TWI425103B - Method and product of making zirconium - based metallic glass coating by multi - independent target - Google Patents

Description

Method and product for preparing zirconium-based metallic glass coating by multiple independent targets

The present invention relates to a method of coating a film, and more particularly to a method of forming a metallic glass coating and a product thereof.

"Metallic glass" is a non-crystalline structural alloy obtained by mixing and melting various specific elements and rapidly cooling and solidifying. It is also called "amorphous alloy" because of its high strength and wear resistance. It has the characteristics of superplastic forming at an appropriate temperature, and because of its lack of grain boundaries, it can be finely filled and formed under a low deformation pressure, so it has received wide attention from all walks of life.

Since the development of metallic glass, Zirconium based metallic glass has excellent properties such as excellent tensile strength, good bending ductility and high hardness. At the same time, it has the characteristics of antibacterial force, corrosion resistance, wear resistance, high toughness, etc., and can be expected to be used for, for example, metal bipolar plates for fuel cells, medical surgical tools, 3C product shells, etc., in particular, if It can form a thick and uniform zirconium-based metallic glass coating on a large-area substrate or other special-purpose substrate to form a composite material with a metallic glass coating, which will be more extensive and practical in industry and commerce. Application value, this has also become the direction of industry and academic circles to study hard.

At present, the method of forming a zirconium-based metallic glass coating by plating can be roughly divided into two types: coating with a single composite target and coating with a plurality of independent targets: a technique of coating with a single composite target, such as US Pat. No. 7,282,123. No. "COMPOSITE SPUTTER TARGET AND PHOSPHOR DEPOSITION METHOD", it is easier to control the coating process, and then obtain a uniform coating thickness and a large area of coating, but the disadvantage is that the composite target is extremely difficult to design and manufacture; and most independent targets are used. The coating technology of the material, for example, the "CORROSION RESISTANT METALLIC GLASS COATINGS" case of the US Patent No. 4965139, although the design and production of the target are relatively simple, the uniformity of the thickness of the coating is relatively large in the process of coating. Control is not easy, and at the same time, it is impossible to grasp a large area of metallic glass coating.

Therefore, although zirconium-based metallic glass has excellent material properties, it still requires continuous innovation in the industry to propose a production method with practical commercial production value for industrial development.

Accordingly, it is an object of the present invention to provide a method of making a zirconium-based metallic glass coating using a plurality of independent targets.

Further, another object of the present invention is to provide a product produced by producing a zirconium-based metallic glass coating film using a plurality of independent targets.

Thus, the method for producing a zirconium-based metallic glass coating film of a multi-independent target of the present invention comprises the following three steps.

Firstly, a primary target and a plurality of secondary targets are prepared in a coating device, wherein the primary target is composed of Zr, and the plurality of secondary targets are selected from the group consisting of Al, Ni, Cu, Ti, and V. Mg, and a combination of these.

A cleaned substrate is then placed in the coating apparatus and the coating apparatus is controlled to a high vacuum chamber pressure having a predetermined atmosphere.

Finally, the target current of the main target is controlled to be 1 amp to 5 amps, and the target current of the plurality of sub-targets is not 0 and not more than 3 amps, and the target current of the main target is higher than the target current of the sub-target. And simultaneously exciting the main target and the constituent elements of the sub-targets onto the substrate to form the zirconium-based metallic glass coating film.

Furthermore, a composite material having a zirconium-based metallic glass coating comprising a substrate and a zirconium-based metallic glass coating formed on the substrate by a plurality of independent targets controlling the target current, wherein the zirconium-based The composition of the metallized glass coating is Zr _a K _b M _c N _d , and K, M, and N are selected from the group consisting of Al, Ni, Cu, Ti, V, Mg, and the like, and the atomic radius ratio of zirconium to K is not Less than 12%, in terms of atomic composition percentage, 40≦a≦30, 20≦b≦10, 30≦c≦20, 10≦d≦5.

The invention has the advantages that the zirconium-based metallic glass coating film can be formed by controlling the target current to excite multiple independent targets, and the film thickness and uniformity of the formed zirconium-based metallic glass coating film can be easily controlled, which is suitable for practical mass production.

The above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments of the invention.

Before the present invention is described in detail, it is noted that in the following description, similar elements are denoted by the same reference numerals.

Referring to Figures 1 and 2, a first preferred embodiment of the method for producing a zirconium-based metallic glass coating of a plurality of independent targets of the present invention is to produce a composite 2 having a zirconium-based metallic glass coating as shown in Figure 2.

Referring first to FIG. 2, the composite material 2 having a zirconium-based metallic glass coating comprises a substrate 21 and a layer of zirconium-based metallic glass coating 22.

The substrate 21 may be made of ceramic, polymer material, stainless steel, aluminum, or aluminum alloy, etc., preferably, the substrate is 316L stainless steel, 1***, 2***, 3*** , 5*** series of aluminum alloy (*** any number of the table).

The zirconium-based metallic glass coating 22 is formed on the substrate 21 by a plurality of independent targets to control the target current (this process will be described in detail later), and the composition is expressed as Zr _a K _b M _c N _d , wherein K, M And N is an element selected from the group consisting of IIA, IVA, VA, VIIIA, and IIIB of the periodic table having the same body-centered cubic structure as Cr. Preferably, K, M, and N are selected from the group consisting of Al, Ni, Cu, and Ti. An element composed of V, Mg, or the like, or an alloy composed of such elements, such as NiV, CuTi, etc., and an atomic radius ratio of zirconium to K of not less than 12%, in terms of atomic composition percentage, 40≦a≦30,20 ≦b≦10, 30≦c≦20,10≦d≦5; in this example, the composition of the zirconium-based metallic glass coating 22 is Zr ₆₀ K _17.5 M ₁₀ N _7.5 , K is CuTi, and M is NiV, N It is Al.

Referring to FIG. 1 and FIG. 3 , a first preferred embodiment of the method for fabricating a zirconium-based metallic glass coating film by using a plurality of independent targets is to perform a step 11 to prepare a main target 31 disposed at intervals in a coating device 3 . And a plurality of sub-targets 32, wherein the main target 31 is composed of Zr, and the plurality of sub-targets 32 are selected from the same body-centered cubic structure as chromium and belong to IIA, IVA, VA, VIIIA, IIIB of the periodic table. An element formed of an element of the family or a composition of the elements, preferably an element selected from the group consisting of Al, Ni, Cu, Ti, V, Mg, or the like, or an alloy of the combination of such elements, for example NiV, CuTi, and the like are formed. In the present embodiment, the three sub-targets 32 are made of Al, CuTi, and NiV, respectively.

Next, in step 12, the substrate 21 is cleaned and placed in the coating device 3, and the coating device 3 is controlled to have a high vacuum chamber pressure having a predetermined atmosphere; more specifically, after the substrate 21 is placed, After the pumping device 3 performs the pumping operation until the chamber pressure is kept below 2×10 ^-5 Torr, the argon gas is introduced and the chamber pressure is controlled at 1.0×10 ^-2 Torr to 1.0×10 ^-3 Torr several times. Finally, Maintaining the high vacuum chamber pressure having a predetermined atmosphere is to introduce Ar _(g) , N _{2 (g)} , and C ₂ H _{2 (g)} at a flow rate of 25 to 35 sccm, 2 to 17 sccm, and 10 to 20 sccm, respectively, and control the pressure. In 1.0 × 10 ^-2 Torr to 1.0 × 10 ^-3 Torr, in this example, the flow rates of Ar _(g) , N _{2 (g)} , and C ₂ H _{2 (g} ) are 30 sccm, 12 sccm, and 15 sccm, respectively. . Further, the gas suitable for carrying out the high vacuum chamber pressure of the present invention may also be selected from He, Ne, Ar, Kr, Xe or N ₂ .

Finally, in step 13, the target current of the main target 31 is controlled to be 1 amp to 5 amps, and the target current of the three sub-targets 32 is not 0 and not more than 3 amps, and the main target 31 is excited and the same The constituent elements of the sub-target 32 are deposited onto the substrate 21 to form the zirconium-based metallic glass coating film 22. In this example, the target current of the main target 32 composed of Zr is controlled to be 0.1 amps to 3 amps, and the target current of the sub-target 32 composed of Al is 0.1 amps to 2 amps, and the target current of the sub-target 32 composed of CuTi is From 0.1 amp to 2 amps, the target current of the sub-target 32 composed of NiV is 0.1 amp to 2 amps, and the constituent elements thereof are excited to form the zirconium-based metallic glass coating film 22.

Referring to Annex 1, Appendix 2, Annex 1 is the X-ray analysis result of the composite material 2 produced by the first preferred embodiment of the method for producing a zirconium-based metallic glass coating film of the multiple independent target of the present invention, and the accessory 2 is As a result of the TEM analysis, it can be confirmed from the attachments 1 and 2 that the zirconium-based metallic glass coating film 22 produced by the method for producing a zirconium-based metallic glass coating film of the multi-independent target of the present invention has an amorphous structure, that is, the invention is indeed achieved in multiple dimensions. The purpose of the target material is to create a zirconium-based metallic glass coating film in combination with the control of the target current. In addition, the composite material 2 produced in the salt spray test is etched in 5% NaCl for 72 hours without corrosion, and the polarization curve is 1 MH _{2 .} Icorr=8.7×10 ^-6 A/cm2 in SO ₄ etching solution, refer to the general 316L stainless steel test piece Icorr=47×10 ^-6 A/cm2, which has obvious corrosion resistance improvement, and secondly, to Staphylococcus aureus, The results of the bacteriostatic test of Pseudomonas aeruginosa and Escherichia coli are 99.9%, which meets the antibacterial requirements and is suitable for various industries such as fuel cells, medical appliances, and 3C product shells.

Referring to Figures 4 and 5, a second preferred embodiment of the method for producing a zirconium-based metallic glass coating of the multi-independent target of the present invention is to produce a composite material 5 having a zirconium-based metallic glass coating as shown in Figure 5.

Referring first to FIG. 5, the second preferred embodiment of the composite material 5 having a zirconium-based metallic glass coating is similar to the composite 2 produced in the first preferred embodiment, except that the substrate 51 is The zirconium-based metallic glass coating film 53 further has an underlying plating film 52 composed of a conductive alloy and having a film thickness of 0.1 to 0.3 μm. The constituent elements of the underlying plating film 52 are the same as those of the zirconium-based metallic glass coating film 53. A better and stable bond between the zirconium-based metallic glass coating film 53 and the substrate 51 is obtained.

Referring to FIG. 4, referring to FIG. 3, a second preferred embodiment of the method for fabricating a zirconium-based metallic glass coating film of the multi-independent target of the present invention is first performed in step 41, and the substrate 51 is cleaned and placed in the coating device 3, And forming the underlying plating film 52 on the substrate 51 by using a composite target comprising Cr, and an element selected from the group consisting of Group VIIIA, IVB, Group, VB of the periodic table or a combination thereof; The composition of the composite targets 31, 32 is the same as that of the zirconium-based metallic glass coating film 53 to be formed later; since this step is a process generally forming an alloy plating film, it will not be described in detail here.

Next, in step 42, a main target 31 and a plurality of sub-targets 32 are disposed in the coating device 3, wherein the main target 31 is composed of Zr, and the plurality of sub-targets 32 are selected from Cr An alloy having the same body-centered cubic structure and belonging to the group IIA, IVA, VA, VIIIA, IIIB of the periodic table or the composition of the elements, preferably selected from the group consisting of Al, Ni, Cu, Ti An element such as V, Mg or the like, or an alloy formed by a combination of these elements, such as NiV or CuTi; in the present embodiment, the three sub-targets 32 are each composed of Al, CuTi, and NiV.

Next, in step 43, the substrate 51 plated with the underlying plating film 52 obtained in the step 41 is placed in the coating device 3, and the coating device 3 is controlled to have a high vacuum chamber pressure having a predetermined atmosphere; more specifically, After the substrate 51 coated with the underlying plating film 52 is placed, the coating device 3 is evacuated until the chamber pressure is kept below 2×10 ^-5 Torr, then argon gas is introduced and the chamber pressure is controlled at 1.0×10 ^{− 2} Torr~1.0×10 ^-3 Torr several times. Finally, maintaining the high vacuum chamber pressure with a predetermined atmosphere is to introduce Ar _(g) and N ₂ at a flow rate of 25 to 35 sccm, 2 to 17 sccm, and 10 to 20 sccm, respectively. _g) , with C ₂ H _{2 (g)} and controlling the pressure at 1.0 × 10 ^-2 Torr to 1.0 × 10 ^-3 Torr, in this example, Ar _(g) , N _{2 (g)} , and C ₂ H _{2 The} flow rates of _(g ) are 30 sccm, 12 sccm and 15 sccm, respectively. Further, the gas suitable for carrying out the high vacuum chamber pressure of the present invention may also be selected from He, Ne, Ar, Kr, Xe or N ₂ .

Finally, step 44 is performed to control the target current of the main target 31 to be 1 amp to 5 amps, and the target current of the three sub-targets 32 is not 0 and not more than 3 amps, and the main target 31 is excited and the same The constituent element of the sub-target 32 is deposited on the underlying plating film 52 to form the zirconium-based metallic glass coating film 53, and the composite material 5 is obtained. In this example, the target current of the main target 32 composed of Zr is controlled to be 0.1 amps to 3 amps, and the target current of the sub-target 32 composed of Al is 0.1 amps to 2 amps, and the target current of the sub-target 32 composed of CuTi is From 0.1 amp to 2 amps, the target current of the sub-target 32 composed of NiV is 0.1 amp to 2 amps, and the constituent elements thereof are excited to form the zirconium-based metallic glass coating film 53.

The composite material 5 produced by the second preferred embodiment of the method for producing a zirconium-based metallic glass coating film of the multi-independent target of the present invention not only significantly improves the corrosion resistance but also achieves the antibacterial requirement, and the underlying coating 52 enables the The zirconium-based metallic glass coating film 53 and the substrate 51 obtain a better and stable combination, especially when the substrate is composed of, for example, ceramics, polymer materials, etc., by the underlying plating film 52, the zirconium-based metal can be substantially made substantially. The glass coating 53 is bonded to the substrate 51 to obtain a more stable material.

It is to be noted that in the second embodiment, the constituent elements of the underlying plating film 52 are the same as those of the zirconium-based metallic glass coating film 53, so that the same main target 31 and the sub-target can be used in the same coating device 3. The material 32 is processed, that is, the underlying plating film 52 (alloy coating film) is formed on the substrate by a general plating process, and then the process gases Ar _(g) , N _{2 (g)} , and C ₂ H _{2 are introduced. (g)} forming a high vacuum chamber pressure, and finally forming the zirconium-based metallic glass coating film 53 on the underlying plating film 52 in such a manner as to control the target current, thereby obtaining the composite material 5 having the zirconium-based metallic glass coating film of the present invention.

In summary, the method for preparing a zirconium-based metallic glass coating film by using multiple independent targets of the present invention can not only easily control the film thickness of the formed zirconium-based metallic glass coating film compared with the current coating method using most independent targets. Uniformity, suitable for large-scale process and low process cost; the composite material with zirconium-based metallic glass coating prepared by the method for preparing zirconium-based metallic glass coating by multiple independent targets according to the present invention not only improves corrosion resistance, but also The antibacterial requirement is achieved, and the degree of bonding between the coating and the substrate is further improved. The applicable industries cover fuel cells, medical appliances, and 3C product shells, etc., so the object of the present invention is achieved.

The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.

11‧‧‧Steps

12‧‧‧ steps

13‧‧‧Steps

2‧‧‧Composite materials with zirconium-based metallic glass coating

21‧‧‧Substrate

22‧‧‧Zirconium-based metal glass coating

3‧‧‧ Coating equipment

31‧‧‧Main target

32‧‧‧Sub Target

41‧‧‧Steps

42‧‧‧Steps

43‧‧‧Steps

44‧‧‧Steps

5‧‧‧Composite materials with zirconium-based metallic glass coating

51‧‧‧Substrate

52‧‧‧Undercoating

53‧‧‧Zirconium-based metal glass coating

1 is a flow chart illustrating a first preferred embodiment of a method for fabricating a zirconium-based metallic glass coating of a plurality of independent targets of the present invention;

Figure 2 is a cross-sectional view showing a composite material having a zirconium-based metallic glass coating film produced by the first preferred embodiment of the present invention;

3 is a schematic view showing the arrangement state of a coating apparatus, a main target, and a sub-target used in the first preferred embodiment of the method for producing a zirconium-based metallic glass coating film by using the multi-independent target of the present invention;

4 is a flow chart showing a second preferred embodiment of a method for fabricating a zirconium-based metallic glass coating film of a plurality of independent targets according to the present invention; and

Figure 5 is a schematic cross-sectional view showing a composite material having a zirconium-based metallic glass coating film produced by the second preferred embodiment of the present invention.

[A brief description of the attachment]

Annex 1 is an X-ray analysis illustrating the crystal structure of a composite material having a zirconium-based metallic glass coating prepared by the first preferred embodiment of the present invention;

Attachment 2 is a TEM analysis showing the crystal structure of a composite material having a zirconium-based metallic glass coating film produced by the first preferred embodiment of the present invention.

11. . . Step Prepare a spaced apart primary target and multiple secondary targets in the coating equipment

12. . . Steps Place the cleaned substrate in the coating equipment and control the coating equipment into a high vacuum chamber pressure with a predetermined atmosphere

13. . . The step control main target current is 1 amp ~ 5 amps, and the target current of the plurality of sub-targets is not 0 and not more than 3 amps, and the main target and the constituent elements of the sub-target are excited to form on the substrate. Zirconium-based metal glass coating

Claims (16)

A method for producing a zirconium-based metallic glass coating film by using a plurality of independent targets, comprising: (a) preparing a main target disposed at intervals in a coating device, and a plurality of sub-targets, wherein the main target is composed of Zr, The plurality of sub-targets are selected from the group consisting of Al, Ni, Cu, Ti, V, Mg, and the like; (b) placing a cleaned substrate in the coating device, and controlling the coating device Forming a high vacuum chamber pressure having a predetermined atmosphere; and (c) controlling the target current of the main target to be 1 amp to 5 amps, and the target current of the plurality of sub-targets is not 0 and not more than 3 amps, and the main The target current of the target is higher than the target current of the sub-target and simultaneously excites the main target and constituent elements of the sub-targets onto the substrate to form the zirconium-based metallic glass coating. A method for producing a zirconium-based metallic glass coating film according to the multi-independent target of claim 1, wherein the step (a) uses three sub-targets, and the three sub-targets are Al, CuTi, and NiV, respectively. Composition. A method for producing a zirconium-based metallic glass coating film according to the multi-independent target of claim 2, wherein the step (b) is to control the high vacuum chamber pressure of the predetermined atmosphere formed by the coating device to be introduced into Ar _(g) , N _{2 (g)} , and C ₂ H _{2 (g)} are controlled at a pressure of 1.0 × 10 ^-2 Torr to 1.0 × 10 ^-3 Torr. A method for producing a zirconium-based metallic glass coating film according to the multi-independent target of claim 3, wherein the substrate is selected from the group consisting of stainless steel, aluminum, or aluminum alloy. A method for preparing a zirconium-based metallic glass coating film by using a plurality of independent targets, comprising: (a) placing a cleaned substrate in a coating device, using a Cr-containing material, and being selected from Group VIIIA, IVB of the periodic table, a composite target composed of a group of elements, a group of VBs, or a combination thereof; forming a primer film on the substrate; (b) preparing a main target and a plurality of sub-targets disposed at intervals in the coating device, Wherein, the main target is composed of Zr, and the plurality of sub-targets are selected from the group consisting of Al, Ni, Cu, Ti, V, Mg, and the like, corresponding to the composition of the zirconium-based metallic glass coating; (c) controlling the coating apparatus to have a high vacuum chamber pressure having a predetermined atmosphere; and (d) controlling the target current of the main target to be 1 amp to 5 amps, and the target current of the plurality of sub-targets is not 0 and not More than 3 amps, and the target current of the main target is higher than the target current of the sub-target and simultaneously excite the constituent elements of the main target and the sub-targets to deposit on the underlying plating film to form the zirconium-based metallic glass coating film. A method for producing a zirconium-based metallic glass coating film according to the multi-independent target of claim 5, wherein the substrate is selected from the group consisting of ceramics, polymer materials, stainless steel, aluminum, or aluminum alloys. A method for producing a zirconium-based metallic glass coating film according to the multi-independent target of claim 6, wherein the constituent elements of the composite target used in the step (a) and the main target and the auxiliary used in the step (b) The constituent elements of the target are the same. Preparation of zirconium-based metal according to multi-independent target described in item 7 of the patent application scope A method of glass coating, wherein the sub-target in the step (b) has three and is composed of Al, CuTi, and NiV, respectively. A method for producing a zirconium-based metallic glass coating film according to the multi-independent target of claim 8 wherein the step (c) is to control the high vacuum chamber pressure of the predetermined atmosphere formed by the coating device to be introduced into the Ar _(g) , N _{2 (g)} , and C ₂ H _{2 (g)} are controlled at a pressure of 1.0 × 10 ^-2 Torr to 1.0 × 10 ^-3 Torr. A composite material having a zirconium-based metallic glass coating obtained by the method according to any one of claims 1 to 4, comprising: a substrate; and a zirconium-based metallic glass coating, which is mostly independent The target control target current mode is formed on the substrate, and the composition is Zr _a K _b M _c N _d , wherein K, M, and N are selected from the group consisting of Al, Ni, Cu, Ti, V, Mg, and the like The combination, and the atomic radius ratio of zirconium to K is not less than 12%, in terms of atomic composition percentage, 40≦a≦30, 20≦b≦10, 30≦c≦20, 10≦d≦5. A composite material having a zirconium-based metallic glass coating according to claim 10, wherein the composition of the zirconium-based metallic glass coating is Zr ₆₀ K _17.5 M ₁₀ N _7.5 , and K is CuTi, M is NiV, and N is Al. A composite material having a zirconium-based metallic glass coating according to claim 10 or 11, wherein the substrate is selected from the group consisting of ceramics, polymer materials, stainless steel, aluminum, or aluminum alloys. A composite material having a zirconium-based metallic glass coating film obtained by the method according to any one of claims 5 to 9, comprising: a substrate; an underlying coating film formed on the substrate; And a zirconium-based metallic glass coating film formed on the underlying coating film by controlling a target current by a plurality of independent targets, and the composition is Zr _a K _b M _c N _d , wherein K, M, and N are selected from Al, Ni, Cu, Ti, V, Mg, and combinations thereof, and the atomic radius ratio of zirconium to K is not less than 12%, in terms of atomic composition percentage, 40≦a≦30, 20≦b≦10, 30≦c≦20 , 10≦d≦5. A composite material having a zirconium-based metallic glass coating according to claim 13 wherein the composition of the zirconium-based metallic glass coating is Zr ₆₀ K _17.5 M ₁₀ N _7.5 , and K is CuTi, M is NiV, and N is Al. A composite material having a zirconium-based metallic glass coating according to claim 14, wherein the constituent elements of the underlying coating are the same as those of the zirconium-based metallic glass coating. A composite material having a zirconium-based metallic glass coating according to claim 14 or 15, wherein the substrate is selected from the group consisting of ceramics, polymer materials, stainless steel, aluminum, or aluminum alloys.