JPH06101022A - Vapor-deposition plating method - Google Patents

Abstract

PURPOSE:To prevent the fluctuation in the lapse of time of the composition of a plating bath or the vapor to be vaporized and to constantly obtain vapor- deposited alloy plating layer having uniform composition, in the case of vapor- deposition alloy plating containing as a component the metal which is impossible of plastic processing and can sublimate. CONSTITUTION:The metal or alloy (metal B) which is impossible of plastic processing is packed or dispersed in the metal or alloy (metal A) which is capable of plastic processing, different from the metal B and capable of forming a molten alloy bath, and vapor-deposition alloy plating is executed while replenishing it into the molten alloy bath for evaporating.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for continuously supplying a wire-shaped evaporation raw material and performing vapor deposition alloy plating from a molten alloy bath.

[0002]

2. Description of the Related Art In a so-called continuous vacuum vapor deposition plating method in which a vapor deposition material is heated and vaporized in a vacuum or a dilute gas atmosphere to continuously form a vapor deposition plating layer on the surface of a material to be treated, the vaporization raw material and An evaporating tank for accommodating the above and a heating source for heating and evaporating the evaporation raw material are provided.

In order to continuously carry out such a vacuum evaporation plating treatment, it is necessary to continuously supply (supplement) the evaporation raw material into the evaporation tank by some method. In this case, the ease and stability of material supply greatly differ between the case where the evaporation raw material is a metal capable of plastic working and the case where it is not.

First, the evaporation raw material is a metal or alloy capable of being plastically processed, for example, Al, Cu, Zn, Fe, Ni, Ti, Z.
In the case of r, Ta, Fe-Ni alloy, Ni-Cr alloy, etc., the raw material supply method and evaporation method as illustrated in FIG. 1 are adopted. That is, the evaporation raw material stored in the evaporation tank 4 is heated by the electron beam 3 or the like emitted from the electron gun 2 to form the melting bath 5, and metal vapor is generated from the surface of the melting bath to move the evaporation vapor on the evaporation tank 4. Metal vapor is vapor-deposited on the surface of the material to be plated (zone to be processed) 1 that continuously runs. Then, the raw material is replenished by continuously supplying the vaporized raw material 6 processed into a wire shape from the pinch roll 7 or the like through the wire guide 8 to the melting bath 5 in the evaporation tank 4.

At this time, the evaporation rate (g / sec) of the evaporation raw material from the surface of the molten bath 5 is very high if the irradiation electron beam output, the molten bath surface level (height) and the bath surface area are kept stable. It is kept stable. In order to keep the molten bath surface level stable, the wire-shaped evaporation source 6 should be adjusted according to the evaporation rate of the evaporation source.
It is necessary to control the feed rate (g / sec) of the material, which controls the diameter (cross-sectional area; cm ² ) of the evaporation raw material used and the feed rate, that is, the number of revolutions (rpm) of the pinch roll 7. Easily achieved by

As described above, if the evaporation raw material is a metal or an alloy that can be plastically processed into a wire shape or the like, the supply of the evaporation raw material can be stably maintained, so that the deposition amount of the vapor deposition plating and the composition change over time. It is possible to manufacture vapor-deposited plated products stably for a long time. Therefore, it can be said that the vapor deposition plating process using the above-mentioned evaporation raw material that can be plastically processed into a wire shape and forms a molten bath is a very advantageous method in terms of quality and production.

By the way, when forming a vapor deposition alloy plating layer of two or more components on the surface of the zone to be treated by using the vacuum vapor deposition method, two types of methods have been conventionally used.
In the first method, as illustrated in FIG. 2, a plurality of evaporation tanks 4a and 4b are arranged in parallel in a vapor deposition chamber and melting baths 5a and 5b made of different kinds of evaporation raw materials are formed in each evaporation tank. Then, the vaporized raw materials 6a and 6b in the form of wires are supplied and heated by a heating source such as the electron beam 3 to simultaneously generate the vapors from the surfaces of the respective melting baths 5a and 5b, and the vapor is deposited on the surface of the zone 1 to be treated. This is a method of forming an alloy plating layer.

In order to control the coating amount and plating composition of the vapor-deposited product by such a method, each evaporation tank 4a,
It is necessary to successfully control the evaporation rate (g / sec) of each material generated from the surface of the evaporation material in 4b. For example, when the electron beam 3 is used as a heating evaporation source, the total output (kW) of the electron beam and the time distribution for irradiating / scanning the surfaces of the respective melting baths 5a, 5b are controlled, and the raw materials are supplied to the respective raw material surfaces. Adjust the electron beam output ratio.

However, when attempting to carry out the above method, at least one of the components constituting the alloy plating layer is a metal that cannot be plastically worked, such as Cr, Mg, Si, Mn,
In the case of Co or an alloy containing these metals as a main component, these evaporation raw materials cannot be plastically processed into a wire shape, so that the raw material replenishment method as shown in FIGS. Can not.

Therefore, for such a metal that cannot be plastically worked, a method illustrated in FIG. 3 has been proposed as a method of supplying the evaporation raw material. That is, FIG. 3 shows the hopper 9
The case where the evaporation raw material 6c is supplied to the inside of the evaporation tank 4 is illustrated by way of example, and the evaporation raw material 6c of various shapes such as granular, pellet-like, briquette-like, and fragment-like is provided in the hopper 9.
Are charged in advance, and are continuously supplied from the outlet of the hopper 9 by a predetermined amount into the evaporation tank 4 by vibrating by the vibrator 10 or the like, while being heated and evaporated by the heating source such as the electron beam 3.

However, in this supply, it is difficult to accurately control the supply rate (g / sec) corresponding to the evaporation rate (g / sec) of the evaporation source, as compared with the method of supplying the raw material in the wire form. Yes, the supply amount tends to be unstable. Further, when the evaporation raw material is a metal such as Cr or Mg that cannot be plastically worked and has sublimability, further inconvenient problems occur as described below.

That is, since the evaporation raw material is a sublimable material,
No molten bath is formed in the evaporation tank 4, and the vapor of the evaporation raw material is generated only from the surface region irradiated with the electron beam 3 or the like. Therefore, when the region for supplying the raw material from the hopper 9 into the evaporation tank 4 and the region for irradiating the electron beam 3 are different, the supplied raw material 6c is not heated and vaporized but is gradually deposited as it is in the supply region, while the electrons are emitted. In the irradiation region of the line 3, since the evaporation raw material is not supplied and disappears over time, the raw material is not substantially supplied.

Therefore, it is necessary to irradiate the electron beam 3 or the like by aiming at the raw material supply region by the hopper 9.
Since the temperature of the supplied evaporation raw material 6c such as granular, pellet-shaped, briquette-shaped, and fragment-shaped is originally low,
When a new low-temperature raw material is suddenly supplied onto the surface of the sublimable raw material in the area where heating and evaporation are continuously performed, the surface temperature of the supplied area drops sharply and stabilizes again by electron beam irradiation. Until a high evaporation rate is obtained, the evaporation rate of the sublimable raw material temporarily decreases.

Such a variation phenomenon of the evaporation rate due to the replenishment of the raw materials is caused by the variation of the deposition amount of the vapor deposition alloy plating layer and the plating composition with time when a strip-shaped material to be treated is continuously vapor-deposited. This means that the quality of the obtained vapor-deposition plated product becomes unstable and the product yield decreases.

Therefore, as shown in FIG. 2, when different metals are heated and evaporated from a plurality of evaporation tanks to perform vapor deposition alloy plating, at least one of the components constituting the alloy plating layer is a metal that cannot be plastically worked. In such a case, the method illustrated in FIG. 4 is also adopted as an alternative to the raw material supply method as shown in FIG.

That is, this method is a method in which the ingot-shaped evaporation raw material 6d is preliminarily provided at the bottom of the evaporation tank 4a having no bottom, and is continuously pushed upward and supplied. The ingot-shaped evaporation raw material 6d can be easily produced by a casting method or the like even if it is a metal that cannot be plastically worked. The side wall of the evaporation tank 4 is usually made of water-cooled copper hearth or the like, and the ingot-shaped evaporation raw material 6d is supplied upward by a driving method such as a hydraulic cylinder, a combination of an electric motor and a gear.

Since this method is not a method of directly supplying the raw material onto the surface of the raw material that is being vaporized, the vaporization rate does not change due to a rapid temperature change, and a relatively stable vaporization rate is easily obtained. . In particular, if this method is adopted, the ingot 6d can be used even if the metal cannot be plastically processed.
A stable molten bath 5a can be formed on the upper surface of
Further, since the bath surface level can be controlled relatively easily by controlling the rising speed of the ingot-shaped evaporation raw material, it is easy to control the evaporation speed to be relatively constant.

However, even with this method, when a metal that cannot be plastically worked and has sublimability is used as the evaporation raw material, various problems still occur, and it is as stable as a material capable of forming a molten bath. It is difficult to achieve a stable feed and thus a stable evaporation rate.

That is, in the case of a sublimable metal raw material, vapor is generated directly from the solid-state evaporation raw material by electron beam heating or the like. Therefore, evaporation proceeds only from the surface of the solid raw material to which heating energy is given, and the surface area and shape of the evaporation raw material are Change significantly.

As a result, even if an electron beam or the like is irradiated with a constant output, the surface area of the irradiated solid surface changes, so the electron beam input output per unit area (electron beam irradiation density;
kW / m ² ) changes and the total evaporation amount (g / sec) cannot be kept constant. Further, when the shape of the surface of the material being evaporated changes, the irradiation (incident) angle of the electron beam with which the surface of the material is irradiated also changes.

The electron beam heating method is a method in which the kinetic energy of electrons is converted into heat energy on the surface of the evaporating raw material to heat and evaporate the raw material, but all the electrons irradiated on the surface of the raw material are converted into thermal energy. However, some of them are reflected by the surface of the raw material (referred to as backscattered electrons) and do not necessarily contribute to the heating and evaporation of the raw material. When the electron beam irradiation angle on the surface of the raw material changes, the ratio of reflected electrons on the surface of the raw material to the total amount of irradiated electrons also changes,
As a result, the amount of electrons consumed for heating and vaporizing the sublimable raw material changes. Therefore, even if an electron beam or the like is irradiated with a constant output, the substantial electron beam output effectively used for evaporation changes, and as a result, the evaporation amount (g / sec) of the sublimable raw material changes. To do.

Such a variation phenomenon of the evaporation rate is the same as the variation of the evaporation rate accompanying the supply of the sublimable evaporation raw material by the hopper method described in FIG. This leads to a decrease in yield.

As described above, the method illustrated in FIGS. 2 to 4 stabilizes the evaporation raw material when one or more of the evaporation raw materials is a metal that cannot be plastically worked (and has sublimation property). It is difficult to obtain a stable amount of deposited plating and a stable plating composition because it is difficult to replenish (and the shape of the evaporation surface changes with time).

On the other hand, as another method for performing vapor deposition alloy plating, there is a method as shown in FIG. That is, a plurality of evaporation raw materials are charged in one evaporation tank 4 and a molten alloy bath 5d is formed in the evaporation tank 4 by the electron beam 3 and the like, and a wire-shaped dissimilar metal is placed in the alloy bath 5d. 6a, 6
b is continuously replenished and evaporated from the surface of the alloy bath in a state where each alloy component is mixed, and the mixed vapor is treated zone 1
It is a method of adhering to the surface to form a desired vapor deposition alloy plating layer.

In terms of products, the greatest advantage of this method is that each component element constituting the alloy plating layer evaporates in a state of being premixed from one bath surface. This means that the plating composition in the depth direction is very uniform. In terms of manufacturing, since there is only one evaporation tank, when using an electron beam as a heating evaporation source, for example, as shown in FIG. The electron beam jumping 8 operation for irradiating the same is unnecessary.

Further, the delicate control of irradiation time distribution for controlling the electron beam output to the surface of each of the melting baths 5a, 5b in each of the evaporation tanks 4a, 4b becomes unnecessary, and one molten alloy bath is provided. Since only the output of the electron beam applied to the surface needs to be adjusted, it is a very simple method from the viewpoint of controlling the electron beam. Therefore, as shown in FIG.
The vapor deposition alloy plating method in which a plurality of metal vapors are generated in a mixed state from one evaporation layer is a very advantageous method in terms of products and manufacturing.

If all of the constituents of the vapor-deposited alloy plating layer are plastically workable metals or alloys,
As shown in FIG. 5, each of the evaporation raw materials 6a and 6b processed into a wire shape is simultaneously supplied into the alloy melting bath 5d at an independent supply rate, and each evaporation raw material is irradiated from the surface of the alloy bath by electron beam irradiation or the like. Can generate mixed vapor.
For example, in order to obtain an Al-Ti-based (or Cu-Zn-based) alloy plated product, one of the two kinds of wire-like evaporation raw materials shown in FIG. 5 is Al (or Cu) and the other 6b is Ti.
(Or Zn), and these 6a and 6b are continuously melted at a desired supply rate by a molten Al-Ti alloy bath (or Cu-Zn).
A method of replenishing the surface end of the alloy bath) 5d is possible.

Here, since the vapor pressures of the respective constituent elements constituting the vapor deposition alloy plating layer are not necessarily the same or substantially equal to each other, the composition of the molten alloy bath and the composition of the mixed vapor generated from the surface of the alloy bath never match. Not a thing. For example, in the above example, since Al (or Zn) is a metal having a higher vapor pressure than Ti (or Cu), Al-T having a higher Al concentration (or Zn concentration) than the alloy bath composition.
i-mixed vapor (or Cu-Zn mixed vapor) is generated from the alloy bath surface. Although the composition of the alloy bath and the composition of the mixed vapor are rarely the same as described above, the composition and the evaporation rate of the obtained Al—Ti mixed vapor (or Cu—Zn mixed vapor) are
It is uniquely determined if the alloy bath composition and the alloy bath surface temperature are constant. Therefore, Al (or Cu) and Ti (or Z
n) the wire-like evaporation raw materials 6a and 6b, respectively, in an amount corresponding to the composition of the mixed vapor to be generated and the evaporation rate, and the alloy bath 5d.
If the gas is supplied while being controlled, the desired vapor composition can be stably secured for a long time.

That is, in the case of alloy plating in which the evaporation raw material itself is made of only a plastically workable metal, it is processed into a wire shape in the same manner as the single plating of the plastically workable metal as shown in FIG. By replenishing each evaporation raw material into the molten bath continuously while controlling the supply rate, a vapor-deposited alloy plating with stable plating thickness and plating composition can be manufactured relatively easily.

[0030]

However, when a vapor-deposited alloy-plated product is produced by producing a mixed vapor of alloy components from a molten alloy bath, a metal that cannot be plastically worked as an element constituting the alloy bath or When the alloy contains one or more components, it is not possible to adopt a method in which only the metal or alloy is processed into a wire shape and continuously supplied to the surface of the molten bath in the evaporation tank. Therefore, it is difficult to obtain a stable raw material supply rate, the composition of the alloy bath is likely to change, and as a result, the vaporization rate and vapor composition of the mixed vapor become unstable, and a uniform vapor-deposited alloy plated product cannot be obtained.

The present invention has been made by paying attention to the problems as described above, and its purpose is to use a metal or an alloy that cannot be plastically worked as an evaporation raw material as a constituent component of the vapor deposition alloy plating layer. An object of the present invention is to provide a vapor deposition plating method that can stably maintain the vaporization rate and vapor composition of a mixed vapor even when it contains one or more components, and can easily obtain a vapor deposited alloy plated product with stable quality.

[0032]

The structure of the vapor deposition plating method according to the present invention, which was able to solve the above-mentioned problems, is to generate mixed vapor from the surface of a molten alloy bath composed of a plurality of metals under a vacuum or a dilute gas atmosphere. In the vacuum vapor deposition plating method of continuously depositing the vapor deposition alloy plating layer on the surface of the zone to be treated which has been previously cleaned, a metal or an alloy capable of plastic working (hereinafter,
A wire-shaped evaporation raw material in which a metal or an alloy different from the metal A (hereinafter referred to as the metal B) is filled or dispersed in the metal A) is continuously introduced into a molten alloy bath composed of the metals A and B. The main point is to generate a mixed vapor of metal A and metal B from the surface of the alloy bath while supplying it to the alloy bath.

This method is most effectively used when the metal B is a metal that cannot be plastically worked (further sublimable) (Cr, etc.), and an electron beam heating method is used as a heating evaporation source. Most effectively by this. In the present invention, the vapor deposition plating method means a vapor deposition plating method in a broad sense including various ion plating methods in addition to the usual vacuum vapor deposition plating method using various heating evaporation sources.

Further, there is no limitation on the kind of the material to be vapor-deposited and it can be applied to metal, non-metal, paper, plastic, etc., and the shape of the material to be treated is
It can be widely applied to various processed materials such as plate, rod, and tube.

[0035]

The structure and effects of the present invention will be described in detail below with reference to the drawings. First, the inventors of the present invention adopted the continuous supply method of the evaporation raw material schematically shown in FIG. 6, and tried to evaporate the evaporation raw material continuously while irradiating the electron beam on the upper surface of the melting bath 5d. That is, in this illustrated example, the plastically workable metal A is the evaporation raw material 6a processed into a wire shape.
The metal B, which cannot be plastically worked, was continuously supplied from the hopper 9 into the molten AB alloy bath 5d as the briquette-shaped evaporation raw material 6c.

When two kinds of evaporation raw materials were continuously supplied by such a method, the metal (or alloy) 6a capable of being plastically worked into a wire could be supplied very stably. As described with reference to FIG. 3, it is difficult to accurately control the supply rate of the metal (or alloy) 6c that cannot be plastically worked, and as a result, the alloy 5d formed in the evaporation tank is formed.
Since the composition of (3) is likely to change and the vaporization rate and vapor composition of the mixed vapor are difficult to stabilize, variations were observed in the deposition amount and the plating composition obtained by vapor deposition.

Also, a block-like evaporation raw material 6c such as a briquette
When the molten alloy bath 5d is replenished by the hopper 9 or the like, there is a case where a scattering phenomenon of the evaporation raw material from the bath surface called splash occurs from the replenishment portion of the alloy bath surface. If it adheres to the surface of the zone 1 to be processed that runs, it may cause a deterioration in the appearance of the vapor-deposited plated product and cause a scratch, which may cause a problem that the product value is significantly reduced.

Therefore, the present inventors abandoned the method as shown in FIG. 6 and studied a vapor deposition alloy plating method by a new raw material supply system. That is, as shown in FIG. 7, the metal A which can be plastically worked is supplied from above the molten alloy bath as the evaporation raw material 6a which is worked into a wire, and the metal B which is not plastically workable.
Is continuously supplied as an ingot-shaped evaporation raw material 6d from the bottom of the evaporation tank 4a, and is melted by irradiation of the electron beam 3 A-B.
The vapor deposition alloy plating was performed while forming the alloy bath 5d.

In this method, the scattering phenomenon (splash) of the evaporation raw material as described with reference to FIG.
It was possible to supply a and 6d with relatively high accuracy, and it was possible to obtain a vapor deposition alloy-plated product having a relatively stable amount of plating and a stable plating composition.

However, this method also has the following problems. That is, in this method, the metal (or alloy) incapable of plastic working is supplied by a method of pushing the ingot-shaped evaporation raw material upward from the bottom of the evaporation tank as in the case of FIG. In order to smoothly push the ingot-shaped evaporation raw material 6d upward while preventing the leakage of the ingot-shaped evaporation raw material 6d from the bottom of the evaporation tank.
Must be a water-cooled evaporation tank (generally a water-cooled copper hearth is used). Therefore, the electron gun 2
Most of the energy given to the molten alloy bath for heating and vaporization is taken by the cooling medium such as cooling water through the contact surface between the evaporation tank 4a and the molten alloy bath 5d, so that the heating efficiency is significantly deteriorated.

Therefore, the evaporation amount of the mixed vapor generated from the molten alloy bath is greatly reduced, and a heating energy source having a large output is prepared to secure the desired amount of coating deposit, or the traveling speed of the zone to be treated is reduced. This is very disadvantageous in terms of production efficiency and manufacturing cost.

Further, when a water-cooling type evaporation tank is used as the evaporation tank 4a, a molten bath is not formed in the entire evaporation tank, and a solidified state is formed near the side wall and the bottom of the evaporation tank. That is, the area where the molten bath is formed is the electron beam 3
It is limited to the portion near the upper surface where the alloy is irradiated, and as a result, the composition of the alloy bath is less likely to be uniform throughout the bath, and the composition of the surface portion of the alloy bath and the solidification of the side wall. Differences may occur between the bath composition in contact with the region and the bath composition near the bottom. This makes it very difficult to control the alloy bath composition to obtain a stable mixed vapor composition. Therefore, this method cannot be said to fulfill the purpose of the invention.

Therefore, the present inventors considered that it is possible to stably supply metals and alloys that cannot be plastically machined to a molten alloy bath as a wire-shaped evaporation raw material like metals that can be plastically machined. Advanced.

Then, as shown in FIG. 9, a metal or alloy (called metal B) that cannot be plastically processed is dispersed in a wire-shaped evaporation raw material made of a metal or alloy (called metal A) that can be plastically processed. A metal B that cannot be plastically processed and a metal A that can be plastically processed by manufacturing a metallized material (Fig. 9a) or a material filled near the center of the wire cross section (Fig. 9b)
As a wire-shaped evaporation raw material in which and are combined, as shown in FIG. 8, while continuously supplying into a molten AB alloy bath, an AB mixed vapor is generated from the surface of the alloy bath to perform vapor deposition alloy plating. It was It was confirmed that the desired deposition amount of the vapor deposition alloy plating and the desired plating composition could be stably obtained by employing this method as described below, and the present invention was completed here.

First, as described above, the coating amount of the vapor deposited alloy plating can be controlled by the surface temperature of the alloy bath if the surface area of the alloy bath is constant. Therefore, if the amount of energy given from a heating evaporation source such as an electron beam is properly controlled, a stable amount of deposited plating can be obtained.

Regarding the plating composition, it is an essential requirement to maintain the alloy bath composition stable, as described above. In this method, however, the amount of the metal B in the wire-shaped metal A is compounded according to the alloy bath composition. The composition of the alloy bath can be kept stable by adjusting It should be noted that the vapor pressures of the metal components constituting the alloy bath are not necessarily the same, and the fact that the alloy bath composition and the mixed vapor composition generated from the surface do not match is as described above. By controlling the amount of energy applied and keeping the temperature of the alloy bath surface constant, the relationship between the arbitrary alloy bath composition and the generated mixed vapor composition is uniquely determined. Therefore, according to the above method, if the AB composite raw material corresponding to the evaporation amount and composition of the mixed vapor evaporated from the surface of the alloy bath is fed into the alloy bath at a wire-like and stable feeding rate, the alloy bath composition and evaporation The mixed vapor composition can be kept constant, and a uniform vapor-deposited alloy plating layer can be formed.

That is, in the present invention, the wire-shaped composite evaporation raw material in which the metal B which cannot be plastically worked is dispersed or filled in the metal A which can be plastically worked is
The composition ratio (weight ratio) of the metal A and the metal B is constant, and by supplying the wire-shaped raw material into the alloy bath at a constant rate, the metal A and the metal B are always maintained at a constant rate (g / g). It will be possible to replenish into the bath in seconds).

Here, in order to keep the alloy bath composition stable, a wire-like evaporation raw material having a composition (content ratio of metal A and metal B in the wire) corresponding to the mixed vapor composition to be evaporated is used. By supplying into the alloy bath at a supply rate (g / sec) corresponding to the evaporation rate (g / sec) of the mixed vapor, the balance balance of the metal A and the metal B of the entire alloy bath is kept substantially constant, As a result, the alloy bath composition will not change.

The composition of the alloy bath and the composition of the generated mixed vapor do not always match, and the composition of the alloy bath, and hence the vapor composition, that is, the plating composition, changes with time unless the raw materials are replenished. If the composite wire-like evaporation raw material having a predetermined composition in which the metal B which cannot be plastically worked is dispersed or filled in the metal A which is plastically workable defined in the present invention, the metal A and the metal B in the alloy bath are used. It becomes possible to easily control the supply rate of the metal, and if the supply amount corresponding to the generation amount of the mixed vapor generated from the alloy bath is replenished by this method, the composition of the metal AB alloy bath, and eventually the mixture of the metal AB are mixed. It becomes possible to easily achieve stabilization of the vapor composition.

That is, according to the present invention, the problems such as the fluctuation of the alloy bath composition and the fluctuation of the mixed vapor composition due to the instability of the feed rate of the raw materials are excellently overcome over the conventional metals or alloys which cannot be plastically worked. It is possible to form a vapor-deposited alloy plating layer of stable quality.

In the method of the present invention, metal B is a metal-A system vapor deposition alloy plating which forms a molten alloy bath with metal A which cannot be plastically worked and has sublimability and which can be plastically worked. The effect is particularly effective when obtaining. That is, as the metal B that cannot be plastically worked and has sublimation property, for example, Cr, Mg, and the like can be cited. However, since these metals cannot be plastically worked, it is easy to control the supply rate as described above. Since it cannot be processed into a wire-shaped raw material and is sublimable, the evaporation rate of metal vapor generated from the solid surface tends to be unstable. However, even if such a metal B is plastically workable and is continuously replenished as a composite wire-like evaporation raw material by being compounded with the metal A that forms an alloy melting bath with the metal B, a stable composition is constantly mixed. Can generate steam.

Therefore, the method of the present invention has a problem of unstable supply of Cr that is sublimable and cannot be plastically worked, for example, in the case of continuously industrially producing a highly corrosion-resistant evaporated Al-Cr alloy plated product. , Can be solved by continuously supplying into the Al-Cr alloy bath as a composite wire with plastically workable Al, whereby it becomes possible to obtain a stable evaporation rate and vapor composition for a long time,
As a result, it becomes possible to continuously obtain a vapor-deposited Al-Cr alloy plated product having a stable coating amount and plating composition.

In the present invention, an electron beam heating system is preferable as the heating evaporation source for generating the mixed vapor from the molten alloy bath. Generally, there are resistance heating method, high frequency induction heating method, electron beam heating method, ion beam heating method, laser beam heating method, arc discharge method, etc. as heating evaporation method of evaporation material in vacuum. It is properly used depending on the evaporation rate, the film forming method, the required quality of the vapor deposition plated film to be obtained, and the like. 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 an electron beam heating method is mainly used for Ti and Zr having a high melting point and a low vapor pressure. ing. However, among these heating methods, the vacuum vapor deposition plating method adopting the electron beam heating method can increase the evaporation rate of the evaporation raw material because the electron beam has high energy and high energy density. It is a very advantageous method in terms of productivity.

Further, in this heating method, since the surface on which the raw material is vaporized is directly irradiated with an electron beam for heating, the heating efficiency (energy efficiency) is high, and the refractory metal and various kinds of vapor having a small vapor pressure are used. It can be easily applied to ceramic materials, and since there are few restrictions on the types of evaporation raw materials to be evaporated, it can be applied to many types of alloy plating and multilayer plating.

Further, since the output of the electron beam can be finely adjusted instantaneously, it is possible to control the evaporation rate of the evaporation raw material for stabilizing the amount of plating adhered and the plating composition of the obtained evaporation plated product. There is also an advantage that it can be dealt with quickly and easily by finely controlling the electron beam output. As described above, the electron beam heating method has various advantages and is recommended as one of the methods capable of achieving the highest productivity in continuously producing vapor-deposited alloy plated products.

As described above, according to the present invention, when the metal that cannot be plastically worked is contained as a constituent component of the alloy plating layer, the evaporation rate and vapor composition of the mixed vapor generated from the desired molten alloy bath can be determined. It is possible to obtain stably,
Therefore, it becomes possible to stably produce an evaporated alloy plated product having a uniform coating amount and a uniform plating composition.

[0057]

EXAMPLES Next, examples of the present invention will be shown, but the present invention is not limited by the following examples. Example 1 A vapor-deposited Al—Cr alloy-plated steel sheet was produced under the following conditions using the continuous vapor deposition plating equipment shown in FIGS. 8 and 10. In FIG. 10, a is a steel strip to be treated, b is a vapor deposition chamber,
c is a connection chamber, d is a deflector roll, e is a table roll, f ₁ is an inlet side vacuum seal device, f ₂ is an outlet side vacuum seal device, g is a seal roll, h is an electron gun, i is an electron beam, j is Evaporation tank, k is molten alloy bath, m is metal AB
Each represents a composite wire.

(Manufacturing conditions) -Material to be plated: Ultra-low carbon Ti killed steel strip-Pre-plating steel strip temperature: 200 to 300 ° C-Pretreatment to material to be plated: Alkaline degreasing-washing-drying, followed by hydrogen-nitrogen mixing Activation treatment by heat reduction of the steel strip surface in a gas atmosphere. After that, the steel strip is cooled in an inert atmosphere and introduced into the deposition chamber via a vacuum sealing device.・ Plating content: Al-Cr alloy plating ・ Amount of coating 10-40 g / m ²・ Plating composition Al-10% Cr

Deposition degree of vapor deposition chamber: 8 × 10 ⁻³ Pa or less ・ Atmosphere gas of inlet / outlet vacuum sealing device: Nitrogen gas with extremely low oxygen content and extremely low moisture content ・ Evaporation source heating source: Pierce type Electron gun, electron beam output 3
5 to 300 kW-Al-Cr alloy bath evaporation tank: Electrofusion high-purity alumina evaporation tank (purity of 98% or more) -Alloy bath composition: Al-45 to 50% Cr-Evaporation raw material: Cr-dispersed Al wire raw material, composition , Al-10% Cr

Under the above manufacturing conditions, Al-10% Cr
The Cr-filled Al wire made of Al is heated and evaporated by the electron beam heating method while being fed to the molten Al-Cr alloy bath to generate an Al-Cr mixed vapor with a stable evaporation rate and vapor composition. I was able to. The vapor-deposited Al-Cr alloy-plated steel strip thus obtained had a certain amount of deposited plating and a certain plating composition, and could be obtained as a vapor-deposited product having excellent appearance quality and plating adhesion.

Further, when the corrosion resistance of the obtained vapor-deposited Al-10% Cr alloy-plated steel sheet (adhesion amount: 20 g / m ² ) was examined, a red rust generation time by a salt spray test was about 5000 hours or more, showing excellent corrosion resistance. It was confirmed that they had.

Example 2 Using the continuous vapor deposition plating equipment shown in FIG. 11, vapor-deposited Zn-Mg alloy plated steel sheet was manufactured under the following conditions. In FIG. 11, n is a heater for heating, p is a heater for evaporation, and other symbols are the same as those shown in FIG. (Production conditions) -Material to be plated: Ultra-low carbon Al-killed steel strip-Pre-plating steel strip temperature: 190 to 210 ° C-Pretreatment to material to be plated: Alkaline degreasing-washing-drying, then in a hydrogen-nitrogen mixed gas atmosphere Activation treatment by heat reduction on the surface of steel strip. After that, the steel strip is cooled in an inert atmosphere and introduced into the deposition chamber via a vacuum sealing device.

[0063] Plating Contents: Zn-Mg alloy plated coating weight 10 to 40 g / m ² · plating composition Zn-10% Mg-deposition chamber vacuum: 1.3 × 10 ^-1 Pa · entry side, the delivery side Atmosphere gas of vacuum sealing device: Nitrogen gas with extremely low oxygen content and extremely low water content ・ Heating source of evaporation raw material: sheath heater resistance heating system, heater output 50 kW ・ Evaporation tank for Zn-Mg alloy bath: Graphitic evaporation tank ・ Evaporation Raw material: Mg dispersed Zn wire raw material, composition, Zn-10% Mg

Under the above manufacturing conditions, Zn-10% Mg
To generate a Zn-Mg mixed vapor at a stable vaporization rate and vapor composition by heating and evaporating the Mg-filled Zn wire made of Mg into a molten Zn-Mg alloy bath by a resistance heating method. I was able to.

Further, when the corrosion resistance of the obtained vapor-deposited Zn-10% Mg alloy-plated steel sheet (having an adhesion amount of 20 g / m ² ) was examined, the red rust generation time by the salt spray test was about 100.
It showed 0 hours or more, and was confirmed to have excellent high corrosion resistance.

[0066]

The present invention is configured as described above, and in the case where a metal that cannot be plastically worked is contained as a constituent component of the vapor deposition alloy plating layer, a metal that cannot be plastically worked is used in another alloy plating configuration. Use as a composite wire-like evaporation raw material dispersed or filled in a metal that can be plastically processed with components to generate a mixed vapor from a molten alloy bath, thereby maintaining a stable evaporation rate and composition of the mixed vapor. As a result, it becomes possible to stably manufacture a vapor-deposited alloy plated product having a uniform coating amount and a uniform plating composition.

[Brief description of drawings]

FIG. 1 is a conceptual diagram showing a conventional vapor deposition plating method.

FIG. 2 is a conceptual diagram showing a conventional vapor deposition plating method.

FIG. 3 is a conceptual diagram showing a conventional vapor deposition plating method.

FIG. 4 is a conceptual diagram showing another example of the vapor deposition plating method.

FIG. 5 is a conceptual diagram showing still another example of the vapor deposition plating method.

FIG. 6 is a conceptual diagram showing a vapor deposition plating method tried by the present inventors.

FIG. 7 is a conceptual diagram showing another vapor deposition plating method tried by the present inventors.

FIG. 8 is a conceptual diagram showing a vapor deposition plating method applied in the present invention.

FIG. 9 is a schematic sectional view illustrating a metal AB composite wire used in the present invention.

FIG. 10 is a schematic explanatory view showing a vapor deposition plating method adopted in Examples.

FIG. 11 is a schematic explanatory view showing a vapor deposition plating method adopted in Examples.

[Explanation of symbols]

 1 Steel strip to be treated (material to be plated) 2 Electron gun 3 Electron beam 4, 4a, 4b Evaporation tank 5, 5a, 5b Molten metal (alloy) bath 6, 6a, 6b Wire (evaporation raw material) 7 Pinch roller

Front page continuation (72) Inventor Junji Kawafuku 1 Kanazawa-machi, Kakogawa-shi, Hyogo Prefecture Kamido Steel Works, Ltd. Kakogawa Steel Works (72) Inventor Koji Irie Kanazawa-cho, Kakogawa-shi, Hyogo Kamido Steel Works, Ltd. Inside the Kakogawa Works (72) Inventor Tota Ayabe 1 Kanazawa-machi, Kakogawa City, Hyogo Prefecture Kamido Steel Works Co., Ltd. Inside the Kakogawa Works (72) Atsushi Kato 1 Kanazawa-machi, Kakogawa City, Hyogo Prefecture Kakogawa Works Co., Ltd. Inside the Steel Works (72) Inventor Shoji Miyake 1 Kanazawa Town, Kakogawa City, Hyogo Prefecture Kado Steel Works Co., Ltd. Inside the Kakogawa Works

Claims (5)

[Claims] 1. A vacuum for forming a vapor-deposited alloy plating layer continuously on a surface of a zone to be treated, which has been cleaned in advance, by generating a mixed vapor from a surface of a molten alloy bath composed of a plurality of metals in a vacuum or a dilute gas atmosphere. In the vapor deposition plating method, a wire-like evaporation in which a metal or alloy (hereinafter, referred to as metal A) that is plastically workable is filled or dispersed with a metal or alloy (hereinafter, referred to as metal B) different from the metal A. A vapor deposition plating method characterized in that a mixed vapor of metal A and metal B is generated from the surface of the alloy bath while continuously supplying the raw material into a molten alloy bath consisting of the metals A and B. 2. The vapor deposition plating method according to claim 1, wherein the metal B is a metal or an alloy that cannot be plastically worked. 3. The vapor deposition plating method according to claim 2, wherein the metal B has a sublimation property. 4. The vapor deposition plating method according to claim 3, wherein the metal A is Al and the metal B is Cr. 5. The vapor deposition plating method according to claim 1, wherein an electron beam heating method is used as the heating evaporation source.