JPH06158285A - Production of al base vapor deposition plating material - Google Patents

Abstract

PURPOSE:To produce an Al alloy plated steel sheet excelling in appearance, workability and chemical conversion when a steel sheet whose surface has been reduced and activated is subjected to Al base metal vacuum vapor deposition plating by an electron beam heating method by controlling the quantity of an oxidizing gas in a plating room and the temperature of the steel sheet to specified values. CONSTITUTION:A steel sheet 1 which has been heated in an atmosphere of a reducing gas to previously reduce and activate its surface is introduced into a vapor deposition room 6 through an intermediate chamber 24. The vapor deposition room 6 is evacuated by vacuum equipment through a vacuum evacuating pipe 22 and the steel sheet 1 is heated so that its temperature T deg.C may be 150 deg.C<=T<=400 deg.C and simultaneously Al 9 in an evaporation tank 11 and metal 10, such as Cr or Ti in an evaporation tank 12 are heated and evaporated by electron beams 8 from an electron gun 2 to give the underside of the steel sheet 1 vapor deposition plating of alloy, such as Al-Cr or Al-Ti. In this case, the composition of the residual gas in the vapor deposition room 6 is controlled to be >=90vol% gaseous hydrogen and <=1X10<-3>Pa total of partial pressures of oxidizing gases, such as moisture, O2, CO2 and CO.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an Al-based vacuum vapor deposition plating method using an electron beam heating method, and more specifically, to obtain an Al-based vapor deposition plating material excellent in appearance, workability, chemical conversion treatment property, etc. The present invention relates to a manufacturing method of.

[0002]

2. Description of the Related Art The so-called vacuum vapor deposition method, in which a vapor deposition material is heated and vaporized in a vacuum or a dilute gas atmosphere to form a vapor deposition plating layer on the surface of a material to be plated, is superior to conventional electroplating methods and hot dip plating methods. It has a high degree of freedom and is characterized in that it is possible to relatively easily produce various types of plating, alloy plating, multi-layer plating, etc. by heating and evaporating one or more of various evaporation raw materials at the same time. There is.

Generally, as the heating and evaporation method used in the vacuum deposition plating method, a resistance heating method, a high frequency induction heating method,
There are an electron beam heating method, an ion beam heating method, a laser beam heating method, an arc discharge method and the like, which are appropriately used depending on the type of evaporation raw material, the film forming method and the like. Among these heating methods, the vacuum evaporation method using 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, and thus the evaporation raw material surface Since it is a method of directly irradiating with an electron beam and heating, it is possible to easily evaporate even a refractory metal or various ceramic materials having high heating efficiency (energy efficiency) and low vapor pressure. Further, since the electron beam can be easily deflected by using a magnetic field, the surface of the evaporation raw material can be arbitrarily scanned (scanned). Furthermore, since it is possible to simultaneously heat and evaporate a plurality of evaporation raw materials with a single electron gun, it is possible to easily produce various alloy plating and multilayer plating by evaporating a plurality of evaporation raw materials. can do. As described above, the electron beam heating method has various advantages, and is one of the methods that can achieve high productivity in continuously producing a vapor-deposited plated material.

By the way, Al and Al alloy materials are more widely used for building materials, home appliances, various containers, etc. because they have better corrosion resistance than steel materials and are lightweight and have a clean appearance. Al-based plated steel sheets that utilize the excellent characteristics of Al materials as a plating layer are also frequently used in machine parts such as automobile exhaust system members, building materials, various heat / light reflecting materials, and garbage incinerator constituent members. That is, the Al-based plated steel sheet is a surface-treated steel sheet in which the excellent corrosion resistance and oxidation resistance of Al are imparted to the surface of the steel sheet.

At present, the hot dipping method is generally used as an industrial method for producing an Al-based plated steel sheet. In this hot dip coating method, the steel sheet is immersed in an Al bath that is in a molten state in the air while passing through it.
It increased to, Fe ₂ in the interface between the steel sheet surface and the Al plating layer
The phenomenon that an Fe-Al-based intermetallic compound layer such as Al ₅ is formed cannot be avoided. Since this intermetallic compound layer is fragile and poor in workability, the Al plating layer is often peeled from the interface with the steel sheet when the hot-dip Al-plated steel sheet is strongly formed and processed. There is a problem in corrosion resistance.

For this reason, a small amount of Si is added to the molten Al bath to make the plating layer contain about 10% of Si.
-By using a Si-based plating layer, the above-mentioned F at the time of manufacturing
A means for suppressing the growth of the e-Al-based intermetallic compound layer and consequently improving the workability of the hot-dip Al-plated steel sheet has been adopted. However, it is impossible to completely eliminate the formation of the intermetallic compound layer by this method in which Si is contained in the plating layer, and the workability cannot be sufficiently improved. Furthermore, the addition of Si to the Al plating layer causes a new problem that the corrosion resistance of the Al plating layer itself is reduced, and an Al-based plated steel sheet having sufficient workability and corrosion resistance after processing by the hot dipping method. It is very difficult to obtain the product.

On the other hand, the Al-plated steel sheet has the following properties under the environment where a large amount of halide ions such as Cl ⁻ ions are present.
The passivation film on the 1 surface is easily destroyed by the halide ions, and pitting corrosion often occurs in the plating layer. A, which is a corrosion product of Al, around the pits
White rust containing l (OH) ₃ as a main component occurs. Further, when pitting corrosion further progresses in the plating thickness direction and reaches the base steel sheet, there is a problem that red rust occurs due to corrosion of the steel sheet. The occurrence of such red rust and white rust is not preferable because it significantly impairs the appearance of the Al-plated steel sheet and reduces the value of the product used.

For the purpose of improving the corrosion resistance of the hot-dip Al-plated steel sheet, an Al-based alloy hot-dip steel sheet in which each element such as Zn is added to the Al-plated layer is also partially used. However, in the above-mentioned hot dip plating method, it is difficult to achieve a sufficient improvement in corrosion resistance because of the manufacturing method, there is a large limitation on the type of metal that can be dissolved in the Al bath and the amount added.

Therefore, as a post-treatment of the molten Al-based plated steel sheet, various chemical conversion treatment films such as chromate treatment and a thin organic resin film are applied to the surface of the plated layer to improve the corrosion resistance. These post-treatments have a great advantage in terms of productivity because they can be continuously performed in a plating line facility for producing hot-dip Al-plated steel sheets. However, since the film formed by the above post-treatment is very thin, it is easily damaged during handling or processing, or due to corrosion, resulting in defect destruction, and the certainty of the effect of improving the corrosion resistance of the hot-dip Al plated steel sheet. Very scarce. Further, there are problems such as working environment during chromate treatment, problems of dissolved Cr ions during use, and deterioration of weldability due to application of an organic resin film.

On the other hand, when the Al-based plated steel sheet is manufactured by the hot dip coating method, the above-mentioned various problems occur. Therefore, the manufacture of the Al-based plated steel sheet by the electroplating method has been researched and developed. Al itself cannot be electrodeposited from an aqueous solution on the surface of a metal substrate due to the problem of hydrogen overvoltage. As the electrodeposition method, various Al-based salts are dissolved in a non-aqueous organic solvent to obtain an electrodeposition from a non-aqueous solution. A deposition method or an electrodeposition method from an Al-based molten salt bath has been studied. Compared to the hot dipping method, the electroplating method has a very high degree of freedom with respect to the kind of metal salt that can be added to the bath used and the content thereof, and the electric pure A
It has an advantage that not only 1-plating but also various electric Al-based alloy plating (for example, Al-Mn alloy plating) can be electrodeposited on the surface of the metal substrate. Further, even if a steel plate is used as the substrate, a fragile Fe-Al-based intermetallic compound is not formed at the interface between the steel plate and the plating layer, so that an Al-based plated steel plate having excellent workability can be obtained. .

However, the electroplating method generally has a problem that the current efficiency is poor as compared with the electrodeposition method from an aqueous solution, or the electrodeposition at a high current density is impossible, and thus the productivity is low. In addition to having the disadvantage of being inferior, in addition to the fact that the plating baths (non-aqueous organic solvent baths, molten salt baths) are electrically unstable, many problems remain for commercialization on an industrial scale. ing.

As described above, while many problems still exist in the hot dipping method and the non-aqueous electroplating method, the vacuum vapor deposition method can perform not only pure Al plating but also various Al alloy plating. It has an advantage that it is easy to obtain an Al-plated steel sheet having good workability.

[0013]

As described above, the vacuum deposition method is superior to the current electroplating method and hot dipping method in that
Since there are many types of raw materials that can be plated and the electron beam as a heating evaporation source has a high energy density, it is advantageous for improving productivity when industrial continuous production is considered.

By the way, in order to industrially continuously perform vacuum vapor deposition plating on a band to be plated, the surface of the vapor deposition chamber is previously kept in advance while maintaining the vapor deposition chamber for performing the vapor deposition plating under a predetermined vacuum. It is necessary to cause the vapor of the vaporized raw material generated to be adhered to the surface of the plated zone by continuously introducing the cleaned plated zone. In industrial continuous production, it is important to grasp and control the suitability conditions in each manufacturing process, but one or two of the performance such as plating adhesion, workability, post-processing corrosion resistance, chemical conversion treatability, etc. Three or more performances are problematic in that an insufficient product may be obtained. In the vapor deposition plating process, the types and gas partial pressures of the gas components remaining in the vacuum in the vapor deposition chamber, the temperature during vapor deposition plating of the zone to be plated, the pretreatment method and conditions for vapor deposition plating of the zone to be plated, and the plating after vapor deposition plating Since there are various condition factors such as the cooling method of the material, the technology for stably and continuously producing products satisfying the above-mentioned performance required for various evaporated Al-based plated materials has not been established yet. Further improvement in the quality of Al-based plated products is desired.

The present invention intends to solve the above problems in the conventional method and to provide optimum manufacturing conditions for obtaining an Al-based plated material of stable quality in the Al-based vacuum deposition plating method using an electron beam heating method. To do.

[0016]

The method for producing an Al-based vapor-deposited plating material of the present invention which has achieved the above-mentioned object is to continuously perform Al-based vapor-deposition plating on at least one surface of a material to be plated which has been pretreated in advance. In the vacuum deposition method to be performed, (1) the residual hydrogen gas in the deposition chamber is
90 vol% or more (2) Of the residual gas in the deposition chamber, the sum of the partial pressures of water, oxygen, carbon monoxide, and carbon dioxide is 1 × 10 ^-3.
It is Pa or less (3) The temperature of the material to be plated at the start of vapor deposition plating; T (° C) satisfies the following formula: 150 ° C ≤ T ≤ 400 ° C. In addition, as a pretreatment of the material to be plated, the material to be plated is heated in a reducing gas atmosphere to reduce and activate the surface of the material to be plated, and then to a predetermined temperature in a non-oxidizing atmosphere. The present invention also includes a pretreatment method of cooling and thereafter introducing the material to be plated into the vapor deposition chamber to continuously perform Al-based vapor deposition plating on at least one surface of the material to be plated.

The vacuum deposition plating method described below is not particularly limited as long as it uses an electron beam as a heating evaporation source. Further, the material to be plated that is subjected to vapor deposition plating is not particularly limited and can be applied to various metal base materials. The shape of the material to be plated is not particularly limited, and it can be applied to various processed materials such as plate, rod, and tube. Hereinafter, a cold-rolled steel strip will be described as an example of the material to be plated.

[0018]

First, the inventors of the present invention will describe Al vapor deposition plating (unless otherwise specified, "plating" means "vapor deposition plating"), Al-Cr alloy plating, Al-Ti alloy plating, and the like. In producing a plated steel sheet, the continuous vapor deposition plating equipment shown in FIGS. 1 and 2 was used to examine the production conditions and the obtained plating quality.

1 and 2 are explanatory views showing examples of continuous plating equipment. The steel strip 1 to be plated, which has been cleaned in advance, is introduced into the vapor deposition chamber 6. The vapor deposition chamber 6 is maintained at a desired degree of vacuum through a vacuum exhaust pipe 22 by a combination of various vacuum exhaust pumps (not shown). In the vapor deposition chamber 6, the evaporation tank 1
Evaporation raw materials 9 and 10 (at least one of which is an Al raw material) are charged in the insides of 1 and 12, and an electron beam 8 generated from an electron gun 7
By scanning and irradiating the surfaces of the evaporation raw materials 9 and 10, the raw materials are heated and evaporated, and the desired Al
Systematic vapor deposition plating is applied. When performing pure Al vapor deposition plating, it is sufficient to prepare only Al as an evaporation raw material in one evaporation tank in the evaporation chamber. The degree of vacuum in the deposition chamber is measured by a vacuum gauge.
The residual gas component in the vapor deposition chamber and its partial pressure are monitored by a gas analyzer 14.

It is generally known that in order to obtain an Al-based vapor deposition plated steel sheet having high performance such as adhesion, it is preferable to make the degree of vacuum in the vapor deposition chamber as high as possible. However, there are cases where good plating adhesion, plating appearance, and the like cannot be obtained simply by controlling the degree of vacuum, and the present inventors have found that when manufacturing vapor-deposited Al-based plating, residual gas components in the vapor deposition chamber and their The influence of the abundance ratio was examined.

As a result, it is always desirable that the total gas partial pressure of water, oxygen, carbon monoxide, and carbon dioxide among the residual gas in the vapor deposition chamber is 1 × 10 ⁻³ Pa or less. It has been clarified that this is a necessary condition for stably obtaining the Al-based vapor-deposited plated steel sheet. Moisture, oxygen,
Since the four gas components of carbon dioxide and carbon monoxide (hereinafter collectively referred to as oxidizing gas) each have an oxygen atom, the surface of the band to be plated is oxidized before vapor deposition plating, or the surface of the band to be plated is deposited. It is an oxidizing gas that causes the oxidation of the Al-based vapor deposition plated layer formed in 1. Therefore, the total of the partial pressures of water, oxygen, carbon monoxide, and carbon dioxide should be 1
It must be less than × 10 ^-3 Pa. If the oxidizing gas component is present in the vapor deposition chamber in an amount of more than 1 × 10 ⁻³ Pa, even if the material to be plated is subjected to a surface reduction treatment, etc. Oxidizing gas components are adsorbed and reacted on the surface of the strip, and a crystalline or amorphous oxide film or a thin reaction film such as an oxyhydroxide film is formed, which is not preferable. In particular, in the case where vapor-deposited strip surfaces in the vapor-deposition equipment illustrated in FIG. 2 are to be vapor-deposited one by one, the surface of the strip to be plated later is plated first. Compared to the surface of the band to be plated, it takes longer time to stay in vacuum after the surface of the band to be plated is cleaned by the pretreatment equipment and before the actual vapor deposition plating is performed. It becomes easy to grow, and the plating adhesion and workability of the obtained Al-based vapor-deposited steel sheet will be lower than those of the previously plated surface.

Furthermore, when Al-based vapor deposition plating is applied to the surface in the state where such an oxide film or the like is grown on the surface, the adhesion of the plating is deteriorated, and thus the obtained vapor-deposited Al-based plating layer and the band to be plated are obtained. Part of the plating layer peels off at the interface, which leads to a decrease in workability of the product, and part of the plating layer falls off due to processing, and corrosion resistance at the location where the plating layer peels off also decreases. However, the desired corrosion resistance cannot be obtained after processing.

Further, when a thin film composed of an oxide film, an oxyhydroxide film or the like due to adsorption / reaction of an oxidizing gas component grows unevenly on the surface of the Al-based vapor-deposited plating layer, this causes visual appearance. It appears as unevenness and the product value is significantly reduced. Further, when the surface or a part of the Al-based vapor deposition plated layer is oxidized, a crystalline or amorphous Al-based oxide is formed inside or on the surface of the plated layer, or
Or because oxygen is supersaturated in the plating layer as a solid solution,
Distortion occurs in the crystal structure (crystal lattice) of the plating layer, the hardness of the plating layer itself increases, and the ductility becomes poor,
When the obtained vapor-deposited Al-based plated steel sheet is subjected to strength processing, cracks, cracks, and plating peeling of the plating layer may occur, resulting in deterioration of workability of the product and corrosion resistance after processing.

Therefore, in the present invention, the oxidizing gas remaining in the vacuum in the vapor deposition chamber is reduced as much as possible, that is, among the residual gas in the vapor deposition chamber, moisture, oxygen, carbon monoxide, and carbon dioxide are respectively contained. The total gas partial pressure of 1 ×
A value of 10 ^-3 Pa or less always has good performance A
This is a necessary condition for obtaining an l-type vapor deposition plated steel sheet stably.

As the kind of residual gas component in the deposition chamber, a gas component having an extremely slight oxidizing property may remain in addition to the above four components, but basically, a special oxidizing property in a vacuum is intentionally set. Unless the gas components are introduced, the above four types are regarded as oxidizing gas components in vacuum, so the total pressure of the four components may be controlled to 1 × 10 ⁻³ Pa or less.

Next, in the method of the present invention, it is essential that the residual hydrogen gas in the vapor deposition chamber occupy 90 vol% or more of the total residual gas in the vapor deposition chamber. Since hydrogen gas is a reducing gas, there is no adverse effect of the oxidizing gas described above, and conversely, the effect of suppressing adsorption / reaction of oxidizing gas components by adsorbing on the surface of the plated zone or the plating layer surface. Have. That is, hydrogen gas is adsorbed on the surface of the band to be plated before vapor deposition plating to prevent the surface of the band to be plated from being oxidized by an oxidizing gas, and to maintain the surface of the band to be plated that has been cleaned and activated in the pretreatment process. By adsorbing on the surface of the Al-based plating layer after vapor deposition, it is possible to prevent oxidation of the surface of the plating layer due to oxidizing gas and obtain a beautiful vapor-deposited Al-based plating product with no uneven surface appearance.

In the present invention, the means for achieving the abundance ratio of the above gas components remaining in the vacuum in the vapor deposition chamber within the range specified by the present invention is not particularly limited, but the following method is recommended, for example.

As the vacuum pump provided in the vapor deposition chamber, it is preferable to use a vacuum pump having a sufficiently large exhaust capacity for ensuring a high degree of vacuum. This is because the higher the vacuum in the vapor deposition chamber, the easier it is inevitably to reduce the total total of the four types of oxidizing gas partial pressures.

It is preferable to reduce the vacuum leak location and the leak amount in the vapor deposition chamber or the vacuum equipment and piping attached to the vapor deposition chamber as much as possible. This is an essential condition for maintaining a high vacuum, and can effectively prevent the oxidizing gas partial pressure from increasing due to leakage.

It is preferable to sufficiently evacuate the vapor deposition chamber before the vapor deposition plating process is performed. By increasing the vacuum evacuation time, a high degree of vacuum can be achieved, and there is also an effect of reducing the amount of water released from the inner wall of the deposition chamber during plating.

It is preferable to perform a baking process in the deposition chamber before the deposition plating process. Oxidizing gas such as moisture adsorbed on the inner wall of the vapor deposition chamber is actively released into the vacuum by various heat treatments before the vapor deposition plating to reduce the amount of moisture in the vacuum in advance. be able to.

A panel, a device such as a pipe, which is cooled to an extremely low temperature (-100 ° C. or less) by various refrigerants, a so-called cold trap is installed at an arbitrary place in the deposition chamber or a head portion of a vacuum exhaust system pipe attached to the deposition chamber. It is introduced, and before or during vapor deposition plating, it adsorbs and captures residual oxidizing gas such as water in vacuum and removes it.

Prior to vapor deposition plating, the gettering action of Al vapor and alloying element vapor evaporated from the surface of the evaporation tank is utilized to adsorb or oxidize the residual oxidizing gas existing in the vacuum in the evaporation chamber in advance. Is preferably performed. Since Al is a metal with a high affinity for oxygen,
By this getter action, the oxidizing gas can be effectively captured.

It is preferable that the inside of the vapor deposition chamber is set to a high vacuum by the above-mentioned method, and further hydrogen gas is intentionally introduced into the vacuum.

By the way, the present inventors have confirmed that, in addition to the conditions of the residual gas components in vacuum, the temperature of the zone to be plated during vapor deposition has an influence on the quality of the Al-based vapor-deposited steel sheet. Generally, it is not limited to Al vapor deposition plating,
The zone temperature T (° C.) to be plated at the time of various vapor deposition plating processes is adjusted in advance to a predetermined temperature range according to various purposes, but in the method of the present invention, plating adhesion, workability is secured, and a good plating surface is obtained. From the viewpoints of appearance, color tone, suppression of alloying between the plating layer and the plated zone, etc., the temperature of the plated zone T during vapor deposition plating
Was set to be in the range of 150 ° C. ≦ T ≦ 400 ° C. as an essential requirement.

When the zone temperature to be plated is less than 150 ° C.,
Since the plating appearance has a dark gray color tone and the glossiness and brightness are also lowered, it is not preferable because even if the above-mentioned oxidizing gas is set to 1 × 10 ⁻³ Pa or less, it is difficult to obtain a beautiful appearance. This is because the size and orientation of the plating crystal grains on the surface of the Al-based vapor deposition plating layer formed on the surface of the plated zone are mainly affected by the temperature of the plated zone, and the temperature of the plated zone is When the temperature is lower than 150 ° C., it is considered that this is because the crystal grains become fine and the unevenness on the surface of the plating layer becomes large, and light having a wavelength in the visible light region is scattered on the surface of the plating layer.

When the zone temperature to be plated is less than 150 ° C., the Al-based vapor deposition plating obtained can be obtained even if all the conditions of the degree of vacuum in the vapor deposition chamber and the partial pressure of the gas component in the vacuum defined above are satisfied. Depending on the coating amount of the steel sheet (especially Al-based alloy plated steel sheet), the plating adhesion and the workability may decrease, which is not preferable. The reason for this is that the bonding force at the interface between the Al-based plating layer formed by adhesion on the surface of the band to be plated and the band to be plated is affected by the temperature of the band to be plated. It is considered that the binding force becomes insufficient.

As another reason, when the temperature of the zone to be plated is low, the crystal structure of the formed Al-based vapor deposition plated layer is likely to be distorted and the residual strain stress of the plated layer becomes large, so that the ductility of the plated layer is increased. It is thought that this is due to the decrease. In this way, the Al-based vapor-deposited steel sheet obtained under the condition that the zone to be plated is less than 150 ° C has cracks and cracks in the plating layer when subjected to the strength forming process, and further, the portion of the plating layer. The temperature T of the zone to be plated must be 150 ° C. or higher, because the target stripping / peeling may occur, resulting in a decrease in the workability as an Al-based vapor deposition plated product and the corrosion resistance after processing.

On the other hand, the upper limit of the zone temperature T to be plated needs to be 400 ° C. When the Al-based vapor deposition plating layer is applied at a plating zone temperature of over 400 ° C, the plating zone temperature after the vapor deposition plating process becomes a high temperature of over 500 ~ 550 ° C, especially for pure Al vapor deposition plated steel sheet. At the interface between the pure Al plating layer and the steel sheet, Fe-A similar to that of the hot dip plated steel sheet
This is not preferable because an l-based intermetallic compound layer may be formed. When this intermetallic compound is formed at the interface, Al
When forming a vapor-deposited steel sheet with high strength, the interfacial bonding force between the plating layer and the intermetallic compound layer is weak, so the plating layer peels off and the workability and corrosion resistance after processing are significantly reduced. .

As described above in detail, in the method for producing an Al-based vapor deposition plated material of the present invention, (1) the residual hydrogen gas in the vapor deposition chamber is the total residual gas in the vapor deposition chamber.
90 vol% or more (2) Of the residual gas in the deposition chamber, the sum of the partial pressures of water, oxygen, carbon monoxide, and carbon dioxide is 1 × 10 ^-3.
It is Pa or less (3) The temperature of the material to be plated at the start of vapor deposition plating; it is an essential requirement to simultaneously satisfy the three conditions of 150 ° C. ≦ T ≦ 400 ° C. at which T (° C.) satisfies the following formula. If these three conditions are satisfied, it is possible to stably secure the required performance such as plating adhesion, workability, post-processing corrosion resistance, and aesthetics of the Al-based vapor deposition plated material.

In the method for producing an Al-based vapor deposition plated steel sheet of the present invention, it is preferable to perform a pretreatment for cleaning and activating the material to be plated before the vapor deposition plating treatment. These pretreatments are necessary to secure the plating adhesion of the Al-based vapor deposition plated layer. As the pretreatment method, an optimal treatment is appropriately performed depending on the material of the plated zone. For example, when the plated zone is Al or Al alloy, an alumite film treatment is performed, and for other metal materials, After degreasing and / or pickling, an extremely thin adhesion amount of undercoating with good adhesion to the band to be plated, which is called pre-coating, is performed and cannot be determined uniquely.

The method for producing the Al-based vapor deposition plated material of the present invention is not particularly limited with respect to these pretreatment methods, and an optimal pretreatment method may be adopted depending on the material of the band to be plated and the like. Generally, in the case where the strip to be plated is various steel plates, the strip to be plated is subjected to a cleaning process such as degreasing and pickling, and then the surface of the strip to be plated is activated by various methods.

As a typical activation treatment method, there is an ion bombardment treatment with an inert gas ion such as Ar ion or nitrogen ion in a vacuum.
In this method, plasma of the above-mentioned gas component is formed in a vacuum by various methods, and the gas component positively ionized from the plasma is collided with the surface of the band to be plated at high speed to bombard the surface of the plate to be plated (sputtering). This is a method of removing the adsorbate, oxide film, etc. on the surface of the plated zone. However, in order to obtain a sufficient activation effect by this method, a relatively long period of time is required, so when continuously producing a vapor-deposited plated material, this activation process becomes the rate-determining factor, resulting in Al-based vapor deposition. It is not preferable because the productivity of plated products will be significantly reduced.

In the present invention, it is preferable that the material to be plated is heated in a reducing gas atmosphere to reduce and activate the surface of the material to be plated. A mixed gas of nitrogen and hydrogen is preferably used as the reducing gas, and the surface of the material to be plated can be reduced and activated by heating it to 600 ° C. or higher in the reducing gas. After the activation treatment, it is a preferred embodiment that the material to be plated is cooled to a predetermined temperature in a non-oxidizing atmosphere, and then the material to be plated is introduced into the vapor deposition chamber to perform vapor deposition plating. By adopting this cleaning and activation pretreatment method, it is possible to further enhance the adhesion between the Al-based vapor deposition plated layer and the surface of the band to be plated, and to obtain excellent plating adhesion and workability.

In order to introduce the plated zone activated by this cleaning pretreatment method into the deposition chamber while keeping the surface state of the plated zone, it is necessary to prevent the surface from being reoxidized. Therefore, after the reduction treatment, the zone to be plated is cooled to a predetermined temperature in a non-oxidizing atmosphere and introduced into the vapor deposition chamber via a desired vacuum sealing device or the like in which a dilute non-oxidizing atmosphere is maintained. do it.

The cooling method of the plating strip after Al-based vapor deposition plating is not particularly limited, but the plating strip temperature after plating is considerably increased by latent heat received from the raw material metal vapor and sensible heat or radiant heat received from the surface of the evaporation tank. However, if it is led from the vacuum to the atmosphere through the specified vacuum seal device in this state, the desired performance may not be obtained, so the vacuum seal device under a dilute non-oxidizing atmosphere may be used. Then, a method of sufficiently cooling in a non-oxidizing atmosphere and then introducing it into the atmosphere is preferable.

When the Al vapor deposition plating material is introduced into the atmosphere in a high temperature state, the surface Al of the plating layer reacts rapidly with oxygen and moisture in the air to form an ultrathin oxide film (passive film). It is formed. When the plating zone temperature is high, the growth of the oxide film is promoted. The oxide film thickly grown on the surface of the Al-based vapor deposition plated band is not preferable because it not only impairs the aesthetic appearance of the Al-based plated surface but also causes deterioration of chemical conversion treatment such as chromate treatment.

In the present invention, for example, when the material to be plated is a steel plate and Al-based alloy plating is performed using the continuous vapor deposition plating equipment illustrated in FIG. 2, a series of steps are performed as follows. First, the steel sheet 1 is degreased in the degreasing device 2 and activated by being heat-treated in a gas reduction furnace 3 in a mixed reducing gas atmosphere of nitrogen and hydrogen. The activated steel sheet 1 is also cooled in the non-oxidizing cooling zone 4 in the reducing gas atmosphere, passed through the inlet side vacuum sealing device 5 in the dilute nitrogen gas atmosphere, and introduced into the first vapor deposition chamber 6. . First deposition chamber 6
After plating one surface (the lower surface in the drawing) of the steel sheet 1 into the second vapor deposition chamber 17 via the intermediate chamber 15, the other surface of the steel sheet 1 is plated. Then, after being sufficiently cooled in a non-oxidizing cooling zone 19 in a nitrogen atmosphere via a vacuum sealing device 18 in a dilute nitrogen gas atmosphere, a skin pass roll
It is introduced into the post-processing device 21 through 20. The first vapor deposition chamber and the second vapor deposition chamber are, of course, adjusted so as to satisfy the specified conditions of the present invention. Other facilities are not limited to those illustrated in FIG.

It has been explained that by adopting the method for producing an Al-based vapor-deposited plated material of the present invention, it is possible to continuously industrially produce products that sufficiently satisfy various performances of the Al-based vapor-deposited plated material. Hereinafter, the present invention will be described in more detail with reference to examples.

[0050]

【Example】

Example 1 Using the continuous vapor deposition plating equipment shown in FIGS. 1 and 2,
As shown in Table 1, pure Al vapor deposition plated steel sheets were manufactured by changing the vapor deposition conditions, and the quality of the obtained plated material was examined. The main manufacturing conditions other than those shown in Table 1 are as follows.

<Main manufacturing conditions> -Strip material: Ultra-low carbon Al-killed cold-rolled steel strip-Stainless steel plate pretreatment: Degreasing cleaning-washing-drying, plating in a hydrogen-nitrogen mixed gas atmosphere Reduction / activation treatment was performed by heating the strip. Hydrogen concentration: 5% (vol%) Plated zone temperature: 600 ° C or higher After that, the zone to be plated is cooled to a predetermined temperature in a mixed gas atmosphere of H ₂ -N ₂・ Evaporation plating content: Pure Al vapor deposition plating ・ Vacuum deposition chamber vacuum Degree: The degree of vacuum in the vapor deposition chamber was measured by an ionization vacuum gauge that was calibrated in advance. -Ratio of residual gas components in vapor deposition chamber: The ratio of residual gas components (composition ratio) was measured by the following analyzer. ULVAC; mass filter type gas analyzer (MASSMATE-200 type)

Atmosphere conditions for inlet / outlet vacuum sealing device: Dilute nitrogen gas atmosphere with extremely low oxygen content and extremely low dew point Oxygen content: 20 ppm or less Dew point: -60 ° C Heating source of evaporation material: Pierce type electron Gun (max output: 3
(00 kW) ・ Evaporation tank: Electrofusion high purity alumina evaporation tank (purity of 98% or more) (only one is used) (equivalent to 11 in FIGS. 1 and 2) ・ Evaporation raw material replenishment method: Pure Al wire (A1050 equivalent)
Is continuously replenished into the molten Al bath by a wire feeder (purity 99.7% or more) -Cooling method for plated zone after vapor deposition plating: Nitrogen gas cooling with extremely low oxygen content and extremely low dew point Gas cooling-circulation injection method Oxygen content : 20ppm or less Dew point: -60 ℃

The vapor-deposited pure A obtained under the above manufacturing conditions
The following performance evaluation tests were performed on the 1-plated steel sheet. 1. Plating adhesion and workability test Attach cellophane tape to the processed part of the ball impact processed test piece, and visually evaluate the presence or absence of the plated piece adhered to the peeled tape. After bending the test piece in close contact with 180 °, a cellophane tape is attached to the bent portion, and the presence or absence of the plated piece attached to the peeled tape is visually evaluated. The above-mentioned two types of processing tests were performed, and the following judgments were made. ◯: Excellent plating adhesion In both tests, peeling of plated pieces is not observed at all. Δ: Plating adhesion is slightly inferior. In at least one of both tests, slight peeling of the plated piece is observed. X: Inferior plating adhesion In at least one of both tests, peeling of the plated pieces is noticeably observed.

2. Surface appearance investigation The presence or absence of color unevenness due to the oxide film on the plated surface and the degree thereof were visually examined in the longitudinal direction of the plated zone and the plate width direction, and the following judgment was made. ◯: No unevenness in color, gloss, and excellent surface appearance. Δ: The color unevenness is hardly noticeable, but the gloss of the color uneven portion is slightly low and the surface appearance is slightly inferior. X: Color unevenness is noticeable, and the gloss of the color unevenness portion is considerably low, resulting in poor surface appearance. The obtained results are summarized in Table 1 together with the results of the comparative material.

[0055]

[Table 1]

As is apparent from Table 1, when the conditions of the ratio of residual gas components in the vacuum in the deposition chamber and the temperature of the zone to be plated during vapor deposition plating are both satisfied at the same time (No. 1 to 11). ) It has excellent plating adhesion and plating surface appearance. On the other hand, if even one of the above three conditions is out of the specified range (Nos. 12 to 25), it is understood that the plating adhesion and the plating surface appearance are inferior. Especially when the vacuum degree of the deposition chamber is low (the residual gas pressure is high) and the proportion of hydrogen gas in the residual gas is very small (No. 15 to 17, 2).
0, 25) is inferior in both plating adhesion and workability, and when the zone temperature to be plated during vapor deposition plating is out of the specified range of the present invention and is low (No. 20) or high
(No.25) is especially poor in both performances.

Example 2 Using the continuous vapor deposition plating equipment shown in FIGS. 1 and 2,
As shown in Table 2, the vapor deposition conditions were changed to manufacture an Al alloy vapor deposition plated steel sheet, and the quality of the obtained plated material was examined. The main manufacturing conditions other than those shown in Table 2 are as follows. The degree of vacuum in the vapor deposition chamber and the residual gas component were measured in the same manner as in Example 1.

<Main manufacturing conditions> • Strip material: Ultra-low carbon Ti-killed cold-rolled steel strip • Plate pretreatment: Same as in Example 1.・ Vapor deposition content: Al alloy vapor deposition plating (type,
The adhesion amount is as shown in Table 2.)-Atmosphere conditions of the inlet / outlet vacuum seal device: the same as in Example 1. Heat source for evaporation raw material: Same as in Example 1.

Evaporation tank: Evaporation tank for Al bath (in FIGS. 1 and 2)
Equivalent to 11) Evaporative high purity alumina evaporation tank (purity 98% or more) Cr evaporation tank (used during Al-Cr alloy plating, equivalent to 12 in Figs. 1 and 2) Graphite evaporation tank (sealing treatment material) ) In addition, a system is used in which a Zr-Cr alloy bath is formed in the evaporation tank and only Cr is selectively evaporated from the alloy bath. Ti evaporation tank (used during Al-Ti alloy plating, 12 in FIGS. 1 and 2) Equivalent) Graphite evaporation tank (sealing material) -Evaporation raw material replenishment method: Al raw material Pure Al wire (A1050 equivalent) is continuously replenished into the molten Al bath by a wire feeder (purity 99.7% or more) Cr raw material Cr briquette With the briquette feeder, the above Zr
-Continuous replenishment into Cr alloy bath (purity 99.7% or more) Ti raw material Continuous replenishment of pure Ti wire by wire feeder (purity
99.7% or more) -Plating zone cooling method after vapor deposition plating: Same as in Example 1.

Under the above manufacturing conditions, the following performance evaluation tests were conducted on the various vapor-deposited Al-based alloy plated steel sheets obtained. 1. Plating adhesion, workability test The test contents and judgment criteria are the same as in Example 1. 2. Chemical conversion treatment After the vapor-deposited Al-based alloy-plated steel strip was skin-pass rolled, a coating type chromate treatment was performed and the appearance of the surface was visually determined. ∘: Excellent chemical conversion treatability A uniform chromate film is formed without uneven chromate treatment. Δ: Slightly inferior in chemical conversion processability A slight amount of chromate treatment unevenness due to unevenness of the plating surface occurred. X: Inferior in chemical conversion processability A considerable amount of uneven chromate treatment due to uneven plating surface occurred.

3. Corrosion resistance after processing Test pieces were subjected to overhanging processing with an Erichsen tester and cross-cut processing from the plating surface with a cutter knife, and the test pieces were subjected to a salt spray test and tested for 1% red rust occurrence time of the steel sheet to be plated. Evaluated. Good: Corrosion resistance after processing is slightly inferior to 1% red rust occurrence time of unprocessed test piece. Δ: Corrosion resistance after processing is slightly inferior, and red rust occurs in half or less of the 1% red rust generation time of the unprocessed test piece. X: Corrosion resistance after processing is considerably inferior. Red rust occurs early in the processed part. The obtained results are summarized in Table 2 together with the results of the comparative material.

[0062]

[Table 2]

As is clear from Table 2, both the Al-Cr alloy vapor-deposited steel sheet and the Al-Ti alloy vapor-deposited steel sheet satisfy all the manufacturing conditions specified in the present invention (No. 1).
~ 6, 15 ~ 17), it is understood that the plating adhesion, chemical conversion treatability, and corrosion resistance after processing are both excellent. On the other hand, the existence ratio of the residual gas component specified in the present invention,
Al-Cr alloy vapor-deposited steel sheet (No. 7 to 14) and Al-Ti alloy plated steel sheet (No. 18 to 26) produced by deviating from the specified range of the present invention under at least one of the conditions of the zone to be plated. ), At least one of the above performances is inferior.

[0064]

The present invention is constituted as described above, and A
In the continuous production of l-based vapor-deposited plating materials, the plating adhesion, appearance and chemical conversion can be determined by defining the existence ratio (composition ratio) of residual gas components in the vacuum of the vapor deposition chamber and the zone temperature to be plated during vapor deposition plating. It has become possible to stably obtain products with excellent processability.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of continuous vapor deposition plating equipment.

FIG. 2 is an explanatory diagram of continuous vapor deposition plating equipment.

[Explanation of symbols]

 1 Plated Material 2 Degreasing Device 3 Gas Reduction Furnace 4 Non-Oxidizing Cooling Zone 5 Inlet Vacuum Sealing Device 6 (1st) Deposition Chamber 7 Electron Gun 8 Electron Beam 9 Evaporation Raw Material A 10 Evaporation Raw Material B 11 Evaporation Tank A 12 Evaporation Tank B 13 Vacuum gauge 14 Gas analyzer 15 Intermediate chamber 16 Deflector roll 17 Second deposition chamber 18 Outgoing side vacuum seal device 19 Non-oxidizing cooling zone 20 Skin pass roll 21 Post-treatment device 22 Vacuum exhaust pipe 23 Table roll 24 Intermediate chamber

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tota Ayabe 1 Kanazawa-machi, Kakogawa-shi, Hyogo Prefecture Kamido Steel Works Kakogawa Works (72) Shoji Miyake 1 Kanazawa-cho, Kakogawa-shi, Hyogo Kami Co., Ltd. To Steel Works, Kakogawa Works

Claims (2)

[Claims] 1. A vacuum vapor deposition method for continuously performing Al-based vapor deposition plating on at least one surface of a material to be plated which has been pretreated in advance, (1) The residual hydrogen gas in the vapor deposition chamber is the total residual gas in the vapor deposition chamber.
90 vol% or more (2) Of the residual gas in the deposition chamber, the sum of the partial pressures of water, oxygen, carbon monoxide, and carbon dioxide is 1 × 10 ^-3.
Pa is less than or equal to (3) The temperature of the material to be plated at the start of vapor deposition plating; T (° C) satisfies the following formula: 150 ° C ≤ T ≤ 400 ° C. Method of manufacturing wood. 2. As a pretreatment of the material to be plated, the material to be plated is heated in a reducing gas atmosphere to reduce and activate the surface of the material to be plated, and then subjected to a predetermined treatment in a non-oxidizing atmosphere. The Al-based vapor deposition plating according to claim 1, wherein the material to be plated is cooled to a temperature, and then the material to be plated is introduced into the vapor deposition chamber to continuously perform Al-based vapor deposition plating on at least one surface of the material to be plated. Method of manufacturing wood.