JPH06116718A - Vapor deposition plating method for sublimable material - Google Patents

Abstract

PURPOSE:To form vapor deposition plating layers having stable quality and thicknesses by floating and disposing many pieces of sublimable materials on the molten bath surface of a material having the sp. gr. larger than the sp. gr. of these materials and irradiating these materials with electron beams, thereby heating and evaporating the materials. CONSTITUTION:The plating raw materials 6a housed in an evaporation chamber 4 are irradiated with the electron beams 3 from an electron gun 2 in a vacuum or dilute gaseous atmosphere, by which the sublimable materials 6a are heated and evaporated and the sublimable material components are plated by vapor deposition on a continuously traveling material 1 to be plated. The molten bath consisting of the material having a low melting pt., low vapor pressure and the sp. gr. larger than the sp. gr. of the sublimable materials 6a is formed in the evaporation chamber 4 in the above-mentioned vapor deposition plating method. The many sublimable materials 6a which have an arbitrary shape and do not react with the molten bath forming material are floated, disposed and laid on the surface of the molten both. The sublimable materials 6a are scanned and irradiated in this state with the electron beams 3. As a result, the sublimable materials are uniformly evaporated and the stable evaporation speed are attained. The plating deposition is thus stabilized.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vapor deposition plating method in which a sublimable plating raw material is heated by an electron beam to be evaporated in a vacuum or a dilute gas atmosphere to be vapor-deposited on the surface of a material to be plated. TECHNICAL FIELD The present invention relates to a vapor deposition plating method of a sublimable material for uniformly vaporizing a functional plating raw material to form a vapor deposition plating layer of stable quality.

[0002]

2. Description of the Related Art As a method of coating the surface of a material to be plated with a metal or ceramics that is difficult to plate by electroplating or hot dipping, heating and evaporation of a plating raw material in a vacuum or a dilute gas atmosphere. The so-called vacuum vapor deposition plating method in which a vapor deposition plating layer is applied to the surface of a material to be plated is adopted. In this method, as a means for evaporating the plating raw material, there are resistance heating, high frequency induction heating, electron beam heating, ion beam heating, laser beam heating, arc discharge heating, etc., which are appropriately used depending on the type of plating raw material and the film forming method. Has been adopted. For example, a resistance heating method or a high frequency heating method is often used for Zn and Al having a low melting point and a high vapor pressure, and Ti and Zr having a high melting point and a low vapor pressure are used.
The electron beam heating method is exclusively used for the above.

Among these heating means, electron beam heating is one in which the electron beam has high energy and high energy density, so that the deposition rate of the plating raw material can be increased and it can be directly applied to the surface of the plating raw material. Since it is a method of heating by irradiating with an electron beam, it has an advantage that it has high heating efficiency (energy efficiency) and can easily evaporate even high melting point metals and various ceramic materials having a low vapor pressure. Further, since the electron beam can be easily deflected by using a magnetic field, not only can the surface of the plating raw material be arbitrarily scanned, but various electron sources can be used for various plating raw materials. It is possible to easily produce various alloy platings and multi-layer platings using a plurality of plating raw materials by simultaneously heating and evaporating the plating raw materials. Furthermore, if the evaporation rate of each plating raw material is controlled by controlling the irradiation time of the electron beam for irradiating the surface of a plurality of plating raw materials, the plating composition and the amount of plating adhered in alloy plating or multi-layer plating can be comparatively controlled. It also has the advantage of being easy to control.

By the way, when performing vacuum vapor deposition of a plating raw material vapor-deposited by electron beam heating on the surface of a long strip-shaped material to be plated, the plating raw material is stored in an evaporation tank and the widthwise direction of the material to be plated is arranged. The plating raw material is evaporated by irradiating it with an electron beam, and vapor deposition is performed on the running material to be plated. At this time, in order to perform a continuous operation while forming a plating layer having a uniform thickness and quality on the material to be plated,
By continuously replenishing the plating raw materials that decrease due to evaporation,
It is necessary to keep the amount of plating raw material almost constant.

In this case, the plating raw material may be a wire-drawable material or may not be a wire-forming material, or a molten bath may be formed in the evaporation tank, or a sublimation behavior may be exhibited. However, the ease of raw material supply and the stability of the evaporation rate are greatly different.

[0006] First, as a material capable of being processed into a wire-like plating raw material, Al, Ti, Zr, Ta, Zn, Cu,
Fe, Ni and alloys containing these as the main components (for example, F
e-Ni alloy) and the like, but these metals and alloys form a molten bath in the evaporation tank when heated by electron beam irradiation. A plating raw material that can be processed into such a wire shape and that is heated and melted by electron beam irradiation is drawn into a desired wire shape and then evaporated with a pinch roll 7 or the like having a drive mechanism as shown in FIG. It is possible to continuously supply to the surface of the molten bath 5 in the tank 4. In FIG. 2, 1 is a material to be plated, 2 is an electron gun, 3 is an electron beam, 6 is a plating raw material, and 8 is a guide pipe. Further, the control of the raw material supply amount according to the evaporation rate of the wire-shaped plating raw material is easily achieved by controlling the wire diameter (cross-sectional area) used and the rotation speed of the pinch roll 7.

Further, as for the evaporation rate of the plating raw material from the surface of the molten bath, if the electron beam output to be irradiated, the level (height) of the molten bath surface and the surface area of the bath are kept stable, a very stable vapor generation rate can be easily achieved. Since it is obtained, there is little change over time in the deposition amount and composition of vapor deposition plating applied to the surface of the plated material,
It is possible to stably manufacture a vapor-deposited plated product for a long time.

[0008]

However, Cr,
When a material that cannot be plastically processed into a wire shape and has sublimability, such as a metal material such as Mg or oxide-based ceramics, is used as the plating raw material, continuous stable supply of the plating raw material to the evaporation tank and its stability There is a problem that the evaporation is extremely difficult. The evaporation of the sublimable material occurs continuously from the surface of the plating raw material that is being irradiated with the electron beam because vapor is generated directly from the surface of the plating raw material in the solid state. Changes over time. In such a case, even if the electron beam is irradiated with a constant output, the surface area of the plating raw material irradiated changes as shown in FIGS. 3 (a) and 3 (b) (S ₀ → S ₁ ). The electron beam input power per unit area (electron beam irradiation density; kW / m ² ) changes, and the total evaporation amount (kg / sec) changes with time. Further, when the shape of the surface of the plating raw material 6a being evaporated changes, the electron beam irradiation (incident) angle when the surface of the plating raw material 6a is irradiated with electron beams changes (θ → θ ′).

The electron beam heating system converts the kinetic energy of electrons into heat energy on the surface of the plating raw material,
This is a method of heating and evaporating the plating raw material, but not all the electrons irradiated on the raw material surface are converted into thermal energy, and some are reflected on the raw material surface (referred to as reflected electrons) to heat the raw material. There is always something that does not contribute to evaporation. Then, when the electron beam irradiation angle on the surface of the plating raw material changes from θ in the initial state [Fig. 3 (a)] to θ'in a certain time [Fig. 3 (b)], the surface of the plating raw material with respect to the total irradiation electron amount is changed. The ratio of reflected electrons also changes, and the amount of electrons consumed for heating and vaporizing the sublimable material also changes. as a result,
Even if the electron beam is irradiated with a constant output, the electron beam output effectively used for evaporation substantially changes, and the total evaporation amount (kg / sec) eventually changes.

When the sublimable material is the plating raw material 6a,
There is also a problem that the evaporation rate is likely to change with the supply of raw materials. FIG. 4 shows a conventional method of supplying a plating raw material 6a to an evaporation tank by a hopper. In the figure, 10 is a hopper, 11 is a vibrator, and other parts corresponding to FIG. Are given the same reference numerals. The running direction of the material 1 to be plated is a direction perpendicular to the paper surface. As shown, the hopper 10
A large amount of the plating raw material 6a having a granular shape, a pellet shape, a briquette shape, a broken piece shape, or the like is filled therein, and a predetermined amount is continuously supplied from the outlet of the hopper 10 into the evaporation tank 4, while the electron beam 3 It is heated and evaporated by irradiation.

However, since the plating raw material 6a is a sublimable material, the melting bath 5 (see FIG. 2) is not formed in the evaporation tank 4, and only the surface region irradiated with the electron beam 3
Steam of the plating raw material 6a is generated. Therefore, if the area for supplying the plating raw material 6a from the hopper 10 to the evaporation tank 4 is different from the area for irradiating the electron beam 3, the supplied plating raw material 6a is not heated and evaporated, By the way, on the other hand, in the region where the electron beam 3 is irradiated, the evaporation raw material is not supplied and disappears over time without being supplied with the electron beam 3, so that the plating raw material 6a is not substantially supplied. . So, inevitably, the hopper 10
It is necessary to supply the raw material by means of the area irradiated with the electron beam 3. However, since the temperature of the supplied plating raw material 6a is originally low,
If a new low-temperature plating raw material 6a is suddenly supplied onto the surface of the sublimable material in the area where heating and evaporation are continuously performed, the surface temperature of the supplied area sharply decreases,
Until the stable evaporation rate is obtained again by electron beam irradiation, the evaporation rate of the plating raw material 6a temporarily decreases.

[0012] Such a phenomenon of variation in the evaporation rate associated with the replenishment of the raw materials means that when the material to be plated continuously runs, it has a direct adverse effect on the stability of the deposited amount of the deposited plating over time. This is a very unfavorable problem because it leads to instability of the quality of the vapor-deposited products to be produced and a reduction in product yield.

As an alternative to the method of supplying the plating raw material by the hopper, for example, a method as shown in FIG. 5 (a) has been proposed and implemented. That is, this system is a system in which an ingot-shaped plating raw material 6b is prepared, and the plating raw material 6b is continuously pushed upward from the bottom of the evaporation tank 4 and supplied. The side wall of the evaporation tank 4 is generally made of water-cooled copper hearth or the like, and the ingot-shaped plating raw material 6b is driven by a combination of a hydraulic cylinder 13, an electric motor and a gear (not shown). Is supplied upward.

Since this method is not a method of directly supplying the plating raw material 6b onto the surface of the plating raw material 6b which is being vaporized, at least a rapid temperature change on the evaporation surface due to the raw material replenishment causes a change in the evaporation rate. It has the advantage that it does not occur and a relatively stable evaporation rate is easily obtained. In particular, when the present method is applied to the evaporation raw material that forms the molten bath 5 by electron beam irradiation, a stable molten bath 5 region can be formed on the upper surface of the ingot-shaped plating raw material 6b. Is easy to control.

However, even if the supply system shown in FIG. 5 (a) is adopted, when a sublimable material is used as the plating raw material 6b, various problems occur, and similar to the material forming the molten bath. Achieving a stable feed (ie, stabilization of the evaporation rate) is difficult.

As described above, since the sublimable material does not form a molten bath by electron beam irradiation, the raw material is vaporized only from the electron beam irradiated region on the solid surface. In other words,
As for the plating raw material in the region where the electron beam is not or hardly irradiated, the raw material in that region remains as it is because the evaporation hardly occurs or does not occur at all. on the other hand,
Since the plating raw material irradiated with the electron beam disappears by evaporation, it is necessary to push up the ingot-shaped plating raw material from the bottom of the evaporation tank in order to supply the raw material.

In this case, since the disappearance rate of the raw material is significantly different between the electron beam irradiation region and the non-irradiation region which are effectively used as the plating raw material, the ingot-shaped plating raw material 6b (sublimable material) is used. When the supply is continued from below and the supply is continued for a long time, the region 14 (electron beam non-irradiation region) where evaporation hardly occurs is high from the upper surface of the evaporation tank 4 like a mountain, as illustrated in FIG. 5B. It rises and finally reaches the height of the material to be plated 1, and it becomes impossible to push up the plating raw material 6b any more, and the production of the vapor deposition plated product must be stopped.

Further, in the method shown in FIGS. 5 (a) and 5 (b),
In order to smoothly push the ingot-shaped plating raw material 6b upward, the evaporation tank 4 must be water-cooled (a water-cooled copper hearth is generally used). For this reason, most of the energy for heating and evaporation given from the electron beam 3 to the surface of the plating raw material 6b is taken by the cooling water through the contact surface between the evaporation tank 4 and the ingot-shaped plating raw material 6b. , Heating efficiency becomes poor. Therefore, the evaporation amount of the vapor generated from the surface of the plating raw material 6b (kg /
Second) is inevitably decreased, and in order to obtain a desired amount of plating deposition in the vapor deposition plated product, the output of the electron beam 3 must be increased or the traveling speed of the material to be plated must be reduced. This is very inconvenient in terms of efficiency and manufacturing cost.

The present invention has been made in order to solve such technical problems, and its purpose is to uniformly evaporate a sublimable material as a plating raw material and to provide a stable quality for a material to be continuously plated. Another object of the present invention is to provide a vapor deposition plating method capable of forming a vapor deposition plating layer with a thickness.

[0020]

Means for Solving the Problems The present invention capable of achieving the above-mentioned object is to heat and evaporate a sublimable material contained in an evaporation tank by an electron beam heating method in a vacuum or a dilute gas atmosphere, In the method of vapor deposition plating a sublimable component on a material to be continuously run, a melting bath made of a material having a low melting point, a low vapor pressure and a larger specific gravity than a sublimable material is formed in the evaporation tank, and the melting is performed. A large number of sublimable materials of arbitrary shape that do not react with the bath-forming material are floated on the surface of the molten bath, the sublimable material is irradiated with an electron beam, and vapor deposition plating is performed while heating and evaporating. is there.

[0021]

[Function] The problems in using a sublimable material as a plating raw material are as follows. (1) The shape of the surface that is undergoing evaporation (sublimation) (evaporation surface) changes over time, which changes the evaporation area and electron beam incident angle, resulting in a very unstable evaporation rate. To become a. (2) When the sublimable material is continuously replenished, if it is replenished directly on the evaporation surface, the evaporation temperature becomes unstable because the surface temperature of the evaporation surface changes rapidly.

The inventors of the present invention have proposed various methods for continuously evaporating the sublimable material without changing the evaporating surface shape as much as possible and continuously supplying the sublimable material to the area other than the evaporating surface at various angles. Repeated examinations. As a result, they have found that the problems described in the above (1) and (2) can be overcome by adopting the above-mentioned configuration, and completed the present invention.

The method of the present invention will be described with reference to the drawings. FIG. 1 is a schematic explanatory view showing an example of a device configuration for carrying out the present invention, and reference numerals 1 to 4 and 6a have the same meanings as shown in FIGS. A sectional view of FIG. 1 is shown in FIG. 6, and 5a in FIG. 6 is a melting bath made of a material having a low melting point and a low vapor pressure.

In carrying out the present invention, first, a predetermined amount of a material having a low melting point and a low vapor pressure (hereinafter referred to as a molten bath forming material) is filled in the evaporation tank 4 and heated by the electron beam 3. To form the molten bath 5a. Next melt bath 5
A plating raw material 6a (sublimable material) having a spherical shape, a lump shape, a flake shape, or the like is put on the surface of a, and a large number of the plating raw material 6a are floated on the surface of the melting bath 5a and spread.
Cover the surface of a. In this state, on the surface of the plating raw material 6a,
As shown at 15 in FIG. 7 (plan view of FIG. 6), the electron beam 3 is irradiated while being scanned to continuously evaporate the plating raw material 6a.

The greatest features of the method of the present invention are the following two points. (1) As shown in FIGS. 3 and 5, the change in shape of the evaporation surface with time due to continuous evaporation of the sublimable material is suppressed to a negligible level, and the evaporation area and electron beam incidence are changed with time. As a result, the evaporation rate is stabilized against the evaporation of the sublimable material for a long time. (2) For replenishment of the sublimable material, it is possible to remove the electron beam irradiation area and supply from any area outside the electron beam irradiation area. In addition, the surface of the molten bath can be moved in any direction while being preheated by the thermal energy given by the temperature of the molten bath. Therefore, when the newly replenished sublimable material reaches the electron beam irradiation region, the evaporation rate from the evaporation surface is unstable without causing a rapid temperature drop on the surface of the evaporation raw material as described in FIG. do not become. Further, the position for replenishing the sublimable material can be any region other than the electron beam irradiation region, and the degree of freedom with respect to the replenishing method and the replenishing device is high.

The molten bath forming material used in the present invention must have a low melting point and a low vapor pressure. The role of the molten bath forming material is to form a molten bath and float a sublimable material as a plating raw material on the bath surface. Therefore, as a matter of course, if the material has a high melting point, a large amount of heat energy must be supplied from the outside in order to hold the molten bath. In particular, the thermal energy applied to the surface of the material for forming the molten bath by electron beam irradiation is inevitably partially transferred to the surface of the molten bath via the sublimable material, but is indirectly provided by heat conduction. If the material has a low melting point that can maintain the molten bath with only thermal energy, it is necessary to purposely provide other heating means (for example, a resistance heating method from the outer periphery of the evaporation tank) to maintain the molten bath state. Disappears. Therefore, the molten bath forming material basically needs to be a low melting point material.

On the other hand, on the surface of the melting bath, most of the bath surface is covered with the sublimable material by floating a large number of sublimable materials to be evaporated, but the gap between the sublimable materials is completely removed. It is virtually impossible to line up the bath surface to fill it. Therefore, although there is a small area, there is a portion where the molten bath surface is exposed. In such a case, when the vapor pressure of the molten bath forming material is relatively high, evaporation of the material occurs from the gap space. In that case, the material is mixed as an impurity in the vapor-deposited plated film of the obtained vapor-deposited plated product, which may impair the desired performance of the vapor-deposited plated product. Therefore, the molten bath forming material basically needs to be a material that is difficult to evaporate, that is, a material having a low vapor pressure. The type of the molten bath forming material used in the present invention is not particularly limited, but a metal material such as Sn, Ga, In, Pb is preferable.

The present inventors also examined a method of more positively avoiding the mixing of the molten bath forming material into the vapor-deposited plating film due to evaporation. As a result, as shown in FIG. 8, powdery or granular carbon 16 is previously floated on the surface of the molten bath 5a to cover the surface of the molten bath 5a, and in this state, the sublimable material is applied to the molten surface 5a. Plating raw material 6a
Float the carbon material 1 between the plating raw materials 6a.
It turned out that it is effective to arrange so that 6 exists. As described above, the plating raw material 6a having various shapes
Since it is virtually impossible to completely cover the surface of the molten bath, there is a small exposed portion of the bath surface, and a slight amount of vapor of the molten bath forming material is generated from the exposed portion. There are cases. Therefore, a powdery or granular form of carbon 16 having a very small vapor pressure and substantially no evaporation is suspended in advance on the surface of the melting bath 5a to cover the bath surface, and in this state, the plating raw material is applied to the bath surface. If a large number of them are floated on the surface, the gaps between the individual plating raw materials 6a become covered with the carbon 16 film, and substantially the molten bath 5
Exposed surface is effectively avoided.

The carbon 16 does not cause evaporation (sublimation) and has a small specific gravity (specific gravity; 2.25) unless it is directly irradiated with the high-power electron beam 3 for a long time. It does not settle. In this way, evaporation of the molten bath forming material can be more positively avoided, and as a result, mixing of the molten bath forming material as an impurity into the vapor-deposited plated film can be more effectively avoided.

The method of the present invention is premised on the fact that the plating raw material 6a made of a sublimable material is suspended on the surface of the molten bath 5a made of the molten bath forming material. Therefore, the plating raw material has a smaller specific gravity than the molten bath forming material. Thus, it is necessary to consider the combination of both as appropriate.

Generally, a sublimable ceramic material has a smaller specific gravity than a metal, and therefore can be floated on the bath surface of most metal species. However, when a sublimable metal is used as 6a, a plating raw material 6a is used. It is necessary to determine the combination in consideration of the specific gravity of the molten bath forming material in advance.

For example, when it is desired to evaporate the Si oxide as the plating raw material 6a, the specific gravity of the Si oxide is 2 to 2.5.
It has a specific gravity of about (g / cm ³ ) and is smaller than most metals. Therefore, by using a molten bath forming material having a specific gravity larger than this (for example, the specific gravity of Sn is 7.29 in the solid state), it is possible to easily float on the surface of the metal bath, and the evaporation of the present invention can be performed. It is a sublimable plating raw material 6a which can effectively use the method. Further, it is needless to say that a combination in which the plating raw material 6a and the molten bath forming material react with each other is not preferable and should be avoided.

In the sublimable material (plating raw material 6a), vapor is generated directly from the solid surface by electron beam irradiation, but the material is heated by the electron beam energy given thereto, and the amount of heat thereof causes the molten bath forming material. When the sublimable material reacts with and is dissolved in the molten bath, selective evaporation of the sublimable material cannot be achieved. Especially when the sublimable material is a ceramic material and the molten bath forming material is a metal, if a combination that causes the above-mentioned dissolution reaction is used, the ceramic material to be originally evaporated is a composite bath or alloy with the molten bath forming material. It becomes a bath, and it becomes impossible to selectively evaporate only the ceramics.

However, since sublimable materials such as Si oxides and Al oxides generally have almost no reaction with low-melting-point metals, unless a special metal bath is used, evaporation of these oxide ceramic materials is not possible. On the other hand, the present invention can be used.

By the way, the present invention is not limited by the method of supplying the sublimable material. For example,
In order to continuously evaporate the sublimable material from the surface of the molten bath, it is necessary to continuously or intermittently replenish the surface of the molten bath with the sublimable material. When replenishing in a granular shape, it is desirable to use a hopper to replenish a predetermined amount from a tank or the like filled with a large amount of the material. However, since the temperature of the replenished sublimable material itself is low, it is not desirable to directly supply the sublimable material to the region where electron beam irradiation is performed, because it causes a destabilization phenomenon of the evaporation rate of the sublimable material. Therefore, the method of replenishing the surface of the molten bath is to remove it from the electron beam irradiation area where evaporation is performed directly, and use the floating behavior on the surface of the bath to naturally reach the electron beam irradiation area. desirable. The sublimable material replenished in this manner reaches the electron beam irradiation region while being preheated by the thermal energy from the molten bath while floating on the bath surface, so that the evaporation rate drops sharply. Suppressed. In addition, since the molten bath composed of the molten bath forming material is not soaked at all, natural bath convection occurs in the evaporating tank, and the sublimable material replenished floats on the bath surface by the bath convection. It is possible to cover the entire bath naturally.

In the present invention, the reason for adopting the electron beam heating method as the heating evaporation source of the sublimable material is that this method is a method of directly applying heat energy to the surface of the raw material to be evaporated (sublimated), and therefore the heating and evaporation efficiency is high. Is high.

Particularly in the present invention, since it is not necessary to maintain the temperature of the molten bath forming material at a higher temperature than necessary, the indirect heating method such as the resistance heating method or the high frequency heating method is very disadvantageous in heating efficiency. Become.

However, regarding the electron beam irradiation method to the surface of the sublimable material, the electron beam scanning is performed as large as possible in the traveling direction of the plated material and the width direction of the plated material to expand the electron beam irradiation area. It may be desirable to reduce the energy (energy density; kW / cm ² ) of the electron beam applied per unit area to evaporate. Even if the total output of the irradiated electron beam is the same, the total amount of evaporation (g / sec) will be somewhat reduced by increasing the irradiated area and decreasing the energy density. If the density is too high, depending on the type of sublimable material, the scattering phenomenon of the evaporation raw material called the splash phenomenon during sublimation becomes remarkable, and the appearance quality of the vapor deposition plated product obtained is impaired, and the molten bath forming material itself There is also the risk of increased evaporation. Therefore, it is preferable that the details of the electron beam sublimation method for the sublimable material be appropriately adjusted depending on each combination of the material and the molten bath forming material.

Up to now, the description has been made on the case where only the sublimable material is used as the plating raw material, but the present invention can be applied as long as it contains at least one sublimable material as the plating raw material. Needless to say, the present invention can be applied to the case where a molten metal material is compounded by vapor deposition in addition to the sublimable material. For example, as shown in FIG. 9, an evaporation tank 4 using a sublimable material as a plating raw material 6a,
The evaporation tank 4a using the molten metal material as the plating raw material 6 may be installed in parallel, and both the evaporation tanks 4 and 4a may be irradiated with the electron beam 3.

The vacuum vapor deposition method in the present invention is not particularly limited as long as it uses the electron beam 3 as a heating evaporation source, and in a broad sense including various vapor deposition methods in addition to the ordinary vapor deposition method. It is a vapor deposition method in the sense. Also,
The material to be plated on which the vapor deposition plating layer is applied is not particularly limited, and may be metal, non-metal, paper, plastic, or other material. Furthermore, the shape of the material to be plated includes various shapes such as a plate, a rod shape, and a tubular shape, and the processed materials of various shapes are not particularly limited.

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples do not limit the present invention.
Any change in design, taking into account the above-mentioned and the following points, is included in the technical scope of the present invention.

[0042]

EXAMPLE A vapor-deposited SiO ₂ / Al _two- layer plated steel sheet was manufactured using the continuous vapor-deposition equipment shown in FIG. 9, and the quality of the obtained plated steel sheet was investigated. Note that FIG. 9 shows equipment for composite vapor deposition plating of a molten metal material together with a sublimable material. In the figure, 17a and 17b vapor deposition chambers, 18 is a connection chamber, 19 is a deflector roll, and 20 is a table roll. , 21a indicates an inlet side vacuum seal device, 21b indicates an outlet side vacuum seal device, 22 indicates a seal roll, and 23 indicates a plating raw material feeder. The manufacturing conditions are as follows.

<Production conditions> (1) Material to be plated: Ultra-low carbon Ti-killed steel strip (2) Steel strip temperature before plating: 200 to 300 ° C (3) Pretreatment to material to be plated: Alkaline degreasing-washing-drying Later, the steel strip surface is activated by heat reduction in a hydrogen-nitrogen mixed gas atmosphere.Then, the steel strip is cooled in an inert atmosphere and introduced into the deposition chamber via a vacuum seal device. (4) Plating content : SiO ₂ / Al _two- layer plating ・ Amount of plating SiO ₂ : 5 g / m ² Al: 20 g / m ² (5) Vacuum degree of deposition chamber: 2 × 10 ^-2 Pa or less (6) Inlet / outlet vacuum seal device atmosphere gas: extremely low oxygen content and very low water content consisting of nitrogen gas (7) the heating source of the plating material: Pierce type electron gun (electron beam output 35~300kW) (8) SiO ₂ evaporable bath: the molten bath forming material ; Sn-plated material; high purity fused SiO ₂ balls (purity of 98% or more ) Evaporation tank material; Fused high-purity alumina (purity 9
(8% or more) (9) Evaporating tank for Al: Evaporating raw material; Pure A
l (Purity 99.8% or higher) Evaporation tank material: Electro-melting high purity alumina (Purity 9
8% or more)

The method of the present invention was carried out under the above production conditions.
Stable SiO ₂ Can generate steam
Became. Also obtained vapor-deposited SiO₂ / Al two-layer plating
Steel plate has less fluctuation with respect to desired coating weight
It is possible to use SiO₂The distribution of the adhesion of the film is the width of the steel strip.
Within ± 20% of target value with respect to direction and longitudinal direction
It is now possible to manage manufacturing.

On the other hand, when the method of the present invention is not adopted and only a large amount of SiO ₂ balls are filled in the same evaporation tank and evaporation is carried out by electron beam irradiation (illustrated in FIGS. 3 and 4). Evaporation method) includes the obtained vapor-deposited SiO ₂ / Al 2
The distribution of the amount of the SiO ₂ film deposited on the layer-plated steel sheet has a target value of ± 40% in the width direction and the longitudinal direction of the steel strip, and the desired corrosion resistance, designability (blackness), electrical insulation, A variation was observed in each performance of far infrared radiation characteristics.

[0046]

The present invention is configured as described above,
A large number of sublimable materials are floated on the surface of the molten bath formed of a material with a low melting point and a low vapor pressure in the evaporation tank.
By heating and evaporating the sublimable material by electron beam irradiation, a stable evaporation rate of the material was obtained, and stabilization of the coating amount of the obtained vapor-deposited plated product was achieved.

[Brief description of drawings]

FIG. 1 is a schematic explanatory diagram showing an example of a device configuration for carrying out the present invention.

FIG. 2 is a diagram for explaining a method of supplying a plating raw material that can be processed into a wire shape.

FIG. 3 is a diagram for explaining a consumption state of a sublimable material.

FIG. 4 is a diagram for explaining a method of supplying a plating raw material by a hopper.

FIG. 5 is a diagram for explaining a state in which an ingot-shaped plating raw material is consumed.

6 is a cross-sectional view of FIG.

FIG. 7 is a plan view of FIG.

FIG. 8 is an enlarged view of a main part showing another embodiment of the present invention.

FIG. 9 is a schematic explanatory diagram of continuous vapor deposition plating equipment used in Examples.

[Explanation of symbols]

 1 Plated Material 2 Electron Gun 3 Electron Beam 4 Evaporation Tank 5, 5a Melting Bath 6, 6a, 6b Plating Raw Material

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Koji Irie Inventor 1 Kanazawa-machi, Kakogawa City, Hyogo Prefecture Kamido Steel Works, Ltd. Kakogawa Steel Works (72) Tota Ayabe Kanazawa-cho, Kakogawa City, Hyogo Prefecture Kamizawa Co., Ltd. Door Steel Works Kakogawa Steel Works (72) Inventor Jun Kato 1 Kanazawa-machi, Kakogawa City, Hyogo Prefecture Kamido Steel Works Co., Ltd. Kakogawa Steel Works (72) Inventor Shoji Miyake 1 Kanazawa-machi, Kakogawa City, Hyogo Prefecture Kadodo Steel Co., Ltd. Tokokagawa Steel Works

Claims (4)

[Claims] 1. A method of vapor-depositing a sublimable component on a material to be plated, which is continuously running, by evaporating a sublimable material stored in an evaporation tank by heating by an electron beam heating method in a vacuum or a dilute gas atmosphere. , A low melting point in the evaporation tank,
While forming a molten bath composed of a material having a low vapor pressure and a larger specific gravity than the sublimable material, a large number of sublimable materials having an arbitrary shape that do not react with the molten bath-forming material are floated on the surface of the molten bath. A vapor deposition plating method for a sublimable material, which comprises performing vapor deposition plating while irradiating an electron beam on a sublimable material to heat and evaporate it. 2. The powdery or granular carbon is floated between floated sublimable materials.
The vapor deposition plating method described in. 3. The vapor deposition plating method according to claim 1, wherein the molten bath forming material is at least one selected from the group consisting of Sn, Ga, In and Pb. 4. The sublimable material is a Si oxide.
The vapor deposition plating method according to any one of 1 to 3.