is fed, and a magnetic field treated water outlet 22 through which the magnetic field treated water c is taken out. The S pole 23a and the N pole 23b to be formed are arranged, and a passage water passage 24 for the charged water b is provided between them.
In the magnetic field treatment tank 2, if the charged water b having a charge is introduced into an electromagnetic field formed by the S pole 23a and the N pole 23b and allowed to pass through the passage water channel 24, Faraday's law is applied. A predetermined induced current is generated, and the charge water b is taken out as more activated magnetic field treated water c. For the purpose of this magnetic field treatment, the intensity of the electromagnetic field is preferably set to 0.10 to 0.80 mG, more preferably 0.30 to 0.80 mG. Such conditions are exactly the same as in the prior invention.

  In this case, even if this magnetic field treatment is not performed, a certain amount of inorganic film can be obtained with the charged water, but when the magnetic field treatment is performed, it is particularly preferable in terms of the stability of film formation and the durability of the formed film. Since a result is obtained, in the present invention, this magnetic treatment tank is an important device that cannot be omitted.

(Film formation tank)
Next, the film formation tank 3 in the present invention includes a magnetic field treatment water inlet 31 for feeding the magnetic field treatment water c obtained in the magnetic field treatment tank 2 and a treatment waste water outlet 32 for taking out the treatment waste water d. As a means for bringing the magnetic field treated water c into contact with the surface of the workpiece 33 arranged, in the example of FIG. 1, a nozzle 34 that ejects the pressurized magnetic field treated water c to the surface of the workpiece 33 is provided.

In the coating film forming tank 3, when the magnetic field treated water c comes into contact with the surface of the work 33, at least each elution component of silicon, aluminum, titanium, magnesium, and iron in the magnetic field treated water c is an electric material according to cathode reduction deposition. An inorganic coating is formed on the surface of the work 33 by a chemical reaction. As a result of photoelectron analysis (ESCA), this inorganic coating is mainly composed of oxides of elution components of silicon, aluminum, titanium, magnesium, and iron, and SiO ₂ —Al ₂ O ₃ — bonded with the respective oxides. It has been found to be a TiO ₂ , MgO, FeO-based glassy coating.

  For such film formation, a method of immersing the work 33 in the magnetic field treated water c is of course possible, but the entire surface of the work 33 is pressurized using an injection nozzle as illustrated in FIG. It is preferable to spray the magnetic field treated water c. The reason is that when an impact is applied by spraying from the nozzle 34, an impact current is generated and the efficiency of film formation is improved.

  In the present invention, the sum of the excitation current, the induction current, and the impact current described above is preferably maintained at 0.05 to 0.07 mA. The reason is that an inorganic coating having excellent durability as described later is reliably formed.

Next, some of the characteristics of the inorganic coating in the present invention are shown in FIGS. It has been found that these characteristics are not substantially different from those of the prior invention.
That is, according to the relationship between the spray pressure shown in FIG. 2 and the thickness of the coating film obtained, it is found that the film thickness can be obtained almost stably in the range of 10 to 60 nm in the pressure range of 10 to 500 N / cm ^2. It was. (Several circles in the figure indicate the case where the film forming conditions are changed. The same applies to FIG. 3)

  Further, according to the relationship between the treatment time of the film forming tank 3 shown in FIG. 3 and the thickness of the obtained film, a film having a thickness of 10 to 100 nm can be obtained even for about 1 second, but the stability of 10 to 60 nm is obtained. In order to obtain a satisfactory coating, 10 seconds or more are preferable, and 60 seconds or more are not economical and unnecessary. In addition, when the charged water is used for the film formation, the temperature of the treatment liquid in the film formation tank 3 of the present invention is preferably maintained at 30 to 50 ° C.

  Further, FIG. 4 relates to the specular reflectivity serving as an index indicating rough skin, fading or gloss deterioration of the coating surface. The once treated surface (symbol f), the twice treated surface (symbol g), and 5 times of the present invention. Even when each of the treated surface (symbol h) and the wax-treated surface (symbol e, which is also shown in the following drawings) is compared, the protective effect of the coating of the present invention on the underlying painted surface is significant. I understand.

  FIG. 5 relates to a coefficient of friction (dynamic friction) that is an index of the difficulty of adhering dust and fouling substances to the paint surface and the ease of cleaning. According to this, the present invention similar to FIG. It is a graph comparing the treated surface and the wax-treated surface, and it can be seen that the adhesion of dust and the like by the coating of the present invention and the ease of cleaning are remarkably excellent.

  Furthermore, according to FIG. 6 showing the surface hardness, which is also an index of the durability of the paint surface, in pencil hardness, the result of comparison of the treated surfaces similar to the above is shown. It is recognized that it is excellent in durability.

FIG. 7 shows the results of photoelectron analysis (ESCA) of the inorganic coating when the eluted components are silicon, aluminum, and titanium. The main components are oxides of the eluted components of silicon, aluminum, and titanium. It has been found that a SiO ₂ —Al ₂ O ₃ —TiO ₂ -based glass-like film bonded with an object is formed as a NM level coating layer having a maximum depth of about 80 nm. In FIG. 7, ◯ indicates the number of photoelectrons / second based on Si, and Δ indicates Ti. In addition, the film in the case of not containing Ti is indicated by ●.

FIG. 8 shows a state in which the coating film of the present invention is formed on a white glass plate, ink ink is applied as a contaminant on the white glass plate, is exposed to the outdoors and fades, and the transparency (completely transparent = 100, opaque = 0). ) Indicates the case of the present invention, Δ indicates the case of a SiO ₂ —Al ₂ O ₃ based coating, □ indicates a case where a titanium oxide photocatalyst is applied, and × indicates a case where no treatment is performed. . According to this, in the case of this invention ((circle)), it turns out that it has a decomposition characteristic comparable to the case ((square)) of a titanium oxide photocatalyst.

  FIG. 9 shows the effect of the magnetic field treatment, and shows the influence of the presence or absence of the magnetic field treatment on the representative thickness of the formed film. It has been found that the thickness of the coating can be increased by a factor of about 2 when the magnetic field treatment is performed regardless of the spray pressure.

Next, FIG. 10 shows the relationship between the iron content in the ceramic particles and the iron content in the charge water.
According to this, the iron content in the charged water is within the allowable range (0.3 mg / l or less) of the heavy metal contained, and 0.01 to 0.3 mg / kg as an appropriate and effective amount as a normal mineral component. l was confirmed to be present. Thus, 1 to 9% of iron contained in the ceramic material is extremely effective for mineral enrichment to the bio-ecological system in the formation of the coating.

Next, the state of the surface modification (glossiness, hydrophilicity, antifogging property, sterilization property, etc.) of the inorganic coating realized by the present invention will be described with reference to FIGS.
Here, the chemical composition of the selected ore used for the ceramic particles is divided into the following two types, and the high Si-Al-Ti system corresponding to the examples: silicon 50-80%, aluminum 10-50%, titanium 1 to 10%, iron 1 to 9% film (indicated by ○ in each figure) and low Si-Al-Ti system corresponding to the comparative example: silicon less than 50%, aluminum less than 20%, titanium 1% Comparison was made with respect to each film with a film (indicated by a circle with a black dot) in the case of less than. For reference, the wax treatment is indicated by □ and the polymer coat is indicated by Δ.

  FIG. 11 shows the superiority or inferiority of the coating by the change in glossiness corresponding to the outdoor exposure period, and it can be seen that the example has the least deterioration and is excellent in outdoor durability. FIG. 12 shows the influence of the composition of silicon and aluminum on the glossiness (the numerical value in the drawing indicates% glossiness), and the examples are those of the low Si—Al—Ti of the comparative example. It has been shown that a film with a glossiness superior to that of the system (low silicon, low aluminum) can be obtained.

  The contact angle (2θ) of the cleaning water on the vehicle body painted surface is 13 ° in the example, 18 ° in the comparative example, and 40 ° in the wax-treated surface, and the example has the highest hydrophilicity. Furthermore, FIG. 13 shows the change in hydrophilicity between the example and the comparative example. Even when active oxygen is generated by ultrasonic irradiation, the tendency of decrease in the contact angle is most remarkable in the example. It can be seen that the hydrophilicity is excellent.

FIG. 14 relates to the antifogging property of the coating, and it can be seen that more active oxygen is generated in the example than in the comparative example. Since this active oxygen contributes to the improvement of the hydrophilicity of the coating surface as described above, it is understood that an antifogging effect (antifogging property) can be obtained.
In this case, the ultrasonic irradiation is a treatment which means that not only the component effect of the present invention but also a synergistic effect with the ultrasonic irradiation exists.

  Next, it shows in Table 2 about the microbe elimination property of an Example. This is a summary of the test results conducted at the Tokyo Food Technology Research Institute, which investigated how harmful bacteria would become after 24 hours of normal drinking water in contact with each film. In the case of the polycontainer, Escherichia coli was proliferated and staphylococci were slightly reduced. However, the container of the example coating proved to have a significant sterilizing effect. In particular, when silver is contained, it turns out that the disinfection effect is remarkable.

  In addition, the water quality test was done in the inspection organization registered by the Minister of Health, Labor and Welfare for the treated water of the present invention, and the following results were obtained. General bacteria: 0, Escherichia coli: not detected, heavy metals (cadmium, mercury, lead, arsenic, hexavalent chromium, zinc, iron, copper, manganese): 0.1 or less of standard, others (cyanide, nitrogen nitrate, fluorine, chlorine) Ion etc.): Conforms to the water quality standards of the Food Sanitation Act as 0.1 or less of the standard.

  As described above, the inorganic coating obtained by the present invention exhibits superior performance compared to wax and polymer processing similar thereto, and, as described above, in the inorganic coating forming method of the present invention, there is no consumable. Since it is almost unnecessary and requires only a small amount of driving power, the operating cost of the apparatus is very small, and the maintenance is easy, so its economic efficiency is particularly excellent. As a result, it is expected to contribute and contribute to pollution prevention, environmental improvement, and global warming control.

  It should be noted that a variety of members such as iron, aluminum, synthetic resin, glass, and rubber used as components of automobiles, railway vehicles, ships, airplanes, home appliances, and the like can be targeted for processing of the present invention. The surface properties of these workpieces can be applied without any problem on either the exposed material surface or the painted surface such as resin paint, but the coated surface is preferable from the viewpoint of protecting the surface of the member. is there.

DESCRIPTION OF SYMBOLS 1 Charge water production tank, 11 Raw water supply port, 12 Charge water extraction port, 13 Ceramic particle loading part, 14 Ceramic particle 2 Magnetic field treatment tank, 21 Charge water inlet, 22 Magnetic field treatment water extraction port, 23a S pole, 23b N Pole, 24 Passage channel 3 Film formation tank, 31 Magnetic field treated water inlet, 32 Treated wastewater outlet, 33 Workpiece, 34 Nozzle a Raw water, b Charged water, c Magnetically treated water, d Treated wastewater

Claims (3)

  One or two or more selected ores selected from quartz porphyry, tourmaline, and barley stone, which can elute silicon components and aluminum components in contact with water, are used as materials, and silicon 50-80 as chemical composition % (Mass%, the same applies hereinafter), aluminum particles 10 to 50%, titanium particles 1.0 to 10%, iron particles 1.0 to 9.0%, or a surface layer containing these ceramic materials as surface layer components The raw water is brought into contact with the particles, and the chemical component charged with the raw water is eluted together with an excitation current to form charged water, and then the charged water is introduced into and passed through the electromagnetic field to generate an induced current. It is characterized in that the charged water subjected to the magnetic field treatment is sprayed on the surface of the workpiece or the workpiece is immersed in the charged water and brought into contact with the workpiece surface to form an inorganic coating mainly composed of the oxide of the eluted component on the surface of the workpiece. Inorganic coating forming method according to.   2. The inorganic film forming method according to claim 1, wherein the ceramic material contains 0.01 to 0.5% of silver.   The inorganic film forming method according to claim 2, wherein the silver is refined and extracted from galena, bright silver ore, and / or square silver ore.

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