Vacuum deposition apparatus and process for coating substrate

Abstract

The invention relates to a vacuum deposition apparatus and a process for coating a substrate for continuously depositing a coating on a traveling substrate formed from a metal alloy comprising a main element and at least one additional element, comprising a vacuum deposition chamber and means for traveling the substrate through the chamber, the apparatus further comprises a vapor jet coater, an evaporator crucible adapted to supply to the vapor jet coater a vapor containing a primary element and at least one additional element, a recharge furnace adapted to supply to the evaporator crucible a primary element in a molten state and capable of maintaining a constant liquid level in the evaporator crucible, a supply unit adapted to supply the primary element in the molten state to the evaporator crucible, the supply unit is adapted to supply at least one additional element in a solid state and to supply at least one additional element in a molten, solid or partially solid state to the evaporator crucible without difference.

Description

[0001] This application is a divisional application of the application filed on July 27, 2017, with Chinese national application number 201780046572.5 (international application number PCT / IB2017 / 000876) and entitled "Apparatus and Method for Vacuum Deposition". Technical Field

[0002] This invention relates to a vacuum deposition apparatus for depositing coatings formed of metal alloys, such as zinc-magnesium alloys, onto a substrate. The apparatus is more specifically used for coating steel strips, but is not limited thereto. The invention also relates to methods for coating such substrates. Background Technology

[0003] Various processes are known for depositing metallic coatings made of alloys on substrates such as steel strips. Among these processes, hot bath coating, electrodeposition, and various vacuum deposition processes such as vacuum evaporation and magnetron sputtering can be mentioned.

[0004] WO2008 / 142222 describes the deposition of metallic alloy layers on a moving substrate using a vacuum deposition apparatus, comprising: an acoustic vapor jet coater; an evaporation crucible adapted to supply vapors containing the metallic element of the coating to the coater; and a recharge furnace adapted to supply molten metallic alloy to the evaporation crucible via a pressure effect. This recharge furnace facilitates the production of a given coating composition. However, if a change in coating composition is required, the height between the recharge furnace and the evaporation crucible must be adjusted. This could result in large-scale engineering work on the recharge furnace, which is industrially impractical.

[0005] EP2937442 also discloses the deposition of metal alloy layers on a moving substrate using a vacuum deposition apparatus, wherein the vacuum deposition apparatus includes: an acoustic vapor jet coater; and an evaporation crucible supplied with an ingot that is slightly molten on top of a metal alloy plating bath. This supply is limited because two types of ingots are necessary: ​​one in the metal alloy plating bath composition to start the apparatus and another in the metal alloy layer composition to compensate for evaporation at operating power. Moreover, such ingots with a given alloy composition may be difficult to manufacture and costly. Furthermore, the melting rate of the ingot limits the apparatus's ability to follow changes in production line speed. Summary of the Invention

[0006] Therefore, the object of the present invention is to overcome the shortcomings of prior art equipment and processes by providing a vacuum deposition apparatus for depositing coatings formed from metal alloys and a process for manufacturing substrates covered with metal alloy layers, which allows for flexible management of variations in metal alloy composition without compromising production line capacity.

[0007] For this purpose, a first subject of the present invention is a vacuum deposition apparatus for continuously depositing a coating formed of a metal alloy comprising a main element and at least one additional element on a traveling substrate. The apparatus includes a vacuum deposition chamber and means for allowing the substrate to travel through the chamber, wherein the apparatus further includes:

[0008] - Vapor jet coating device

[0009] - An evaporation crucible adapted to supply vapor containing a main element and at least one additional element to a vapor jet coater.

[0010] - A recharge furnace, adapted to supply molten main elements to an evaporation crucible and maintain a constant liquid level within the crucible.

[0011] - A supply unit adapted to supply at least one additional element in solid form, and adapted to supply at least one additional element in molten, solid or partially solid form to an evaporation crucible without discrimination.

[0012] The device according to the invention may also have the following optional features, individually or in combination:

[0013] - The supply unit includes the supply pipe,

[0014] - The lower end of the supply pipe is below the liquid level in the evaporation crucible.

[0015] - The evaporation crucible includes a cover, to which a supply pipe is connected.

[0016] - The supply tube includes an ingot holder adapted, on the one hand, to hold at least one additional element while it is being heated, and on the other hand, to release at least one additional element into the evaporation crucible.

[0017] - The ingot retainer is a valve with a U-shaped cross-section.

[0018] - The supply tube includes an inert gas inlet, which is adapted to provide a pressure higher than the pressure in the evaporation crucible, at least in the lower portion of the supply tube.

[0019] - The supply unit includes a preheating furnace,

[0020] - The supply unit includes a heating device.

[0021] - The vapor jet coating device is an acoustic vapor jet coating device.

[0022] - The steam for the vapor jet coater is supplied via an evaporation tube that connects the evaporation crucible to the vapor jet coater.

[0023] - The refill furnace is positioned below the evaporation crucible and is designed to be maintained at atmospheric pressure.

[0024] The main element for the evaporation crucible is supplied via a pipe that connects the refill furnace to the evaporation crucible.

[0025] - The evaporation crucible includes an induction heater.

[0026] - The refill furnace is connected to the metal ingot supply device.

[0027] A second aspect of the present invention is a process for coating a substrate, the process comprising:

[0028] - (i) Supplying molten main elements to the metal alloy plating bath,

[0029] - (ii) Heating at least one additional element in solid form above the metal alloy plating bath, and indiscriminately supplying at least one additional element in molten, solid, or partially solid form to the metal alloy plating bath.

[0030] - (iii) Evaporation of a metal alloy plating bath containing a main element and at least one additional element,

[0031] - (iv) Spraying a substrate with a vapor containing a main element and at least one additional element, and

[0032] - (v) Continuously depositing a metal alloy layer containing a main element and at least one additional element on a substrate.

[0033] A third aspect of the present invention is a process for coating a substrate, the process comprising:

[0034] - (i) Evaporation of a metal alloy plating bath containing a main element and at least one additional element,

[0035] - (ii) Spraying a substrate with a vapor containing a main element and at least one additional element, and

[0036] - (iii) Continuously depositing a metal alloy layer containing a main element and at least one additional element on a substrate,

[0037] The metal alloy plating solution is supplied with a molten main element on one hand and at least one additional element in at least a partially solid state on the other hand.

[0038] The two processes according to the invention may also have the following optional features, either individually or in combination:

[0039] - Vapor is ejected onto the substrate at the speed of sound.

[0040] - The metal alloy plating bath is continuously supplied with main elements.

[0041] - Continuous supply is achieved through the effect of air pressure.

[0042] - Remove oxides that may be present on the surface of at least one additional element before heating the metal alloy plating bath.

[0043] - Oxide removal is achieved through chemical polishing.

[0044] - The metal alloy plating bath is discontinuously supplied with at least one additional element.

[0045] - At least one additional element is in the form of an ingot.

[0046] - By controlling the size of the ingot and / or the frequency of feeding, the composition of the metal alloy plating solution can be kept constant over time.

[0047] - The metal alloy plating bath is continuously supplied with at least one additional element.

[0048] - At least one additional element is in the form of wire.

[0049] - By controlling the wire diameter and / or feed rate, the composition of the metal alloy plating solution remains constant over time.

[0050] - At least one additional element has a lower density than the main element.

[0051] - The main element is zinc.

[0052] - At least one additional element is magnesium.

[0053] - The process involves continuously depositing a zinc-based metal alloy layer with a magnesium content of 0.1% to 20% by weight on the substrate by evaporating a zinc-based metal alloy plating bath with a magnesium content of 8% to 43% by weight.

[0054] It is evident that this invention is based on a dual supply system for the evaporation crucible, which utilizes both the supply of the main element of the metal alloy and the supply of additional elements of the metal alloy. Specifically, this invention utilizes:

[0055] - The main element is continuously supplied to the evaporation crucible in a molten state, while...

[0056] - A very flexible supply of additional elements, based on ingots or wires that can be kept in a solid, partially molten, or fully molten state without distinction.

[0057] Because of this dual supply, the composition of the metal alloy plating bath, and thus the composition of the metal alloy layer, can be easily altered by adjusting the supply frequency of the additional elements and / or by adjusting the properties of the additional elements. Furthermore, rapid variations in production line speed are possible due to the capacity of the recharge furnace and its ability to continuously supply the evaporation crucible.

[0058] Other features and advantages of the invention will be described in more detail in the following description. Attached Figure Description

[0059] Reference Figure 1 The invention will be better understood by reading the following description, which is provided for illustrative purposes only and is in no way intended to be limiting. Figure 1 This is a cross-section of an embodiment of the device according to the present invention. Detailed Implementation

[0060] It should be noted that, as used in this application, terms such as "below" or "under" refer to the position and orientation of different components of the equipment when the equipment is installed on a vacuum deposition production line.

[0061] The object of this invention is to deposit a coating on a substrate formed of a metal alloy comprising a main element and at least one additional element. This object is particularly aimed at obtaining a zinc-magnesium coating. However, the process is not limited to these coatings, but preferably includes any coating based on a metal alloy whose elements have a vapor pressure difference of no more than 10% at the plating bath temperature, as this helps to control the relative content of each element.

[0062] To provide guidance, it is therefore possible to mention coatings made of zinc as the main element and additional elements such as chromium, nickel, titanium, manganese, magnesium, silicon and aluminum, considered alone or in combination.

[0063] Furthermore, although binary metal alloys are preferred, it goes without saying that the deposition of ternary metal alloys such as zinc-magnesium-aluminum or even quaternary alloys such as zinc-magnesium-aluminum-silicon is also possible.

[0064] The metal alloy layer preferably contains at least 50%, and more preferably at least 80% by weight of the main element. In the case of zinc-magnesium deposition, the metal alloy layer preferably contains 0.1% to 20% by weight of magnesium. Below 0.1%, the improvement in corrosion resistance provided by magnesium is no longer sufficient. On the other hand, above 20%, the higher proportion of magnesium leads to the premature consumption of the metal alloy layer and thus results in reduced corrosion resistance. In a preferred embodiment, the metal alloy layer contains at least 0.4%, preferably at least 2% by weight of magnesium. In a preferred embodiment, the metal alloy layer contains less than 15% by weight of magnesium. These preferred magnesium contents offer a better trade-off between corrosion resistance and layer flexibility.

[0065] It goes without saying that the main or secondary elements may include unavoidable impurities resulting from the manufacture of raw materials used to supply the vacuum deposition equipment. Even though the present invention is intended to prevent the metal alloy plating bath from being contaminated by these impurities, the presence of impurities in the metal alloy layer cannot be ruled out.

[0066] The coating thickness is preferably between 0.1 μm and 20 μm. On the one hand, a thickness below 0.1 μm poses a risk of insufficient corrosion protection for the substrate. On the other hand, to achieve the level of corrosion resistance required, particularly in the automotive or construction sectors, a thickness exceeding 20 μm is unnecessary. Typically, for automotive applications, the thickness can be limited to 5 μm.

[0067] Reference Figure 1 The apparatus 1 according to the invention firstly includes a vacuum deposition chamber 2 and a device for allowing a substrate to travel through the chamber.

[0068] The deposition chamber 2 is preferably maintained at 10. -8 bar and 10 -3 A sealable box-like structure with pressure between bars. The deposition chamber 2 has an inlet lock and an outlet lock (not shown), and the substrate S, such as the steel strip, can travel between the inlet lock and the outlet lock.

[0069] Depending on the nature and shape of the substrate, the substrate S can be moved by any suitable device. In particular, a rotating support roller on which a steel strip can be pressed can be used.

[0070] In the deposition chamber 2, a vapor jet coater 3 is located next to the surface of the substrate S that must be coated. This coater is adapted to jet metallic alloy vapor onto the traveling substrate S. The coater may advantageously include an extraction chamber with a narrow vapor outlet orifice 31, the length of which is approximately equal to the width of the substrate to be coated. This chamber may be made, for example, of graphite.

[0071] The vapor outlet orifice 31 can have any suitable shape, such as a groove that can be adjusted in both the longitudinal and transverse directions. The possibility of adjusting the width of the vapor outlet orifice 31 allows the vapor jet to be maintained within a wide range of evaporation metal surface temperatures, and therefore within a wide range of evaporation rates. Furthermore, the possibility of adapting its length to the width of the substrate to be coated allows for minimizing the loss of evaporated metal.

[0072] The coating apparatus is preferably an acoustic vapor jet coating apparatus, that is, a coating apparatus capable of generating a vapor jet at the speed of sound. This type of coating apparatus is also commonly referred to as a JVD (jet vapor deposition) apparatus. The reader can refer to patent application WO97 / 47782 for a more comprehensive description of the details of this type of apparatus.

[0073] The vapor jet coater 3 is mounted directly or indirectly on the evaporation crucible 4, which is adapted to supply vapor containing a main element and an additive element to the vapor jet coater. The evaporation crucible 4 is adapted to contain a metal alloy bath that generates the vapor to be deposited on the substrate S. The evaporation crucible 4 is preferably located in the deposition chamber 2.

[0074] The evaporation crucible 4 mainly comprises a container 5, a cover 6, and an evaporation tube 7, which is connected to the cover on one side and to the vapor jet coater 3 on the other side. These different parts can be made of, for example, graphite.

[0075] The evaporation crucible 4 is equipped with a heating element 8, which enables the metal alloy vapor to be formed and supplied to the vapor jet coater 3. The evaporation crucible 4 is advantageously equipped with an induction heater, which has the advantage of making it easier to stir and homogenize the composition of the metal alloy plating solution.

[0076] The pressure in evaporation crucible 4 depends on the temperature of the plating bath and the composition of the metal alloy plating bath. This pressure is typically around 10... -3 bar and 10 -1 The pressure varies between bars. Therefore, the pressure in deposition chamber 2 remains above the pressure in the evaporation crucible. For example, for a zinc-magnesium plating solution at 700°C, the pressure in the evaporation crucible is approximately 5.10. -2 bar and the pressure in the deposition chamber is maintained at approximately 10. -4 The pressure difference between the enclosed evaporation crucible and the deposition chamber generates metallic alloy vapor, which is then transported to the vapor jet coater 3 via the evaporation tube 7. The evaporation tube 7 is advantageously equipped with a valve V1 for regulating the vapor flow rate.

[0077] The evaporation crucible 4 is connected to a recharge furnace 9, which is adapted to supply the main elements of the molten metal alloy to the evaporation crucible. The recharge furnace is preferably located outside the vacuum deposition chamber 2.

[0078] Due to the heating system, the recharge furnace 9 is adapted to melt and maintain the main element in a molten state. Advantageously, the recharge furnace itself is connected to the metal ingot supply device.

[0079] The supply of the main element to the vapor crucible 4 is preferably made via a pipe 10, which connects the recharge furnace 9 to the vaporization crucible 4. The pipe inlet is adapted to be inserted into the main element plating solution so that impurities present on the surface of the plating solution are not drawn into the vaporization crucible. The pipe outlet is preferably located in the lower part of the vaporization crucible to avoid disturbing the surface of the plating solution where evaporation occurs.

[0080] The recharge furnace 9 is preferably positioned below the evaporation crucible 4 and is adapted to be maintained at atmospheric pressure. Due to the height difference between the evaporation crucible 4 and the recharge furnace 9, and the pressure difference generated between them, the molten main element rises into the evaporation crucible through the pressure effect when the metal alloy plating solution evaporates. This ensures a continuous supply to the evaporation crucible and helps maintain a constant liquid level in the evaporation crucible regardless of the production line speed.

[0081] In one embodiment of the present invention, the height between the evaporation crucible 4 and the refill furnace 9 can be adjusted to regulate the liquid level in the evaporation crucible.

[0082] The evaporation crucible 4 is also connected to a supply unit 8, which is adapted to supply solid additive elements, such as ingots or wires, and is adapted to supply molten, solid or partially solid additive elements to the evaporation crucible in an indifferent manner.

[0083] Because of the supply of solid additional elements by supply unit 12, the size and supply frequency of the solid elements are easily controlled, which allows the plating solution to maintain a constant composition over time. Where appropriate, this also allows for very easy modification of the composition of the metal alloy plating solution.

[0084] The supply unit 11 preferably includes a supply pipe 12 connected to the evaporation crucible 4 and preferably connected to the cover 6 of the evaporation crucible to utilize gravity.

[0085] The supply tube 12 can be made of different parts and different materials. For example, the lower part can be graphite to resist the temperature of the evaporation crucible, while the upper part can be a low-resistance material such as metal.

[0086] The supply of solid additive elements to supply unit 12 is readily made via the upper end of the supply pipe. To remove any water adsorbed on the surface of the additive elements, the upper end of the supply pipe 12 is preferably connected to a preheating furnace, which is part of the supply unit. The preheating furnace itself is preferably connected to a vacuum-locked arrangement.

[0087] The lower end of the supply pipe 12 is preferably below the liquid level in the evaporation crucible 4. Therefore, as will be explained in more detail later, the rise of vapor in the supply pipe can be limited.

[0088] The lower portion of the supply tube 12 is preferably equipped with a heating device 14, which is ultimately shared with the heating device surrounding the evaporation tube 7. Therefore, the additive element can be heated before it is released into the metal alloy plating solution. Depending on the temperature of the lower portion of the supply tube and the residence time of the additive element in the lower portion of the supply tube, the additive element remains solid, partially molten, or completely molten. Due to this flexibility in the state of the additive element at the outlet of the supply unit, one can utilize one state or another according to preference.

[0089] - If it is preferable to limit the temperature difference between the additive element and the metal alloy plating bath, so that the plating bath is not cooled when the additive element is introduced into the plating bath, and the deposition rate is not reduced, then the additive element will be advantageously melted.

[0090] - If one wishes to avoid depositing additional elements on the inner surface of the supply pipe, then the additional elements will advantageously be heated to a temperature close to the plating bath temperature but remaining solid.

[0091] - If a compromise is needed, then the additional elements will advantageously partially melt.

[0092] The supply pipe 12 advantageously includes an inert gas inlet 13, which is preferably located in the lower half of the supply pipe 12. Due to this inlet, an inert gas pressure higher than that in the evaporation crucible 4 can be supplied in the supply pipe. Therefore, the rise of vapor in the supply pipe is avoided.

[0093] In the case of ingot supply, the supply tube 12 advantageously includes an ingot holder 15, which is adapted on the one hand to hold the ingot with the additional element while it is being heated, and on the other hand to release the additional element into the evaporation crucible. The ingot holder 15 is preferably located in the lower half of the supply tube, at the height of the heating device 14. Due to this ingot holder, the residence time of the ingot in the supply unit can be effectively controlled, and therefore, the temperature and state of the ingot can be effectively controlled. The ingot holder also allows for precise control of the frequency of ingot release into the evaporation crucible.

[0094] The ingot retainer 15 is preferably a valve. This valve advantageously has a U-shaped cross-section to easily retain and release the ingot. The bottom portion of the U-shape can be advantageously covered with a shock absorber so that an ingot falling into the valve will not damage it.

[0095] Those skilled in the art will know how to adjust the shape of the supply tube 12 so that the ingot does not get stuck in the supply tube 12 and does not fall violently into the evaporation crucible or ingot holder 15.

[0096] In the case of wire supply, those skilled in the art will know how to adjust the shape of the supply tube to the diameter of the wire, thereby making it easy to place the wire under a vacuum through pressure loss. Those skilled in the art will also know how to adjust the speed of the wire to control the residence time of the wire in the supply unit, and thus control the temperature and condition of the wire.

[0097] It is important to note that several supply units can be connected to the evaporation crucible to supply several additional elements independently.

[0098] When it is necessary to operate equipment 1, the ingot of the main element is introduced into the refill furnace 6.

[0099] Once the ingot has melted, the evaporation crucible 4 and pipe 10 are heated, and a vacuum is then created in the evaporation crucible 4. The liquid main element contained in the refill furnace 9 is then used to fill the evaporation crucible 4.

[0100] First, the composition of the metal alloy to be deposited on the substrate is determined. Then, the composition of the plating bath is determined, which is used to obtain vapors with the desired coating composition in equilibrium with the plating bath. For example, by evaporating plating baths containing zinc-based metal alloys with magnesium contents of 8% to 43% and 10% to 38% by weight, respectively, zinc-based metal alloy layers with magnesium contents of 0.1% to 20% and 0.4% to 15% by weight, respectively, can be obtained.

[0101] Therefore, an appropriate amount of solid additive element is introduced into the supply unit 11 located above the metal alloy plating bath. The solid additive element is heated near the plating bath to a temperature close to the plating bath temperature. During this heating, the additive element remains solid, partially molten, or completely molten. The additive element is then released into the metal alloy plating bath, where it mixes with the main element.

[0102] Then it is possible that:

[0103] (i) Evaporation of metal alloy plating solutions containing main and secondary elements,

[0104] (ii) Using a vapor jetting substrate containing both main and secondary elements, and

[0105] (iii) Continuously depositing a metal alloy layer containing a main element and an additional element on a substrate.

[0106] In order to compensate for evaporation during operation and maintain a constant composition of the plating solution, when the main elements are refilled into the metal alloy plating solution through the refill furnace 9, an appropriate amount of additional elements are continuously or discontinuously added to the metal alloy plating solution.

[0107] Preferably, the additional element is added at least partially in solid form to the evaporation crucible 4 to limit the deposition of the additional element on the inner surface of the supply tube.

[0108] When the density of the additive element is lower than that of the main element, the released additive element floats on the surface of the metal alloy plating solution at the lower end of the supply pipe 12 and melts on that surface when appropriate. This creates a cap in the additive element in the lower part of the supply pipe, located between the lower end of the supply pipe 12 and the liquid metal level. This cap restricts the rise of the main element vapor in the supply pipe. Furthermore, if the additive element contains impurities, the impurities are retained in the cap and do not contaminate the metal alloy plating solution. Simultaneously, due to the supply of the additive element, it is released from the lower end of the supply pipe into the evaporation crucible.

[0109] Appropriate control:

[0110] Ingot size and / or supply frequency in the additional elements, or

[0111] The diameter and / or supply speed of the wire in the additional elements.

[0112] This allows the composition of the plating solution to remain constant over time.

[0113] To limit impurity levels in the evaporation crucible, solid additives can be selectively cleaned before being introduced into the feed unit. Oxides that may be present on the surface of the ingot / wire can be significantly removed by chemical pickling.

[0114] The process according to the invention is more specifically, but not only, applicable to the treatment of both pre-coated and bare metal strips. Of course, the process according to the invention can be used on any coated or uncoated substrate, such as aluminum strip, glass strip, or ceramic strip.

[0115] This process is more specifically applicable to substrates that are susceptible to degradation of their properties during diffusion heat treatment, such as bake-hardened steel strips containing a large amount of carbon in the solid solution, which must not precipitate before the steel has been formed by stretching or any other suitable process. By implementing the process according to the invention, it is therefore possible to make the metal alloy deposition compatible with most metallurgies.

Claims

1. A vacuum deposition apparatus (1) for continuously depositing a coating of a metal alloy comprising a main element and at least one additional element on a traveling substrate (S), the apparatus comprising a vacuum deposition chamber (2) and means for allowing the substrate to travel through the chamber, wherein, The device also includes: Steam jet coating device (3). An evaporation crucible (4) is adapted to mix the at least one additional element and the main element in a molten state, form a metal alloy vapor containing the main element and the at least one additional element, and supply the vapor containing the main element and the at least one additional element to the vapor jet coater. A refill furnace (9) is adapted to melt the main element to maintain it in a molten state and to continuously supply the molten main element to the evaporation crucible via a pressure effect and to maintain a constant liquid level in the evaporation crucible. A supply unit (11) adapted to supply the at least one additional element in solid form, and adapted to supply the at least one additional element in molten, solid, or partially solid form to the evaporation crucible indiscriminately by gravity. The supply unit (11) includes a supply tube (12), and the supply tube (12) includes a spindle holder (15) configured to control the residence time of the at least one additional element in the supply unit (11) and the release frequency of the at least one additional element.

2. The vacuum deposition apparatus according to claim 1, wherein, The lower end of the supply pipe (12) is below the liquid level in the evaporation crucible (4).

3. The vacuum deposition apparatus according to claim 1 or 2, wherein, The evaporation crucible (4) includes a cover (6), and the supply pipe (12) is connected to the cover (6).

4. The vacuum deposition apparatus according to claim 1, wherein, The ingot holder (15) is adapted, on the one hand, to hold the at least one additional element when it is heated, and on the other hand, to release the at least one additional element into the evaporation crucible (4).

5. The vacuum deposition apparatus according to claim 4, wherein, The ingot retainer (15) is a valve with a U-shaped cross-section.

6. The vacuum deposition apparatus according to any one of claims 1, 2, 4, and 5, wherein, The supply pipe (12) includes an inert gas inlet (13) adapted to provide a pressure higher than that in the evaporation crucible (4), at least in the lower portion of the supply pipe.

7. The vacuum deposition apparatus according to any one of claims 1, 2, 4, and 5, wherein, The supply unit (11) includes a preheating furnace.

8. The vacuum deposition apparatus according to any one of claims 1, 2, 4, and 5, wherein, The supply unit (11) includes a heating device (14).

9. The vacuum deposition apparatus according to any one of claims 1, 2, 4, and 5, wherein, The vapor jet coating device (3) is an acoustic vapor jet coating device.

10. The vacuum deposition apparatus according to any one of claims 1, 2, 4, and 5, wherein, The steam supply to the steam jet coater (3) is made through an evaporation tube (7), which connects the evaporation crucible (4) to the steam jet coater (3).

11. The vacuum deposition apparatus according to any one of claims 1, 2, 4, and 5, wherein, The refill furnace (9) is placed below the evaporation crucible (4) and is adapted to be kept at atmospheric pressure.

12. The vacuum deposition apparatus according to any one of claims 1, 2, 4, and 5, wherein, The main element supply to the evaporation crucible (4) is carried out through a pipe (10) that connects the refill furnace (9) to the evaporation crucible (4).

13. The vacuum deposition apparatus according to any one of claims 1, 2, 4, and 5, wherein, The evaporation crucible (4) includes an induction heater (8).

14. The vacuum deposition apparatus according to any one of claims 1, 2, 4, and 5, wherein, The refill furnace (9) is connected to the metal ingot supply device.

15. A process for coating a substrate, the process comprising: (i) Supplying molten main elements to the metal alloy plating bath, (ii) Heating at least one additional element in solid form above the metal alloy plating solution in a supply pipe, and supplying the at least one additional element in molten, solid, or partially solid form to the metal alloy plating solution indiscriminately through the supply pipe by gravity. (iii) Evaporating the metal alloy plating bath containing the main element and at least one additional element, (iv) Spraying the substrate with a vapor containing the main element and at least one additional element, and (v) Continuously depositing a metal alloy layer comprising the main element and at least one additional element on the substrate, Wherein, the lower end of the supply pipe is below the liquid level of the metal alloy plating solution, and wherein the at least one additional element has a lower density than the main element.

16. The process according to claim 15, wherein, The vapor is injected onto the substrate at the speed of sound.

17. The process according to claim 15 or 16, wherein, The metal alloy plating solution is continuously supplied with the main element.

18. The process according to claim 17, wherein, The continuous supply is achieved through the effect of air pressure.

19. The process according to any one of claims 15, 16, and 18, wherein, Before heating the metal alloy plating solution above the at least one additional element, remove any oxides that may be present on the surface of the at least one additional element.

20. The process according to claim 19, wherein, The oxides were removed by chemical polishing.

21. The process according to any one of claims 15, 16, 18, and 20, wherein, The metal alloy plating solution is supplied with at least one additional element intermittently.

22. The process according to claim 21, wherein, The at least one additional element is in the form of an ingot.

23. The process according to claim 22, wherein, The composition of the metal alloy plating solution is kept constant over time by controlling the size of the ingot and / or the supply frequency.

24. The process according to any one of claims 15, 16, 18, and 20, wherein, The metal alloy plating solution is continuously supplied with at least one additional element.

25. The process according to claim 24, wherein, The at least one additional element is in the form of wire.

26. The process according to claim 25, wherein, By controlling the diameter and / or supply speed of the wire, the composition of the metal alloy plating solution is kept constant over time.

27. The process according to any one of claims 15, 16, 18, 20, 22, 23, 25, and 26, wherein, The main element is zinc.

28. The process according to claim 27, wherein, The at least one additional element is magnesium.

29. The process of claim 28, comprising continuously depositing a zinc-based metal alloy layer having a magnesium content of 0.1% to 20% by weight on the substrate by evaporating a zinc-based metal alloy plating bath having a magnesium content of 8% to 43% by weight.

30. A process for coating a substrate, the process comprising: (i) Supplying molten main elements to the metal alloy plating bath, (ii) Heating at least one additional element in solid form above the metal alloy plating solution in a supply pipe, and supplying the at least one additional element in molten, solid, or partially solid form to the metal alloy plating solution indiscriminately through the supply pipe by gravity. (iii) Evaporating the metal alloy plating bath containing the main element and at least one additional element, (iv) Spraying the substrate with a vapor containing the main element and at least one additional element, and (v) Continuously depositing a metal alloy layer comprising the main element and at least one additional element on the substrate, Specifically, the release frequency of at least one additional element in the supply pipe is controlled to maintain a constant composition of the metal alloy plating solution over time.

31. A vacuum deposition apparatus (1) for continuously depositing a coating of a metal alloy comprising a main element and at least one additional element on a traveling substrate (S), the apparatus comprising a vacuum deposition chamber (2) and means for allowing the substrate to travel through the chamber, wherein, The device also includes: Steam jet coating device (3). An evaporation crucible (4) is adapted to mix the at least one additional element and the main element in a molten state, form a metal alloy vapor containing the main element and the at least one additional element, and supply the vapor containing the main element and the at least one additional element to the vapor jet coater. A refill furnace (9) is adapted to melt the main element to maintain it in a molten state and to continuously supply the molten main element to the evaporation crucible via a pressure effect and to maintain a constant liquid level in the evaporation crucible. A supply unit (11) adapted to supply the at least one additional element in solid form, and adapted to supply the at least one additional element in molten, solid, or partially solid form to the evaporation crucible indiscriminately by gravity. The lower end of the supply pipe (12) of the supply unit (11) is lower than the liquid level in the evaporation crucible (4).

Images