DE202015103646U1 - Film-forming structure on a produce - Google Patents

Abstract

A film-forming structure on a product, comprising: a product having a surface on which a film is formed; and a thin first film formed of a suboxide or a metal-containing oxide deposited on the top of the article, and wherein the first film is a porous film.

Description

Technical part

The present device or invention relates to a film-forming structure and a film-forming method on a product, which include the dense deposition of a thin first film on a product, wherein the first film is a suboxide or an oxide is soft and has insulating properties and wear resistance. The product is integrated with the first film to prevent the first film from peeling, thereby improving workability. A thin second film, such as a coating, is applied close to the first film, thereby reducing the amount of ink required. The first film is integrated with the second film so as to prevent the second film from peeling and cracking, thereby improving the workability after the formation of the second film, thereby efficiently and efficiently disposing the first and second films Way be formed.

State of the art

Since a metallic film is present during coating or plating, small holes produced by electrolysis are unavoidable and thus lead to a corrosion problem due to the potential difference of different metals. In coating, since rust generated by oxygen entry on metallic surfaces is unavoidable, thick layers are formed to counteract the problem. Therefore, there is a need for an improved surface treatment which takes advantage of and eliminates the disadvantages of plating and coating.

To meet such needs, there is, for example, a coated steel plate in which a hot-dip galvanized steel plate comprising aluminum is heated prior to coating, whereby the surface to be coated is prepared by, for example, chromium plating, a primer layer having a thickness of 2 to 15 μm is applied to the surface and an upper coating having a thickness of 5 to 30 μm is applied thereto (see, for example, Patent Document 1).

However, the coated steel plate described above must be prepared by subjecting the coated surface to a chemical conversion treatment before it is coated. Furthermore, the primer layer and the top layer are required, resulting in a very time-consuming process. Further, because the coating becomes thick, it tends to peel off, resulting in peeling and cracking during subsequent treatment. As a result, the coated steel plate has poor machinability. Because it is difficult to form a uniform chromium film, a surface conditioning treatment is required in which an acid-based surface-treating agent is applied to an original plate to be coated before a chromating treatment. This leads to a time-consuming process. Further, the oxide on the uppermost surface layer of the plating is etched by the surface treatment agent, so that wear resistance of the interface between the surface layer of the plated layer and the primer layer of the starting plate of the coating is reduced.

In order to solve the above problems, a method is proposed in which magnesium ions are previously contained in the surface treatment agent, the conditioned surface of the plated layer is further further conditioned with an aqueous acid solution including magnesium, and magnesium is replaced and deposited to prevent corrosion to prevent the interface between the surface layer of the plated layer and the primer layer of the coated base plate (see, for example, Patent Document 2).

However, the method described above can only be used with certain types of hot-dip galvanized steel plates. The surface conditioning or the surface state of the coated starting plate is too complicated, which also complicates the preparation of the surface treatment agent. Furthermore, the coating process is still complicated, unproductive and inefficient.

To meet such needs, another surface treatment method is proposed in which a chromium plating and a chromium oxide are deposited in separate processes, metallic chromium is actively applied to combine with the chromium oxide in the mechanical treatment bath, a high-coulomb treatment is carried out at a high density in the chemical treatment bath, wherein in the chemical treatment bath of a chromic anhydride alone iron ions are included to form a coating to adhere to the surface of the chrome-plated steel plate (see, for example, Patent Document 3).

However, the process described above takes time for the treatment because the chromium plating and the chromium oxide are applied separately. Further, because the metallic chromium is actively applied to combine with the chromium oxide, the conductivity of the chromium oxide is improved and the hardness is increased. For this reason, corrosion may occur due to the potential difference between the chromium oxide and the chromium steel plate. Furthermore, the increase in the hardness of the chromium oxide results in poor workability after the formation of the film. When the coated product is bent, the coating tends to peel off and crack.

CITATION

Patent document

• [Patent Document 1] JP-A-2002-248415
• [Patent Document 2] JP-A-2003-171779
• [Patent Document 3] JP-A-57-35699

Summary of the device or invention

Technical problem

The present apparatus and / or invention addresses these problems and has as its object to provide a film-forming structure on a product which includes the dense deposition of a thin first film on a product, the first film being a suboxide or an oxide that is soft and has insulating properties and wear resistance. The product is integrated with the first film to prevent the first film from peeling, thereby improving machinability. A thin second film, such as a coating, is applied closely to the first film, thereby reducing the amount of ink required. The first film is integrated with the second film to prevent the second film from peeling off and cracking, thereby improving the workability after the second film is formed, thereby forming the first and second films in a rational manner.

the solution of the problem

According to a first aspect of the device, a film-forming structure on a product comprises a product having a surface on which a film is formed; and a thin first film formed of a suboxide or a metal-containing oxide and deposited on the top of the product, and wherein the first film is a porous film. As a result, the first film becomes thinner and softer, which improves the insulating properties and the wear resistance. In addition, the suboxide is combined with oxygen from the air to form a rigid oxide film, whereby the second film can be more easily formed on the first film, which improves the adhesion between the first film and the second film. Furthermore, it prevents the films from peeling off and breaking. A second aspect of the apparatus includes an impregnating layer formed by the first film on the surface of the product. Consequently, the product is integral with the first film on the surface layer of the product, preventing the first film from peeling and cracking. The porous structure of the first film allows the second film to adhere firmly and rigidly, preventing peeling. According to a third aspect of the device, the first film has a surface with minute irregularities. Consequently, the adhesion of the second film to the first film can be improved. Further, the first film functions when a coating constituting the second film is formed on, for example, the first film instead of the primers which are frequently used, thereby replacing the coating in a rational manner ,

According to a fourth aspect of the device, the suboxide is a chromium suboxide and the oxide is a chromium oxide. Consequently, the surface of the film is formed with minute irregularities, thereby improving the adhesion of the second film. According to a fifth aspect of the device, the first film is softer than metallic chrome and has insulating properties and wear resistance. Consequently, the first film, which is lighter than metallic chromium, has improved machinability, insulating properties and wear resistance. A sixth aspect of the device comprises a thin second film formed on the surface with the irregularities of the first film. As a result, the second film on the first film having a porous structure is solid and rigid, preventing the second film from peeling and cracking. Furthermore, the workability of the product after the formation of the second film is improved. A seventh aspect of the device comprises an impregnating layer formed by the second film on a surface layer of the first film. Thus, the first film is integral with the second film, preventing the second film from peeling and cracking. The porous structure of the first film causes the second film to adhere firmly and rigidly. According to an eighth aspect of the device, fine particles or crystals of the second film are arranged on the irregularities of the first film independently and at a high density. Thereby, when a stress is applied to a part of the fine particles and crystals of the second film, the rest of the fine particles and crystals are not affected. As a result, when the product is bent or the surface of the second film is damaged after the formation of the second film, peeling or tearing of the second film does not occur. With the improved Machinability of the product, various processing techniques can be applied to the product.

According to a ninth aspect, the first film has a thickness of 1 μm or more and the second film has a thickness of 5 μm or more. As a result, thinner first and second films are formed. When the second film, such as a coating, is formed, the first film is allowed to rationalize, unlike conventional primers. In addition, for example, a thinner version of the second film uses less ink and the second film, such as a coating, is formed in a rational manner and at a low cost. According to a tenth aspect of the device, the second film comprises any one of a polymer material, an inorganic or organic coloring layer, a functional material or ceramics. As a result, various materials can be used for the second film. According to an eleventh aspect of the device, the product is any of stainless steel, nickel, iron, copper, aluminum, brass, other metals, alloy, plastic, glass, ceramics, paper, fiber or wood. Consequently, various materials can be used.

According to a twelfth aspect of the device, the first film is a thin and porous film obtained by arranging the product and an anode part in a bath for receiving a treatment liquid, applying positive and negative voltages to the product and the anode part, adjusting a bath temperature of the treatment liquid to a low temperature; and depositing a metal oxide-containing suboxide or oxide in the treatment liquid on the article by electrochemical action or by depositing a thin and porous first film formed by a metal ion-containing suboxide or oxide in the treatment liquid in an electroless bath on the article by chemical reaction is formed. As a result, various kinds of the first films are formed at a low cost by electrochemical action or chemical reaction. In particular, the first film may be formed with simple equipment by chemical reaction as compared to a case of electrochemical action.

According to a thirteenth aspect of the device, the electrochemical effect treatment liquid comprises chromanhydride and a reduction inhibitor. Consequently, during electrolysis of the treating liquid, dispersion of chromate is achieved while preventing a current flowing through the product, thereby preventing the deposition of metallic chromium and inhibiting the conductivity and hardness of the first film. According to a fourteenth aspect of the device, the electrochemical action treatment liquid comprises means for supplying metal ions, a reducing agent and an additive such as ceramics. Consequently, deposition of the additive, which is the suboxide or oxide such as ceramics, is promoted. According to a fifteenth aspect of the apparatus, a bath temperature of the electrochemical action treatment liquid is set to 10 ° C or less. Consequently, the deposition of the first film is promoted and the deposition of the metallic chromium is inhibited, thereby promoting the deposition of the chromium suboxide. A sixteenth aspect of the device comprises a thin second film, wherein the second film is attached or adsorbed to the first film, or the second film is formed by impregnation or firing. As a result, the second film such as a coating is firmly and rigidly formed on the porous first film. According to a seventeenth aspect of the device, the second film comprises any one of a polymer material, an inorganic or organic coloring layer, a functional material or ceramics, and any of the polymer material, the inorganic or organic coloring layer of the functional material or the ceramic on the first film coated, sprayed or baked, or the material comprising the first film is immersed in one of the above-mentioned materials, or a voltage or an electric field is applied to the product having the ink and the primary film, and further the ceramic is fired. Consequently, the second film of the above-mentioned materials is attached to or adsorbed on the first film, or the second film is formed by impregnation or firing.

Advantageous effect of the device

According to a first aspect of the apparatus, a thin first film formed of a suboxide or metal-containing oxide is deposited on top of the product, and wherein the first film is a porous film. As a result, the first film becomes thinner and softer, which improves the insulating properties and the wear resistance. In addition, the suboxide is combined with oxygen from the air to form a rigid oxide film, whereby the second film can be more easily formed on the first film, which improves the adhesion between the first film and the second film. Furthermore, it can be prevented that the films peel off and tear. A second aspect of the device includes an impregnating layer passing through the first film on the Surface of the product is formed. Consequently, the product is integral with the first film on the surface layer of the product, preventing the first film from peeling and cracking. The porous structure of the first film allows the second film to adhere firmly and rigidly, preventing peeling. According to a third aspect of the device, the first film has a surface with minute irregularities. Consequently, the adhesion of the second film to the first film can be improved. Further, the first film functions when a coating constituting the second film is formed on, for example, the first film instead of the primers which are frequently used, thereby replacing the coating in a rational manner ,

According to a fourth aspect of the device, the suboxide is a chromium suboxide and the oxide is a chromium oxide. As a result, the surface of the film is formed with minute irregularities, and the adhesion of the second film can be improved. According to a fifth aspect of the device, the first film is softer than metallic chrome and has insulating properties and wear resistance. Consequently, the first film, which is lighter than metallic chromium, has improved machinability, insulating properties and wear resistance. A sixth aspect of the device comprises a thin second film formed on the surface with the irregularities of the first film. As a result, the second film on the first film having a porous structure is solid and rigid, preventing the second film from peeling and cracking. Furthermore, the workability of the product after the formation of the second film can be improved. A seventh aspect of the device comprises an impregnating layer formed by the second film on a surface layer of the first film. Thus, the first film is integral with the second film, preventing the second film from peeling and cracking. The porous structure of the first film allows the second film to adhere firmly and rigidly. According to an eighth aspect of the device, fine particles or crystals of the second film are arranged on the irregularities of the first film independently and at a high density. Thereby, when a stress is applied to a part of the fine particles and crystals of the second film, the rest of the fine particles and crystals are not affected. As a result, when the product is bent or the surface of the second film is damaged after the formation of the second film, peeling or tearing of the second film does not occur. The workability of the product is improved, and thus various processing techniques can be applied to the product.

According to a ninth aspect, the first film has a thickness of 1 μm or more and the second film has a thickness of 5 μm or more. As a result, thinner first and second films are formed. When the second film, such as a coating, is formed, the first film functions rationally as opposed to instead of conventional primers. In addition, for example, less color is used by forming a thinner second film, and the second film, such as a coating, can be formed rationally and at a low cost. According to a tenth aspect of the device, the second film comprises any one of a polymer material, an inorganic or organic coloring layer, a functional material or ceramics. As a result, various materials can be used for the second film. According to an eleventh aspect of the device, the product is any of stainless steel, nickel, iron, copper, aluminum, brass, other metals, alloy, plastic, glass, ceramics, paper, fiber or wood. Consequently, various materials can be used.

According to a twelfth aspect of the device, the first film is a thin and porous film obtained by arranging the product and an anode part in a bath for receiving a treatment liquid, applying positive and negative voltages to the product and the anode part, adjusting a bath temperature of the treatment liquid to a low temperature; and depositing a metal oxide-containing suboxide or oxide in the treatment liquid on the article by electrochemical action or by depositing a thin and porous first film formed by a metal ion-containing suboxide or oxide in the treatment liquid in an electroless bath on the article by chemical reaction is formed. As a result, various kinds of the first films are formed at a low cost by electrochemical action or chemical reaction. In particular, the chemical reaction makes it easier to produce the first film with simpler equipment compared to a case of electrochemical action.

According to a thirteenth aspect of the Device comprises the treatment liquid for the electrochemical effect chromanhydride and a reduction inhibitor. Consequently, during the electrolysis of the treating liquid, dispersion of chromate is achieved while preventing a current flowing through the product, and thereby the deposition of metallic chromium can be prevented, and the conductivity and hardness of the first film can be inhibited become. According to a fourteenth aspect of the device, the electrochemical action treatment liquid comprises means for supplying metal ions, a reducing agent and an additive such as ceramics. Consequently, the deposition of the additive, such as ceramic, which is the suboxide or oxide, is promoted. According to a fifteenth aspect of the apparatus, a bath temperature of the electrochemical action treatment liquid is set to 10 ° C or less. Consequently, the deposition of the first film is promoted and the deposition of the metallic chromium is inhibited, and thereby it is possible to promote the deposition of the chromium suboxide. A sixteenth aspect of the device comprises a thin second film, wherein the second film is attached or adsorbed to the first film, or the second film is formed by impregnation or firing. Consequently, the second film, such as a coating, can be formed firmly and rigidly on the porous first film. According to a seventeenth aspect of the device, the second film comprises any one of a polymer material, an inorganic or organic coloring layer, a functional material or ceramics, and any of the polymer material, the inorganic or organic coloring layer of the functional material or the ceramic on the first film is applied, sprayed or baked, or the material comprising the first film is immersed in one of the above-mentioned materials, or a voltage or an electric field is applied to the product comprising the ink and the primary film, and further the ceramic is fired. Consequently, the second film of the above-mentioned materials is attached to or adsorbed on the first film, or the second film is formed by impregnation or firing. In addition, the second film of the above materials is optimally formed.

Brief description of the drawings

1 Fig. 10 is an explanatory view showing a state in which the first film is deposited on the product by the electrochemical action applied to the present device.

2 Fig. 12 is an explanatory view showing a state in which a coating, which is the second film, is formed on the first film of the product by a spraying method applied to the present apparatus.

3 are micrographic images representing the surface states of chromium suboxide of the first film deposited by setting the bath temperature at -5 ° C in a deposition process of the first film by the electrochemical action applied to the present apparatus. The images are shown enlarged at different time periods after deposition.

4 are micrographic images representing the surface states of chromium suboxide of the first film deposited by setting the bath temperature at 15 ° C in a deposition process of the first film by the electrochemical action applied to the present apparatus. The images are shown enlarged at different time periods after deposition.

5 FIG. 11 is an enlarged micrograph showing a deposition state after twenty minutes of deposition of the chromium suboxide in FIG 3 have passed.

6 FIG. 11 is an enlarged micrograph showing a deposition state after twenty minutes of deposition of the chromium suboxide in FIG 4 have passed.

7 are stepwise magnified scanned micrographic images showing a deposition state of the chromium suboxide in 3 demonstrate.

8th are stepwise magnification micrographic images showing a cross section of the deposition state of the chromium suboxide.

9 Fig. 10 is a cross-sectional view schematically showing a state of impregnation when the suboxide constituting the first film is deposited on the surface of the product.

10 (a) and 10 (b) are explanatory views of the enlarged main parts in FIG 9 and show the product with different surface conditions.

11 is an enlarged micrographic image of the main part 9 ,

12 Fig. 10 is a sectional view schematically showing a state of forming a coating which is the second film after the deposition of the suboxide, which is the first film, on the surface of the product.

13 is an enlarged explanatory view of the main part 12 , The surface of the first film acts like a rod holder and the second film is embedded in the holes for holding rods.

14 FIG. 10 is an enlarged sectional view illustrating a state of a coating which is the conventional second film that is formed.

15 Fig. 10 is an enlarged sectional view schematically showing the product bent after the formation of the second film.

16 is an enlarged schematic view of the bent portion of the product from 15 ,

Description of embodiments

Embodiments of the present apparatus applied to a surface treatment in which a first film is formed on the surface of a product to be treated or a component made of a stainless steel plate, and then a second film on the First film is formed, will now be described below with reference to the drawings. In the 1 to 16 the reference number refers 1 to a bath, which is a treatment liquid 2 or an electrolyte in it. The treatment liquid 2 has the same structure as a Schwarzchrombad and the composition of 300 to 400 g / l Chromanhydrid CrO ₃ , 5 to 10 g / l sodium silicon fluoride NaSiF ₆ and 2 to 5 g / l barium acetate C ₄ H ₆ O ₄ Ba. The bath temperature of the treatment liquid 2 is adjusted to 10 ° C or lower by using a later-described refrigerator to prevent the deposition of the suboxide of chromium suboxide CrO ₃ on the surface of the product 3 to assist and inhibit the deposition of metallic chromium Cr. In this case, the bath temperature to deposit a predetermined suboxide should preferably be 0 ° C or less, so that the treatment liquid 2 not frozen. In some embodiments, the bath temperature is set from -5 to 10 ° C.

The product or workpiece 3 which serves as a cathode part 3 is formed, a metallic chromium or an anode part 4 , which is a soluble electrode, and a carbon or lead, which is a non-soluble anode, become in the treatment liquid 2 soaked or immersed in the same and arranged in the same. A wiring 5 . 6 for applying a positive and negative voltage are connected to the components described above. A voltage is taken from a power source 8th via a control unit 7 applied, which has the function of a rectifier. These units control the current density of the product 3 and the anode part 4 to 20 A / dm ² . In some embodiments, a stainless steel plate (SUS304) having a thickness of 0.5 mm is used as the product 3 used, the product 3 however, it can not be limited to a metal part and may be any of nickel, iron, copper, aluminum, brass, other metals, alloys, plastic, glass, ceramics, paper, fibers or wood on which an oxide can be deposited.

A cooling bath 9 for receiving a predetermined amount of the treatment liquid 2 is in the immediate vicinity of the bath 1 arranged and a zigzag or coil-like cooling line 11 the cooling device 10 is in the cooling bath 9 arranged. In the drawing, the reference numeral 12 a compressor for circulating a coolant contained in a cooling circuit of the cooling device 10 is provided, the reference numeral 13 denotes a cooling cylinder for storing the cooling bath 9 and the reference numeral 14 is a filter located in a drain line at the bottom of the cooling bath 9 is provided inserted.

A supply line 15 for the treatment liquid is at the upper position of the cooling bath 9 provided and a discharge line 16 for the treatment liquid is at the lower part of the cooling bath 9 intended. One end of the supply line 15 for the treatment liquid is in the treatment liquid 2 in the bathroom 1 immersed and a liquid feed pump 17 for sucking the treatment liquid 2 is in the supply line 15 introduced for the treatment liquid. Furthermore, there is an end of the discharge line 16 for the treatment liquid with the filter 14 connected and the other end is via a check valve 18 with the lower part of the bath 1 connected.

2 is a state in which the suboxide, which represents the first film, on the product 3 is deposited and then by spraying a paint, which is the second film, a coating is formed on the first film. The reference number 19 denotes a small paint gun used for spraying. The paint gun 19 has a cylindrical paint container 20 which is arranged so that it is on the side of the nozzle of the paint gun 19 slanting and a compressed air line 21 is with the lower part of the paint gun 19 connected. Then, by the operation of a release lever 22 a synthetic resin paint in the paint container 20 on the first movie 23 on the product 3 is deposited, sprayed. In some embodiments, chromium suboxide CrO _{3 is} on the product 3 deposited as the suboxide, which is the first film 23 represents.

The other methods of forming the coating which constitutes the second film include: brush or roller application, a back-finishing technique in which a paint is heated and cured; a Immersion coating technique in which the product 3 immersed in the paint with the first film; an electro-deposition coating technique in which the product 3 is coated in a water color by applying static electricity of opposite polarity; and an electrostatic coating technique in which a coating on the product 3 by charging the product 3 and a spray paint of opposite polarity is electrically absorbed. The optimal technique can be selected depending on the machining conditions.

Next, in the method of the present apparatus, the suboxide, which is the first film 23 is, or chromium oxide Cr ₂ O ₃ , which is the oxide of the suboxide, first on the product 3 deposited. Then the coating, which is the second film 24 represents, on the first film 23 educated. If the suboxide, which is the first movie 23 is, or chromium oxide Cr ₂ O ₃ , which is the oxide of the suboxide, first on the product 3 is deposited and then a coating, which is the second film 24 is on the first movie 23 is formed, become the bath 1 for receiving the treatment liquid 2 , the product 3 , which is a cathode part, and the anode part 4 , prepared, and then a predetermined voltage is applied to the product 3 and the anode part 4 created. The power source 8th , which works with a certain voltage density, and the control unit 7 for controlling the power source 8th , are mounted on the above components. Furthermore, the cooling bath 9 near the bath 1 arranged.

The cooling bath 9 is with the cooling unit 10 equipped and the coolant line 11 is in the cooling bath 9 intended. The feed line 15 for the treatment liquid is at the upper position of the cooling bath 9 provided and the discharge line 16 for the treatment liquid is at the lower part of the cooling bath 9 intended. The liquid feed pump 17 is in the supply line 15 introduced for the treatment liquid. One end of the supply line 15 for the treatment liquid is in the treatment liquid 2 in the bathroom 1 provided and one end of the discharge line 16 for the treatment liquid is with the lower part of the bath 1 over the check valve 18 connected.

The treatment liquid 2 is then prepared. The treatment liquid 2 has the composition of 300 to 400 g / l chromanhydride CrO ₃ , 5 to 10 g / l sodium silicofluoride NaSiF ₆ , which is a reduction inhibitor, and 2 to 5 g / l barium acetate C ₄ H ₆ O ₄ Ba and the treatment liquid 2 is in the bathroom 1 added. In this case, sodium silicon fluoride and barium acetate inhibit in the treatment liquid 2 a flow of electricity, causing the deposition of metallic chromium Cr on the surface of the product 3 and promote the deposition of chromium suboxide CrO ₃ , which is the suboxide.

The product 3 and the anode part 4 be in the bathroom 1 recorded, the wiring 5 . 6 the same will be with the control unit 7 and the power source 8th connected. The power source 8th is turned on to apply a predetermined voltage and the current density of the product 3 and the anode part 4 be through the control unit 7 set. In some embodiments, the current density of the product becomes 3 and the anode part 4 set to 20 A / dm ² .

Then the liquid feed pump 17 started to the treatment liquid 2 in the bathroom 1 to suck and the sucked treatment liquid 2 becomes the cooling bath 9 sent. Furthermore, the cooling unit 10 started to the compressor 12 to drive and the coolant to the coolant line 11 to circulate. The treatment liquid 2 in the cooling bath 9 is then cooled and to the lower part of the bath 1 from the discharge line 16 sent the treatment liquid. Thus, the treatment liquid becomes 2 in the bathroom 1 cooled and in some embodiments, the bath temperature is set to 10 ° C or lower. In this case, the bath temperature to deposit a predetermined suboxide or a predetermined amount of suboxide should preferably be 0 ° C or lower, so that the treatment liquid 2 not frozen. In some embodiments, the temperature is set between -5 to 10 ° C.

When a voltage to the product 3 and the anode part 4 is created on the side of the product 3 Hydrogen gas generated and in the treatment liquid 2 moved up and then released to the air while on the side of the anode part 4 Oxygen gas generated and in the treatment liquid 2 moved up and then released into the air. Chromanhydride, which is the main component of the treatment fluid 2 is, is at the anode 4 ionizes and the chromium ions are from the anode part 4 separated. The separated chromium ions move and spread in the treatment liquid 2 and move towards the interface of the product 3 , Then the chromium ions are reduced to trivalent chromium. The trivalent chromium will be at the interface of the product 3 deposited.

At this time, trivalent chromium is at the interface of the product 3 deposited based on the metal Cr and the metallic Cr, respectively. The deposited metal Cr combines with the chromium suboxide CrO ₃ , which is the suboxide 23 and then the metal Cr and the chromium suboxide are sequentially bonded thereto adhered to form a suboxide film. When the thickness of the film reaches 1 to 2 μm, the conductivity of the suboxide film is lost and the formation of the suboxide ceases. The chromium suboxide film is semi-glossy black and a thin film having a thickness of 1 to 2 μm. Thereafter, the chromium suboxide film is bonded with oxygen in the air and changes into an oxide of Cr ₂ O ₃ , making the first film stiffer.

In the deposition of the suboxide film, the bath temperature is set to a low temperature, which is 10 ° C or less. In some embodiments, the temperature is set at -5 to 10 ° C. The current is through sodium silicon fluoride and barium acetate in the treatment liquid 2 inhibited. Furthermore, because the current density of the product 3 and the anode part 4 is set to 20 A / dm ² , the deposit of metallic chromium Cr on the produce 3 be inhibited. Thus, it is considered that the first film made of the suboxide 23 softer than the metal Cr and has a lower conductivity.

The inventors tested the components of the deposited suboxide film by a quantitative analysis using a SHIMADZU CORPORATION electron sample microanalyzer (EPMA 1720). The following data were obtained: C: 24.91%; O: 18.82%; Si: 35.75%; Cr: 11.16%; and Ni: 9.36%. These data show that the deposition of Cr is inhibited.

Next, the inventors examined the surface state of the first film 23 by using a field emission type high resolution scanning electron microscope (SU-10) manufactured by Hitachi High Technologies Corporation. The in the 3 and 4 The results obtained were obtained. 3 are photographic images of the surface states after 5 minutes, 10 minutes and 20 minutes after the onset of deposition of the first film 23 forming suboxide with the bath temperature of -5 ° C and the current density of 20 A / dm ² , with an enlargement of 10 K, 20 K, 50 K and 100 K (K: × 1000). Plural or multiple masses or granular structures occur in each state, and these structures grow over time after deposition and the distances thereof also increase. It was observed that irregularities were distributed and clearly formed.

4 are photographic images of the surface states after 5 minutes, 10 minutes and 20 minutes after the onset of deposition of the first film 23 forming suboxide with the bath temperature of 15 ° C and the current density of 20 A / dm ² , with a magnification of 10 K, 20 K, 50 K and 100 K. Plural grains or scale-like structures occur in each state and these structures increase and grow in the course of time after the deposition and the distances of the same also increase. Thus, a distribution of irregularities was observed.

5 is a photographic image of the surface state after 20 minutes after the start of deposition of the first film 23 at the bath temperature of -5 ° C with a magnification of 100 K. The size of the masses or granular structures are shown for comparison with a reference scale. Masses or granular structures with the size of 25 to 200 nm were observed. 6 is a photographic image of the surface state after 20 minutes after the start of deposition of the first film 23 at the bath temperature of 15 ° C with a magnification of 100 K. The size of the structures of grains or edges is shown for comparison with a reference scale. Structures of grains or edges having a width of 25 to 50 nm and a length of 400 to 650 nm were observed.

Additionally included 7 Photographic images of the surface state of 5 from a scanning microscope at a magnification of 10 to 50 K. It was observed that the suboxide film had a fine porous structure, that the surface was formed like a cake with minute irregularities or a sponge, and the surface had many irregularities with the surface Size of 50 to 200 nm had. 8th is a photographic image of a cross section of the suboxide or the first film 23 out 3 , It was observed that tiny irregularities on the surface of the first film 23 were formed around the surface of the product 3 cover.

As can be seen from above, the surface of the product can 3 , as in 9 represented, represented schematically. As in 10 (a) (b) in further enlarged pictures of 9 shown, the first film seems because of various irregularities and serrations on the surface of the product 3 with the irregularities of the porous first film 23 in contact, close to the product 3 to be attached and deposited. This condition is further enlarged and in 11 shown. The first movie 23 is arranged in a striped pattern with certain intervals and with the surface layer of the product 3 connected, so the first movie 23 firmly attached to the product 3 adheres.

Thus, an impregnating layer made of the first film 23 is formed on the surface of the product 3 formed, so that the product 3 in one piece with the first film 23 is. Consequently, the first film is liable 23 on the surface layer of the product 3 stiff and tight, which prevents the first movie 23 peels off and breaks or breaks. Furthermore, the second movie 24 on the porous structure of the first film 23 firmly and rigidly formed, allowing a detachment of the second film 24 is prevented.

Next, when forming a coating on the product, which is the second film 23 an inorganic or organic color layer on the product 3 deposited or absorbed on deposited suboxide or oxide. In some embodiments, a spray method is used to coat with the spray gun 19 As an application or Absorbierverfahren the coating applied, but other techniques can be used. In these cases, because oxygen can penetrate or penetrate the coating, the coating immediately after the formation of the first film 23 or it can be made later. The coating should only be formed at the end of the rigid oxide. Thus, the timing of the formation of the coating does not affect the quality.

Then, the surface of the suboxide or the oxide of the first film becomes 23 on the product 3 is deposited, cleaned and dried before forming the coating. The product 3 for example, on a suitable device or template 25 arranged. Then a desired color in the paint container 20 the coating gun 19 filled. By holding the coating gun 19 in connection with the compressed air line 21 The color is achieved by pressing the shutter button 22 sprayed with the nozzle in the direction of the product 3 is held. This condition is in 2 shown.

In the manner described above on the product 3 Applied color becomes on the surface of the first film 23 of the suboxide or oxide and then heated and cured. In this case, the formed state of the coating, which is the second film 24 represents, in the 12 and 13 shown. While making the second movie 24 the present device becomes the thin first film 23 which on the product 3 deposited suboxide or oxide, instead of using primers which have been widely used in a conventional coating. Any fine particles or crystal of the coating will become independent and with a high density on the first film 23 deposited.

At this point in time, in principle, the coating only has to be formed once, and a primer, middle and top coat, which are required in the usual procedure and very time-consuming, are not necessary. The film is formed in a thin film having a thickness of 5 μm, which is one-fifth to one-third of the usual values. The thin film goes with the tiny irregularities of the first film 23 engaged to closely attach. Thus, the amount of the ink used is reduced and the coating is easily formed in comparison with the conventional coating method, whereby the coating is formed in a rational manner and at a low cost.

In this case, due to the porous structure of the first film 23 the many irregularities or holes or depressions on the surface like a rod holder and the second film 24 illustrative coating is fitted and embedded in the holes. Consequently, the density of the embedded coating can also be adjusted through the holes and the polymer chains of the plastic coating can be adjusted, and thereby the second film 24 distributed in high density and the second movie 24 firmly attached to the irregularities and holes. An impregnating layer of the second film 24 becomes on the surface layer of the first film 23 educated. Because the second movie 24 integral or integral with the first film 23 is, prevents the second movie 24 peels off. The porous structure of the first film causes the second film to adhere firmly and rigidly thereto.

As described above, the present device or invention includes an impregnation of the product 3 and the first movie 23 and an impregnation of the first film 23 and the second movie 24 which encourages their integration. Consequently, they are firmly and rigidly attached to each other. Furthermore, peeling and cracking are prevented when the first film 23 and the second movie 24 be bent. In addition, the suboxide or oxide has insulating properties such that a current does not pass through the product 3 passes over the suboxide or oxide, even if the coating is made thinner. As a result, corrosion due to the potential difference does not occur, thereby improving the corrosion resistance. Because the first movie 23 porous and soft, the fine particles of the coating enter more easily and go with the product 3 engaging and disengaging with the product 3 will be prevented. The film is embedded in a simple manner and acts like an anchor component, so that the coating is solid and rigid. A combination with other coatings applied thereto is also promoted to form the coating in a rational manner.

As described above, grains and crystals of the coating are each arranged independently and at a high density. Consequently, if a tension or stress is applied to a portion of the grains and crystals, the rest of the grains and crystals are not affected. This will when the product 3 as in the 15 and 16 shown after the formation of the coating is bent, the stress is distributed. Further, when the surface of the coating is damaged, peeling or cracking does not occur. This shows the product 3 With the coating formed thereon, good workability and various processing techniques can be applied to the product 3 be applied. The surface of the coating was cut in a grid pattern and the peeling of a cut-out part was tested. No peeling was observed and a high adhesion coating was observed.

On the other hand shows 14 a state of a conventionally formed coating 27 , The grains and crystals of the coating 27 are loose and distributed with a low density. In order to prevent the corrosion caused by a potential difference, such as very small holes, a very thick coating having a thickness of, for example, 50 to 100 μm is needed. Such a coating is made by applying the primer 26 on the product 3 and then applying the coating 27 formed in individual layers. The coating process described above requires work and the amount of ink used also increases, which also increases processing costs. As described above, the grains and crystals of the coating are not independent and loosely dispersed at a low density, so that when a stress is applied to a part of the grains and crystals, it has an effect on the rest of the grains and crystals. If the product 3 is bent or the surface of the coating is damaged after Bliden the coating, the coating dissolves 27 and breaks or breaks, resulting in poor processability.

In the embodiment described above, an electroplating technique based on the electrochemical action becomes a deposition method of the first film 23 on the product 3 used. Other deposition techniques that may be used include electroless plating. If additives such as nickel sulfate which is a metal ion supplying agent, sodium hypophosphite which is a reducing agent and powder ceramics in the composition of the treating liquid 2 in the electroless bath, the deposition of the suboxide or oxide or a ceramic can be promoted by using a simple equipment in comparison with the equipment for the electrochemical action.

In the embodiment described above, the second film becomes 24 As a coating, however, functional materials, ceramics, Teflon (registered trademark) or fluorine may be used instead of the coating. The functional materials include, for example, a polymeric material, difluoride material, tetrafluoride material, fluorine compound, titanium dioxide, zinc oxide, manganese dioxide, alumina, bentonite, hydroxyapatite, zeolite, talc, collinite, porous silicon, gold, platinum, palladium, boron nitride, titanium nitride, aluminum nitride, DLC, magnetic material, metallic material and carbon material. You can on the surface and the interface of the first movie 23 be used or within the first movie 23 are stored for improving the functionality of the first and second films 23 . 24 such as corrosion resistance, adsorptive properties, abrasion resistance, catalytic properties, thermal conductivity, low friction properties and antibiotic properties.

As described above, respective fine particles and crystals of the coating become independent and high-density on the first film 23 of the suboxide or oxide that is on the product 3 deposited, deposited. The film is formed in a thin film having a thickness of one-fifth to one-third of the usual thicknesses. The fine particles and crystals become attached to the tiny irregularities of the surface of the first film 23 tightly and firmly attached. Thus, when a tension on a part of the fine particles and crystals of the second film 24 performing coating is applied, the rest of the fine particles and crystals are not affected, resulting in an improvement in the workability of the product 3 after the formation of the coating leads.

Industrial applicability

The present device or invention is suitable for a film-forming structure and a film-forming method on a product, which include the dense deposition of a thin first film on the product, wherein the first film is a suboxide or an oxide which is soft and insulating properties and corrosion resistance. The product is integrated with the first film to prevent the first film from peeling, thereby improving workability. The thin second film, such as a coating, is applied close to the first film, thereby reducing the amount of ink used. The first film is integrated with the second film to prevent the second film from peeling off, thereby improving the workability after the formation of the second film and thereby improving the second film first and second films are made in a rational way.

LIST OF REFERENCE NUMBERS

1

bath

2

treatment liquid

3

Product (cathode part)

4

anode part

23

first film (suboxide, oxide)

24

second film (coating)

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• JP 2002-248415 A [0008]
• JP 2003-171779 A [0008]
• JP 57-35699 A [0008]

Claims (17)

A film-forming structure on a product, comprising a product having a surface on which a film is formed; and a thin first film formed of a suboxide or a metal-containing oxide and deposited on the top of the product, and wherein the first film is a porous film. A film-forming structure on the product according to claim 1, further comprising an impregnating layer formed by the first film on the surface of the product. A film-forming structure on the product according to claim 1, wherein the first film has a surface with minute irregularities. A film-forming structure on the product of claim 1, wherein the suboxide is a chromium suboxide and the oxide is a chromium oxide. A film-forming structure on the product according to claim 1, wherein the first film is softer than metallic chromium and has insulation properties and wear resistance. A film-forming structure on the product according to claim 3, further comprising a thin second film formed on the surface having the irregularities of the first film. The film-forming structure on the product according to claim 6, further comprising an impregnation layer formed by the second film on a surface layer of the first film. A film-forming structure on the product according to claim 6, wherein fine particles or crystals of the second film are arranged on the irregularities of the first film independently and at a high density. A film-forming structure on the product according to claim 6, wherein the first film has a thickness of 1 μm or more and the second film has a thickness of 5 μm or more. A film-forming structure on the article of claim 6, wherein the second film comprises any of a polymeric material, an inorganic or organic color layer, a functional material or ceramic. A film-forming structure on the product of claim 1, wherein the product is any of stainless steel, nickel, iron, copper, aluminum, brass, other metals, an alloy, plastic, glass, ceramic, paper, fiber or wood. The film-forming structure on the product according to claim 1, wherein the first film is a thin and porous film which is set by arranging the product and an anode part in a bath for receiving a treatment liquid, applying positive and negative voltages to the product and the anode part a bath temperature of the treatment liquid to a low temperature; and depositing a metal oxide-containing suboxide or oxide in the treatment liquid on the article by electrochemical action or by depositing a thin and porous first film formed by a metal ion-containing suboxide or oxide in the treatment liquid in an electroless bath on the article by chemical reaction is formed. A film-forming structure on the product according to claim 12, wherein the electrochemical action treatment liquid comprises chromanhydride and a reduction inhibitor. A film forming structure on the product according to claim 12, wherein the electrochemical action treating liquid comprises metal ion supplying agent, reducing agent and an additive such as ceramics. A film-forming structure on the product according to claim 12, wherein a bath temperature of the electrochemical action treatment liquid is set to 10 ° C or less. A film forming structure on the product according to claim 12, further comprising a thin second film, wherein the second film is attached or adsorbed to the first film, or the second film is formed by impregnation or firing. The film-forming structure on the article of claim 16, wherein the second film comprises any one of a polymer material, an inorganic or organic color layer, a functional material or ceramic, and any of the polymer material, the inorganic or organic color layer of the functional material or the ceramic the first film is applied, sprayed or baked, or the material comprising the first film is immersed in one of the above-mentioned materials, or a voltage or an electric field is applied to the product having the ink and the primary film, and further the ceramic is fired is.

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