Metal surface modification method, metal and fiber composite material bonding method and metal and fiber composite material composite body

Abstract

The invention provides a metal surface modification method, a metal and fiber composite material bonding method and a metal and fiber composite material composite body. The metal surface modification method comprises the following steps: providing a metal workpiece, wherein the metal workpiece is provided with a first surface and a second surface which are opposite; cleaning the first surface of the metal workpiece; applying etching liquid to the first surface of the metal workpiece, and performing corrosion pore-forming treatment to form a plurality of holes in the first surface of the metal workpiece; a silane solution is applied to the first surface where the multiple holes are formed, silanization treatment is carried out, and silane modified layers are formed on the inner walls of the multiple holes; the metal workpiece is cleaned; and the metal workpiece is dried.

Description

Technical Field

[0001] The present invention relates to a method for modifying a metal surface, and particularly to a method for modifying a metal surface, a method for joining a metal and a fiber composite, and a composite of a metal and a fiber composite. Background Art

[0002] With the vigorous development of technology, the goal of Net Zero carbon emissions is the current world trend. However, in currently commonly used composites, it is necessary to join metal workpieces and fiber composites by using a bonding adhesive, which not only increases the production process and cost, but also has the problem of reducing the bonding strength over time / temperature. Moreover, when disassembling the composite to recycle its constituent materials, there is an environmental pollution problem of using organic solvents to remove the bonding adhesive. Summary of the Invention

[0003] The present invention provides a method for modifying a metal surface by performing corrosion pore-forming treatment and silanization treatment, a joining method for enabling a fiber composite to be tightly combined with a metal workpiece, and a composite.

[0004] A method for modifying a metal surface according to the present invention includes: providing a metal workpiece having opposite first and second surfaces; cleaning the first surface of the metal workpiece; applying an etching solution to the first surface of the metal workpiece to perform corrosion pore-forming treatment to form a plurality of holes on the first surface of the metal workpiece; applying a silane solution to the first surface having the plurality of holes to perform silanization treatment to form a silane modified layer on the inner walls of the plurality of holes; performing a cleaning treatment on the metal workpiece; and performing a drying treatment on the metal workpiece.

[0005] In an embodiment of the present invention, the above silane solution includes a silane compound having a functional group. The functional group includes an amino group, an alkenyl group, an acryloyloxy group, or a combination thereof.

[0006] In an embodiment of the present invention, the above silane solution includes a silane compound represented by the following formula (1).

[0007]

[0008] In formula (1), R represents an alkyl group or a hydrogen atom,

[0009] L represents an alkylene group, -NH-, -CO-, or a combination thereof,

[0010] Y represents an amino group, an alkenyl group, or an acryloyloxy group,

[0011] n represents an integer from 1 to 3.

[0012] In an embodiment of the present invention, the above silanization treatment further includes: performing a hydrolysis process on the silane solution. The hydrolysis process is performed at a temperature of 25°C to 40°C for 4 hours to 7 hours.

[0013] In one embodiment of the present invention, the components constituting the above-mentioned silane solution include alcohols, water, and a silane compound having a functional group. The functional group includes an amino group, an alkenyl group, an acryloyloxy group, or a combination thereof. Based on the total amount of the silane solution being 100% by weight, the content of the alcohol is 10% to 40% by weight, the content of water is 60% to 90% by weight, and the content of the silane compound having a functional group is 1% to 5% by weight.

[0014] A method for joining a metal and a fiber composite material of the present invention includes: providing a surface-modified metal workpiece, which is prepared by the above-mentioned method for surface modification of a metal; and heating the surface-modified metal workpiece in a molding die so that a thermoplastic resin in a molten state in the fiber composite material infiltrates into a plurality of holes to join the fiber composite material and the metal workpiece.

[0015] In one embodiment of the present invention, the above-mentioned thermoplastic resin includes polycarbonate, polypropylene, polyamide, or acrylonitrile-butadiene-styrene copolymer.

[0016] A composite body of a metal and a fiber composite material of the present invention includes a metal workpiece, a silane modification layer, and a fiber composite material. The metal workpiece has opposite first and second surfaces. The first surface has a plurality of holes. The silane modification layer is located on the first surface of the metal workpiece and covers the surfaces in the plurality of holes. A bond is formed between the silane modification layer and the metal workpiece. The fiber composite material includes a thermoplastic resin. The fiber composite material is located on the silane modification layer. The thermoplastic resin infiltrates into the plurality of holes to form an anchoring effect. A bond is formed between the fiber composite material and the silane modification layer.

[0017] In one embodiment of the present invention, the above-mentioned plurality of holes are formed in a lateral barb shape along the radial direction of the metal workpiece.

[0018] Based on the above, the method for surface modification of a metal and the method for joining a metal and a fiber composite material of the present invention each include a step of performing a silanization treatment on the surface of the metal workpiece. Thereby, the surface-modified metal workpiece formed by the method for surface modification of a metal can be tightly bonded to the material joined above it, the metal workpiece in the composite body formed by the method for joining a metal and a fiber composite material can be tightly bonded to the fiber composite material, and no bonding adhesive is required during bonding. In addition, the composite material containing the silane modification layer formed by the method for surface modification of a metal and the method for joining a metal and a fiber composite material of the present invention can be recycled and reused, achieving effects such as carbon reduction benefits.

[0019] To make the above features and advantages of the present invention more obvious and understandable, specific embodiments and accompanying drawings are hereinafter given in detail as follows. Description of the Drawings

[0020] Figure 1 is a step diagram of a method for modifying a metal surface according to an embodiment of the present invention;

[0021] Figure 2 is a cross-sectional view of a composite of a metal and a fiber composite according to an embodiment of the present invention;

[0022] Figure 3 is a step diagram of a method for joining a metal and a fiber composite according to an embodiment of the present invention;

[0023] Figure 4A is an optical microscope image of a composite of a metal and a fiber composite according to an embodiment of the present invention;

[0024] Figure 4B is an optical microscope image of a composite of a metal and a fiber composite according to a comparative example of the present invention.

[0025] Description of Reference Numerals

[0026] S100, S102, S104, S106, S108, S110, S300, S302: Step 200: Composite of metal and fiber composite

[0027] 210: Metal workpiece

[0028] 210a: First surface

[0029] 210b: Second surface

[0030] 212: Hole

[0031] 220: Silane modification layer

[0032] 230: Fiber composite

[0033] 232: Thermoplastic resin

[0034] 234: Glass fiber Detailed Description of the Invention

[0035] The following are embodiments that describe the content of the present invention in detail. The implementation details proposed in the embodiments are for illustrative purposes and do not limit the scope of protection of the content of the present invention. Any person skilled in the art can modify or change these implementation details according to the needs of the actual implementation method.

[0036] Exemplary embodiments of the present invention will be described fully hereinafter with reference to the accompanying drawings. However, the present invention can be implemented in various different forms and should not be construed as limited to the embodiments described herein. In the drawings, for clarity, the sizes and thicknesses of components, parts, and layers may not be drawn to actual scale. Directional terms mentioned herein, such as "upper", "lower", "front", "rear", etc., are only with reference to the directions of the attached drawings. Therefore, the directional terms used are for the purpose of illustration and understanding of the present application, rather than for limiting the present application. Additionally, in the specification, unless explicitly described to the contrary, the word "comprising" will be understood to mean including the components described, but not excluding any other components. For ease of understanding, the same components will be denoted by the same reference numerals in the following description.

[0037] Figure 1 is a step diagram of a method for modifying a metal surface according to an embodiment of the present invention. Figure 2 is a cross-sectional view of a composite of a metal and a fiber composite material according to an embodiment of the present invention.

[0038] Please refer to Figure 1 and Figure 2 , in step S100, a metal workpiece 210 is provided. The metal workpiece 210 has opposite first surface 210a and second surface 210b. The material of the metal workpiece 210 may include aluminum, titanium, chromium, stainless steel, or their alloys, preferably aluminum or its alloys.

[0039] Then, in step S102, the surface of the metal workpiece 210 is cleaned. In this embodiment, the first surface 210a of the metal workpiece 210 is cleaned. The cleaning method may be immersion and oscillation cleaning. For example, the metal workpiece can be immersed and oscillated in a solvent for 10 to 20 minutes. The solvent may include acetone, ethanol, or other suitable solvents.

[0040] Next, in step S104, an etching solution is applied to the surface of the metal workpiece 210 to form a plurality of holes 212 on the surface of the metal workpiece 210. In this embodiment, the etching solution is applied to the first surface 210a of the metal workpiece 210 for corrosion and hole-making treatment to form a plurality of holes 212 on the first surface 210a of the metal workpiece 210. The first surface 210a of the metal workpiece 210 can be subjected to corrosion and hole-making treatment in only one pass. In this embodiment, the plurality of holes 212 are formed in a lateral barb shape along the radial direction of the metal workpiece 210. Thereby, the surface roughness of the metal workpiece can be reduced and the interfacial specific surface area can be increased, so that the metal workpiece 210 and the material bonded thereto are tightly bonded. The opening length (i.e., the hole size) of the holes in the lateral barb shape on the first surface 210a can be 2 micrometers to 12 micrometers, preferably 2 micrometers to 6 micrometers. The roughness (Rz) of the holes can be 8 micrometers to 18 micrometers, preferably 8 micrometers to 12 micrometers. The etching depth of the holes can be 5 micrometers to 20 micrometers, preferably 10 micrometers to 20 micrometers.

[0041] The etching solution may include chloride ions, copper ions, iron ions, manganese ions, sulfate ions, a combination thereof, or other suitable etching solutions. For example, the etching solution may include concentrated sulfuric acid with a weight percentage concentration of 5% to 10%, copper chloride with a weight percentage concentration of 0.1% to 0.5%, ferric chloride with a weight percentage concentration of 10% to 20%, manganese sulfate with a weight percentage concentration of 0.5% to 1%, and the balance of water (such as pure water). The etching time of the etching solution on the metal workpiece 210 can be 15 seconds to 60 seconds, preferably 20 seconds to 30 seconds, more preferably 25 seconds.

[0042] Then, in step S106, a silane solution is applied to the surface on which the plurality of holes 212 are formed for silanization treatment. In this embodiment, the silane solution is applied to the first surface 212a on which the plurality of holes 212 are formed for silanization treatment. The first surface 212a on which the plurality of holes 212 are formed can be subjected to silanization treatment in only one pass. Thereby, a silane modified layer 220 can be formed on the first surface 212a of the metal workpiece 210 and on the surfaces in the plurality of holes 212 (i.e., the inner walls of the plurality of holes 212). The silane modified layer 220 can form a chemical bond (such as a covalent bond) with the metal workpiece, thereby improving the bonding strength between the metal workpiece and the silane modified layer. In addition, the formation of the silane modified layer 220 on the surfaces in the plurality of holes 212 increases the number of silane compounds bonded to the surface of the metal workpiece 210, so that the metal workpiece 210 and the material bonded thereto are tightly bonded.

[0043] In this embodiment, the components constituting the silane solution may include alcohols, water, and a silane compound having a specific functional group. The specific functional group may include an amino group, an alkenyl group, an acryloyloxy group, or a combination thereof. The components of the silane solution may further include an Si-R' compound as needed, where R' represents an alkyl group.

[0044] In this embodiment, the silane solution may include a silane compound having a specific functional group. The specific functional group may include an amino group, an alkenyl group, an acryloyloxy group, or a combination thereof. The silane compound may be represented by the following formula (1).

[0045]

[0046] In formula (1), R represents an alkyl group or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms; L represents an alkylene group, -NH-, -CO-, or a combination thereof, preferably an alkylene group having 2 to 6 carbon atoms; Y represents an amino group, an alkenyl group, or an acryloyloxy group; n represents an integer of 1 to 3, preferably 1. When n is 1, multiple Rs may be the same or different; when n is 2, multiple Rs may be the same or different, multiple Ls may be the same or different, and multiple Ys may be the same or different; when n is 3, multiple Ls may be the same or different, and multiple Ys may be the same or different. In this embodiment, the silane compound may be bonded to the metal workpiece 210 through the R group in formula (1). The silane compound may be bonded to the material subsequently joined to the metal workpiece (such as the thermoplastic resin in the fiber composite) through the Y group in formula (1).

[0047] The alcohols in the silane solution may include ethanol (such as absolute ethanol) or other suitable alcohols. The water may be pure water or deionized water (DI water). There is no particular limitation on the Si-R' compound, and an appropriate Si-R' compound may be selected according to requirements. R' is preferably a methyl group, an ethyl group, or a propyl group. When the silane solution includes an Si-R' compound, the grafting rate and stability can be improved.

[0048] The method of the silanization treatment may include a hydrolysis process, an application process, and a curing treatment. The hydrolysis process may be carried out at a temperature of 25°C to 40°C for 4 hours to 7 hours. There is no particular limitation on the method of the application process, but an impregnation method, a spraying method, a coating method, or other suitable methods may be used. The application process may be carried out at a temperature of 25°C to 40°C for 10 minutes to 30 minutes. The curing treatment may be carried out at a temperature of 80°C to 120°C for 1 hour to 6 hours.

[0049] In the steps of the hydrolysis process, the pH value of the silane solution can be adjusted to the corresponding appropriate range according to the functional groups of the silane compounds. For example, when the functional group of the silane compound is an amino group, the pH value of the silane solution can be adjusted to 3 to 5; when the functional group of the silane compound is other functional groups other than the amino group, the pH value of the silane solution can be adjusted to 10 to 13. Thereby, the degree of hydrolysis can be improved. For example, the silane compound can be completely hydrolyzed. Based on the total amount of the silane solution being 100% by weight, the content of alcohols can be 10% to 40% by weight, the content of water can be 60% to 90% by weight, the content of the silane compound with functional groups can be 1% to 5% by weight, and the content of the Si-R' compound can be 1% to 5% by weight.

[0050] Next, in step S108, the metal workpiece 210 is cleaned. The solvent used for the cleaning process may include pure water, alcohols, ketones, or other suitable solvents. During the cleaning process, a flowing solvent can be used for rinsing, and agitation can be used as an auxiliary. The agitation method is not particularly limited, but agitation can be performed using ultrasonic waves, jet flow, air introduction, or other suitable methods.

[0051] Then, in step S110, the metal workpiece 210 is cured. The curing process can be carried out at a temperature of 80°C to 120°C for 1 hour to 6 hours. Thus, a surface-modified metal workpiece can be obtained.

[0052] Figure 3 It is a step diagram of a method for joining a metal and a fiber composite according to an embodiment of the present invention.

[0053] Please refer to Figure 2 and Figure 3 , in step S300, a surface-modified metal workpiece is provided. The surface-modified metal workpiece is prepared by the above-described method for surface modification of a metal (steps S100 to S110).

[0054] In step S302, the fiber composite 230 is joined to the surface-modified metal workpiece 210. In this embodiment, the surface-modified metal workpiece 210 is placed in a molding die and heated so that the thermoplastic resin 232 in a molten state in the fiber composite 230 infiltrates into the plurality of holes 212 to form an anchoring effect. A bond is formed between the fiber composite 230 and the silane modification layer 220 on the surface of the metal workpiece 210. Thereby, the fiber composite 230 can be tightly joined to the surface-modified metal workpiece 210 to form a composite body 200 of a metal and a fiber composite.

[0055] The fiber composite material 230 may include a thermoplastic resin 232 and glass fibers 234. There are no particular limitations on the thermoplastic resin 232, and an appropriate thermoplastic resin can be selected according to requirements. For example, the thermoplastic resin 232 may include polycarbonate (PC), polypropylene (PP), polyamide (PA), acrylonitrile-butadiene-styrene (ABS) copolymer, or other suitable thermoplastic resins. The thermoplastic resin 232 can form a bond with specific functional groups in the silane compound forming the silane modified layer 220. Thereby, a bond is formed between the fiber composite material 230 and the silane modified layer 220, so that the fiber composite material 230 is tightly joined to the surface-modified metal workpiece 210.

[0056] Hereinafter, the present invention will be described in detail with reference to examples. The following examples are provided for describing the present invention, and the scope of the present invention includes the scope described in the following claims and their substitutes and modifications, and is not limited to the scope of the examples.

[0057] Examples

[0058] Place the aluminum alloy component in a container filled with acetone and clean it by soaking and shaking for 5 - 10 minutes. After rinsing with an appropriate amount of pure water, dry it. Then, place the component in a container filled with an etching solution (8 - 10% concentrated sulfuric acid, 0.3 - 0.5% copper chloride, 14 - 16% ferric chloride, 0.5 - 0.8% manganese sulfate, and the remaining amount of pure water) and perform a single-pass corrosion and pore-forming treatment. The etching process is carried out at room temperature for 20 - 40 seconds.

[0059] Next, apply the silane solution to the aluminum alloy with holes formed on the surface, and sequentially perform a hydrolysis process, a fiber implantation process, and a curing treatment. Among them, the hydrolysis process is carried out in a water-containing environment and at a temperature of 30 - 40 °C for 4 - 6 hours. The fiber implantation process is carried out at room temperature for 10 - 30 minutes by an impregnation method, a spraying method, or a coating method. The curing treatment is carried out at a temperature of 80 - 120 °C for 2 - 5 hours.

[0060] Then, wash the aluminum alloy with pure water at room temperature for several minutes. Next, dry the aluminum alloy at a temperature of 110 °C for 120 minutes or longer to obtain a surface-modified metal component. Make a specimen according to the ISO-19095 standard. Place the surface-modified metal component in a mold and perform a hot pressing process at a mold closing temperature of 160 - 190 °C, so that the polycarbonate in the fiber composite material containing polycarbonate and glass fibers becomes in a molten state, so as to join the fiber composite material with the surface-modified metal component, and a composite of metal and fiber composite material can be obtained.

[0061] The obtained metal-fiber composite can be used to measure the pore size by a scanning electron microscope (SEM), and the tensile strength can be measured by a universal testing machine with reference to the ISO-19095 standard. The measured results are shown in Table 1.

[0062] [Table 1]

[0063]

[0064] Comparative Example

[0065] The composite of the metal and fiber composite in the comparative example was prepared by the same steps as in the example, and the difference was that it did not have a silane modification layer.

[0066] The surfaces of the composites of the metal and fiber composites prepared in the example and the comparative example were observed by an optical microscope after the fiber composites were removed by heating. When the composite of the metal and fiber composite included a silane modification layer ( Figure 4A ), after the fiber composite was removed, there was no fracture on the surface of the metal workpiece 210 and the surface of the fiber composite 230. When the composite of the metal and fiber composite did not include a silane modification layer ( Figure 4B ), after the fiber composite was removed, there was a part of the metal workpiece 210 remaining on the surface of the fiber composite 230.

[0067] The tensile strengths of the composites of the metal and fiber composites prepared in the example and the comparative example were measured by a universal testing machine. The tensile strength of the composite of the metal and fiber composite in the example was about 34 MPa, and the tensile strength of the composite of the metal and fiber composite in the comparative example was about 27 MPa.

[0068] In summary, the method for surface modification of a metal and the method for bonding a metal and a fiber composite according to the present invention each include a step of performing a silanization treatment on the surface of a metal workpiece. Thereby, the silane modification layer can be tightly bonded to the material (such as a fiber composite) joined thereto, and no bonding agent is required during bonding. In addition, the method for surface modification of a metal, the method for bonding a metal and a fiber composite, and the composite according to the present invention can perform only one pass of corrosion pore formation treatment and only one pass of silanization treatment, so that the silane modification layer can be tightly bonded to the material (such as a fiber composite) joined thereto, and no bonding agent is required during bonding. In addition, the materials of the composites containing a silane modification layer formed by the method for surface modification of a metal and the method for bonding a metal and a fiber composite according to the present invention can be recycled, achieving effects such as carbon reduction benefits.

[0069] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for modifying a metal surface, comprising: providing a metal workpiece having opposite first and second surfaces; cleaning the first surface of the metal workpiece; applying an etching solution to the first surface of the metal workpiece to perform corrosion pore-forming treatment to form a plurality of holes on the first surface of the metal workpiece; applying a silane solution to the first surface forming the plurality of holes to perform silanization treatment so that a silane modified layer is formed on the inner walls of the plurality of holes; performing a cleaning treatment on the metal workpiece; and performing a drying treatment on the metal workpiece.

2. The method for modifying a metal surface according to claim 1, wherein the silane solution comprises a silane compound having a functional group, and the functional group comprises an amino group, an alkenyl group, an acryloyloxy group or a combination thereof.

3. The method for modifying a metal surface according to claim 1, wherein the silane solution comprises a silane compound represented by the following formula (1): In formula (1), R represents an alkyl group or a hydrogen atom, L represents an alkylene group, -NH-, -CO- or a combination thereof, Y represents an amino group, an alkenyl group or an acryloyloxy group, n represents an integer from 1 to 3.

4. The method for modifying a metal surface according to claim 1, wherein the silanization treatment further comprises: performing a hydrolysis process on the silane solution, and the hydrolysis process is carried out at a temperature of 25°C to 40°C for 4 hours to 7 hours.

5. The method for modifying a metal surface according to claim 1, wherein the components constituting the silane solution include alcohols, water and a silane compound having a functional group, and the functional group comprises an amino group, an alkenyl group, an acryloyloxy group or a combination thereof, based on the total amount of the silane solution being 100% by weight, the content of the alcohols is 10% to 40% by weight, the content of the water is 60% to 90% by weight, and the content of the silane compound having a functional group is 1% to 5% by weight.

6. A method for joining a metal and a fiber composite, comprising: providing a surface-modified metal workpiece, and the surface-modified metal workpiece is prepared by the method for modifying a metal surface according to any one of claims 1 to 5; and heating the surface-modified metal workpiece in a molding die so that a thermoplastic resin in a molten state in the fiber composite infiltrates into the plurality of holes to join the fiber composite and the surface-modified metal workpiece.

7. The method for joining a metal and a fiber composite according to claim 6, wherein the thermoplastic resin comprises polycarbonate, polypropylene, polyamide or acrylonitrile-butadiene-styrene copolymer.

8. A composite of a metal and a fiber composite, comprising: a metal workpiece having opposite first and second surfaces, and the first surface has a plurality of holes; a silane modified layer located on the first surface of the metal workpiece and covering the surfaces in the plurality of holes, and a bond is formed between the silane modified layer and the metal workpiece; and The fiber composite material includes a thermoplastic resin. The fiber composite material is located on the silane-modified layer. The thermoplastic resin penetrates into the plurality of holes to form an anchoring effect, and a bonding is formed between the fiber composite material and the silane-modified layer.

9. The composite body of the metal and the fiber composite material according to claim 8, wherein the plurality of holes are formed in a lateral barb shape along the radial direction of the metal workpiece.

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