Fiber-metal composite laminate and method of manufacturing the same

Abstract

A fiber and metal composite laminate and a method of manufacturing the same. The fiber and metal composite laminate includes an aluminum-based metal layer and a composite material layer. A surface of the aluminum-based metal layer includes a plurality of holes and a plurality of micro-holes in the holes, and the surface has a specific content of (200) crystal planes. The surface of the aluminum-based metal layer has the plurality of micro-holes, which facilitates embedding at least a portion of the composite material layer in the holes and the micro-holes of the aluminum-based metal layer, thereby improving the lap strength and stability of the composite laminate.

Description

Technical Field

[0001] This disclosure relates to a technique for manufacturing a hybrid material, and more particularly to a fiber-metal composite laminate and its manufacturing method. Background Technology

[0002] Lightweight materials are widely used in various industries, such as 3C, aerospace, and bicycles. As the industry's requirements for lightweight materials become increasingly stringent, manufacturers need to optimize and improve the bonding of dissimilar materials, such as metals and composites, to produce lighter and higher-performing products.

[0003] Nanomolding technology (NMT) is a technique that combines nano-surface-treated metals with composite materials (such as resins) to form fiber-metal composite laminates. In NMT, adhesives can be used to bond the metal and composite materials to increase the lap strength of the composite. However, the use of adhesives increases manufacturing costs, and adhesives are susceptible to environmental factors that can affect the overall properties of the composite laminate. Furthermore, the size and distribution of pores on the metal surface and the properties of the composite material itself also affect the lap strength of the composite.

[0004] In view of the above, there is still a need to provide a new fiber-metal composite laminate and its manufacturing method to overcome the aforementioned problems. Summary of the Invention

[0005] This disclosure provides a fiber-metal composite laminate. The fiber-metal composite laminate comprises an aluminum-based metal layer and a composite material layer. The surface of the aluminum-based metal layer includes multiple pores and multiple micro-side holes located within the pores, and the surface has a (200) crystal plane content of not less than 40%. Within a depth range below the surface, the surface has at least 20 micro-side holes per unit cross-section, with a depth range of 40 μm and a unit cross-section of 1 mm. The composite material layer comprises a thermoplastic polymer and a fiber material, wherein at least a portion of the composite material layer is embedded in the multiple pores and multiple micro-side holes of the aluminum-based metal layer.

[0006] In some implementations, the surface of the aluminum-based metal layer has a porosity of over 70%.

[0007] In some embodiments, the average surface roughness of the aluminum-based metal layer is 15 μm to 35 μm.

[0008] In some embodiments, the overlap strength between the aluminum-based metal layer and the composite material layer is 20 MPa to 27 MPa.

[0009] In some implementations, the aperture of one opening of each of the plurality of holes is 50 μm to 90 μm.

[0010] This disclosure provides a method for manufacturing a fiber-metal composite laminate, comprising the following steps: An aluminum-based metal layer is provided, wherein the surface of the aluminum-based metal layer has a (200) crystal plane content of not less than 40%. A chemical etching operation is performed on the surface of the aluminum-based metal layer to form a plurality of pores and a plurality of micro-side holes located within the plurality of pores on the surface, wherein the pores contain a plurality of micro-side holes. After the chemical etching operation, the surface has at least 20 micro-side holes per unit cross-section at a depth of 40 μm below the surface. A composite material layer is provided, wherein the composite material layer comprises a thermoplastic polymer and a fiber material. A hot-pressing process is performed to embed at least a portion of the composite material layer into the plurality of pores and the plurality of micro-side holes of the aluminum-based metal layer.

[0011] In some implementations, the etching time for the chemical etching operation is from 15 seconds to 300 seconds.

[0012] In some implementations, the etching solution used in chemical etching operations contains sulfuric acid and chloride ions.

[0013] In some implementations, after the chemical etching operation, the surface of the aluminum-based metal layer has a porosity of over 70%.

[0014] In some implementations, the average surface roughness of the aluminum-based metal layer is 15 μm to 35 μm after the chemical etching operation. Attached Figure Description

[0015] The various aspects of this disclosure can be best understood by reading in conjunction with the accompanying drawings, and the following detailed description is provided. It should be understood that, in accordance with industry standard practice, the various features are not drawn to scale. In fact, the dimensions of the various features can be arbitrarily increased or decreased for clarity.

[0016] Figure 1 This is a partially enlarged top view of an aluminum-based metal layer after chemical etching, according to some embodiments of this disclosure;

[0017] Figure 2 For along Figure 1 A partially enlarged cross-sectional schematic diagram of the aluminum-based metal layer;

[0018] Figure 3 This is a perspective view of a fiber-metal composite laminate according to some embodiments of the present disclosure;

[0019] Figure 4 A flowchart illustrating a method for manufacturing a fiber-metal composite laminate according to one embodiment of this disclosure;

[0020] Figure 5X-ray diffraction analysis diagrams of aluminum-based metal layers in comparative examples, experimental example 1, and experimental example 2 according to the present disclosure;

[0021] Figure 6 A scanning electron microscope image of the surface of the aluminum-based metal layer in Experimental Example 1 according to the present disclosure;

[0022] Figure 7 A scanning electron microscope image of a cross section of an aluminum-based metal layer in Experimental Example 1 according to the present disclosure.

[0023] Figure 8 Scanning electron micrograph of the surface of the aluminum-based metal layer in Experimental Example 2 according to the present disclosure;

[0024] Figure 9 Scanning electron microscopy image of the cross section of the fiber-metal composite laminate of Experimental Example 2 according to the present disclosure.

[0025] [Symbol Explanation]

[0026] 100: Fiber-Metal Composite Laminate

[0027] 110: Aluminum-based metal layer

[0028] 110a: Surface

[0029] 112: Hole

[0030] 114: Hole Area

[0031] 116: Micro-side hole

[0032] 120: Composite material layer

[0033] 122: Thermoplastic polymer

[0034] 124: Fiber Materials

[0035] 400: Manufacturing Method

[0036] 410: Steps

[0037] 420: Steps

[0038] 430: Steps

[0039] 440: Steps

[0040] L: Line

[0041] D: Opening diameter

[0042] X, Y, Z: Direction Detailed Implementation

[0043] The following disclosure provides many different implementations or embodiments for achieving various features of this disclosure. Specific embodiments of components and arrangements are described below to simplify this disclosure. These are, of course, merely embodiments and are not intended to be limiting. For example, in the following description, the formation of a first feature above or on a second feature may include an implementation where the first and second features are formed in direct contact, or an implementation where another feature may be formed between the first and second features so that the first and second features are not in direct contact. Furthermore, reference numerals or text may be repeated in different instances in this disclosure. The purpose of repetition is to simplify and clarify the description, not to define the relationships between the different implementations and configurations discussed.

[0044] In addition, spatial relative terms such as "below," "below," "lower than," "above," "above," and other similar terms are used here for the convenience of describing the relationship between one element or feature and another element or feature in the figure. Spatial relative terms cover not only the orientation depicted in the figure but also other orientations of the device during use or operation. That is, when the orientation of the device differs from that in the figure (rotated 90 degrees or in other orientations), the spatial relative terms used in this disclosure can also be interpreted accordingly.

[0045] In this document, the use of "from one value to another" to indicate a range is a concise way of representing a range to avoid listing all the values ​​within that range in the specification. Therefore, the description of a particular value range encompasses any value within that range and the smaller range of values ​​defined by that range, just as if the arbitrary value and the smaller range were explicitly stated in the specification. Furthermore, when a number or range of numbers is described as "approximately," "about," or other similar terms, this is to cover numbers described within a reasonable range, such as + / - 10%, as those skilled in the art will understand.

[0046] In the bonding technology of hybrid materials, the size, density, distribution of pores on the metal surface and the properties of the composite material layers will affect the anchoring effect of the hybrid material. If the composite material cannot penetrate smoothly into the pores of the metal, the lap strength between the metal and the composite material cannot be increased. The fiber-metal composite laminate disclosed herein has multiple micro-side holes on the surface of the metal, and the composite material can be embedded into the micro-side holes of the metal, thereby forming a composite laminate with high lap strength and a stable bond. The fiber-metal composite laminate disclosed herein does not require the use of adhesives for dissimilar bonding between the aluminum-based metal and the composite material layers, so there is no situation where the overall properties of the composite laminate are affected by adhesives. In addition, the pores and micro-side holes formed by the aluminum-based metal in the preferred (200) orientation allow the composite material to be embedded smoothly, so a stable bonded composite laminate can be obtained without modifying the properties of the composite material, which can reduce the number of process steps.

[0047] Please refer to Figure 1 This is a partially enlarged top view of an aluminum-based metal layer 110 after chemical etching according to some embodiments of the present disclosure. Before chemical etching of the aluminum-based metal layer 110, the surface 110a of the aluminum-based metal layer 110 has a preferred orientation of (200) crystal planes. Specifically, the aluminum-based metal layer 110 is obtained with a preferred orientation of (200) crystal planes by a preferred orientation process. The preferred orientation process can be, for example, cold rolling and annealing processes. In some embodiments, the thickness of the aluminum-based metal layer 110 is about 0.1, 0.3, 0.8 or 1.5 mm. It is understood that the aluminum-based metal layer 110 mainly has four crystal planes: (111), (200), (220) and (311). It should be noted that, in this embodiment, considering the four crystal planes as the total, when the proportion of the (200) crystal plane is 40% or more and greater than the proportion of other crystal planes, it can be determined that the aluminum-based metal layer 110 has a preferred orientation of (200) crystal planes. The surface 110a of the aluminum-based metal layer 110 can be made to have (200) crystal planes with an amount of not less than 40%, such as 45% or more, 50% or more, 55% or more, or 60% or more.

[0048] like Figure 1 As shown, the surface 110a of the aluminum-based metal layer 110 has multiple holes 112. In some embodiments, the holes 112 can be circular, elliptical, rectangular, or polygonal. In some embodiments, the hole coverage of the surface 110a of the aluminum-based metal layer 110 is more than 70%. After etching, the aluminum-based metal layer 110 forms unevenly distributed hole regions 114, such as... Figure 1As shown, there are 5 perforated regions 114. However, the number of perforated regions 114 is not intended to limit the content of this disclosure, but only to illustrate the method of calculating the perforation coverage. The perforation coverage of this disclosure satisfies the following formula:

[0049] Pore ​​coverage rate = Pore area / Total area

[0050] in, Figure 1 The entire schematic diagram boundary is the "total area", while the total area of ​​the 5 hole regions 114 is the "hole area".

[0051] Please refer to Figure 2 , it is along Figure 1 A partially enlarged cross-sectional view of line L of the aluminum-based metal layer 110. (See diagram below.) Figure 1 and Figure 2 As shown, line L passes through two holes 112. Figure 2 As shown, each hole 112 has multiple micro-side holes 116. In some embodiments, within a depth range of 40 μm below the surface 110a of the aluminum-based metal layer 110, the surface 110a has at least 20 micro-side holes 116 per unit cross-section. It should be noted that the term "unit cross-section" in this document is 1 mm, meaning the distance of line L is 1 mm. Figure 1 and Figure 2 The length of line L, the number of holes 112 spanned by line L, and the number of micro-side holes 116 are merely illustrative and used to explain the micro-side holes under line L; their dimensions and numbers are not intended to limit the invention. Furthermore, the micro-side hole 116 herein is defined as a lateral (different from direction Z) micro-hole under a hole 112, and the number of micro-side holes 116 is an average value. In some embodiments, the length of the micro-side hole 116 is from about 2 μm to about 6 μm. In some embodiments, the opening diameter D of the hole 112 is from about 50 μm to about 90 μm, for example, about 60, 70, or 80 μm. When the opening diameter D of the hole 112 is from about 50 μm to about 90 μm, the subsequent composite material layer 120 (see reference)... Figure 3 It is relatively easy to embed into the holes 112. Furthermore, because each hole 112 has multiple micro-side holes 116 in the X and Y directions, the overlap strength between the aluminum-based metal layer 110 and the composite material layer 120 can be increased. In some embodiments, the average roughness (Rz) of the surface 110a of the aluminum-based metal layer 110 is about 15 μm to about 35 μm, for example, about 20, 25, or 30 μm.

[0052] Please refer to Figure 3This is a perspective view of a fiber-metal composite laminate 100 according to some embodiments of the present disclosure. The fiber-metal composite laminate 100 includes an aluminum-based metal layer 110 and a composite material layer 120. Specifically, the composite material layer 120 is disposed above (in the Z direction) a chemically etched aluminum-based metal layer 110. In other words, the aluminum-based metal layer 110 and the composite material layer 120 are stacked on top of each other. The composite material layer 120 includes a thermoplastic polymer 122 and a fiber material 124 dispersed in the thermoplastic polymer 122. In some embodiments, the thermoplastic polymer 122 may be, for example, polypropylene (PP), polyvinyl chloride (PVC), ABS plastic, polycarbonate (PC), polyamide resin (PA), polyacetal (POM), polyetheretherketone (PEEK), thermoplastic polyimide (TPI), or polyphenylene sulfide (PPS). In some embodiments, the fiber material 124 may be, for example, glass fiber, Kevlar fiber, basalt fiber, boron fiber, PE fiber, natural fiber, or carbon fiber. At least a portion of the composite material layer 120 is embedded in a plurality of pores 112 and a plurality of micro-side holes 116 of the aluminum-based metal layer 110 (see reference). Figure 2 In some embodiments, the lap strength between the aluminum-based metal layer 110 and the composite material layer 120 is about 20 MPa to about 27 MPa, for example about 21, 22, 23, 24, 25, or 26 MPa. When the porosity of surface 110a is less than 70%, surface 110a cannot provide a sufficient number of porosity locations for the composite material layer 120 to embed, thereby reducing the lap strength of the fiber-metal composite laminate 100.

[0053] Please also refer to Figure 1 and Figure 4 ,in Figure 4This is a flowchart of a method 400 for manufacturing a fiber-metal composite laminate 100 according to one embodiment of the present disclosure. The manufacturing method 400 includes steps 410 to 440. In step 410, an aluminum-based metal layer 110 is provided, wherein the surface 110a of the aluminum-based metal layer 110 has a (200) crystal plane content of not less than 40%. In step 420, a chemical etching operation is performed on the surface 110a of the aluminum-based metal layer 110 to form a plurality of holes 112 and a plurality of micro-side holes 116 located in the holes 112. After the chemical etching operation, within a depth range below the surface 110a, a unit cross-section of the surface 100a has at least 20 micro-side holes, and the depth range is 40 μm. In some embodiments, the etching time of the chemical etching operation is from about 15 seconds to about 300 seconds, for example, about 30, 60, 120, 180, or 240 seconds. In some embodiments, the etching solution of the chemical etching operation contains sulfuric acid and chloride ions. In some embodiments, the etching solution for the chemical etching operation is composed of a solution containing sulfuric acid, chloride ions, and iron ions. In some embodiments, the etching solution for the chemical etching operation is composed of a solution containing sulfuric acid, chloride ions, and copper ions. The addition of iron ions and copper ions can increase the etching efficiency of the aluminum-based metal layer 110. In step 430, a composite material layer 120 is provided, wherein the composite material layer 120 comprises a thermoplastic polymer 122 and a fiber material 124. In step 440, a hot pressing process is performed to embed at least a portion of the composite material layer 120 into a plurality of pores 112 and a plurality of micro-side holes 116 in the aluminum-based metal layer 110. If the content of the (200) crystal plane is less than 40%, although the chemical etching operation can still form pores 112, the number of micro-side holes 116 will be greatly reduced, or there will be no micro-side holes 116, thus failing to effectively improve the overlap strength and stability of the fiber-metal composite laminate 100.

[0054] Figure 5 The images show X-ray diffraction analysis of the aluminum-based metal layer 110 in Comparative Examples, Experimental Example 1, and Experimental Example 2, based on this disclosure. Figure 2 As shown, the aluminum-based metal layer 110 mainly has four crystal planes: (111), (200), (220), and (311). In the comparative example, the (200) crystal plane accounts for approximately 10% of the total number of the four crystal planes. In Experimental Example 1, the (200) crystal plane accounts for approximately 55% of the total number of the four crystal planes. In Experimental Example 2, the (200) crystal plane accounts for approximately 64% of the total number of the four crystal planes.

[0055] The inventors of this case discovered that, compared to the (111), (220), and (311) crystal planes of the aluminum-based metal layer 110, the (200) crystal plane can generate more micro-side holes, which is related to the strain energy of each crystal plane. Specifically, during the etching process of the aluminum-based metal layer, the aluminum oxide on the metal surface is more fragile in the direction of higher strain energy, making it easier for the etching solution to penetrate, thereby generating more micro-side holes. In addition, if the (200) crystal plane is not preferred, the etching solution usually etches in the depth direction (direction Z) and is less likely to generate micro-side holes in the left and right directions (directions X and Y).

[0056] Please refer to Figure 6 It is a scanning electron microscope image of the surface 110a of the aluminum-based metal layer 110 according to Experimental Example 1 of this disclosure. Figure 6 The area contains approximately 18 holes (area 114). Please refer to [reference needed]. Figure 7 This is a scanning electron microscope image of a cross section of the aluminum-based metal layer 110 in Experimental Example 1 according to the present disclosure. Figure 7 The holes in the middle have about 4 micro-side holes 116.

[0057] The following uses the results of comparative examples, experimental example 1 and experimental example 2 to illustrate the technical content and effects of the embodiments of the present invention in more detail, but it is not intended to limit the present invention.

[0058] The characteristics of the etched aluminum-based metal layer 110 and the overlap strength of the fiber-metal composite layer in the embodiment are shown in Table 1 below.

[0059] Table 1

[0060]

[0061]

[0062] The number of micro-side holes in Table 1 is the average number per 1 mm. The units for average roughness are μm, the units for aperture diameter are μm, and the units for lap strength are MPa. In this case, the lap strength between the aluminum base metal layer 110 and the composite material layer 120 was tested according to ASTM D1002 standard, and the bonding area of ​​the specimen was (25.4 mm ± 0.254 mm) × (12.7 mm ± 0.010 mm).

[0063] In the embodiments listed in Table 1, the aluminum-based metal layer uses an aluminum alloy sheet of model AA5052-H32 with a thickness of 1.5 mm. The etching solution for chemically etching the aluminum alloy sheet contains 10 wt.% sulfuric acid, 15 wt.% hydrochloric acid, and 75 wt.% deionized water. The etching solution in this embodiment does not contain manganese ions. The etching time is approximately 60 seconds. After etching, the aluminum alloy sheet is cleaned with nitric acid, rinsed with deionized water for approximately 300 seconds, and then dried. The drying temperature is approximately 80°C, and the drying time is approximately 6 hours. The thermoplastic polymer of the composite material layer in each embodiment is polycarbonate (PC). The hot-pressing temperature of the composite material layer and the aluminum alloy sheet in each embodiment is approximately 230°C, and the hot-pressing pressure is approximately 50 kfg / cm. 3 The hot pressing time is approximately 300 seconds.

[0064] As shown in Table 1 above, the lap strength of Experimental Example 1 is 20.7 MPa, and the lap strength of Experimental Example 2 is 26.1 MPa. Therefore, compared with the comparative example, the fiber-metal composite laminates of Experimental Example 1 and Experimental Example 2 can provide better lap strength.

[0065] Please refer to Figure 8 This is a scanning electron microscope image of the surface 110a of the aluminum-based metal layer 110 according to Experimental Example 2 of this disclosure. The holes 112 on the surface 110a have a polygonal morphology.

[0066] Please refer to Figure 9 This is a scanning electron microscope image of a cross-section of the fiber-metal composite laminate 100 according to Experimental Example 2 of this disclosure. From Figure 9 It can be seen that the composite material layer 120 is embedded in multiple pores 112 and multiple micro-side holes 116 of the aluminum-based metal layer 110.

[0067] In summary, the fiber-metal composite laminate disclosed herein has multiple micro-pores on the surface of the metal, allowing the composite material to be embedded into these micro-pores, thus forming a composite laminate with high lap strength and a stable bond. The fiber-metal composite laminate disclosed herein does not require the use of adhesives for the dissimilar bonding between the aluminum-based metal layer and the composite material layer; therefore, there is no situation where adhesives affect the overall properties of the composite laminate. Furthermore, the holes and micro-pores formed by the aluminum-based metal in the preferred (200) orientation allow for smooth embedding of the composite material, so the properties of the composite material can be directly hot-pressed together with the aluminum-based metal layer to form a stable composite laminate without modifying the composite material's properties, thus simplifying the process steps. The hot-pressing process does not require vacuuming, thus reducing mold costs. The composite laminate formed by the aluminum-based metal layer and the composite material layer in this invention is at least 15% lighter than aluminum alloys, thereby increasing the added value of the product.

[0068] The foregoing overview of the features of various embodiments enables those skilled in the art to better understand the nature of this disclosure. Those skilled in the art should understand that this disclosure can be readily used as the basis for designing or modifying other processes and structures to achieve the same purpose and / or realize the same advantages of the embodiments described herein. Those skilled in the art should also recognize that such equivalent constructions do not depart from the spirit and scope of this disclosure, and that various changes, substitutions, and modifications can be made without departing from the spirit and scope of this disclosure.

Claims

1. A fiber and metal composite laminate characterized by, The aluminum-based metal layer comprises a surface comprising a plurality of holes and a plurality of micro-holes in the plurality of holes, and the surface has a (200) crystal plane accounting for not less than 40% of the total of (111), (200), (220) and (311) crystal planes of the aluminum-based metal layer. A unit cross section of the surface has at least 20 micro-holes in a depth range below the surface, and the depth range is 40 μm, and the unit cross section is 1 mm. A composite material layer comprising a thermoplastic polymer and a fiber material, wherein at least a portion of the composite material layer is embedded in the plurality of holes and the plurality of micro-holes of the aluminum-based metal layer. The surface of the aluminum-based metal layer has a hole coverage rate of more than 70%.

2. The fiber-metal laminate according to claim 1, characterized in that The surface of the aluminum-based metal layer has an average roughness of 15 μm to 35 μm.

3. The fiber-metal laminate according to claim 1, wherein The lap strength between the aluminum-based metal layer and the composite material layer is 20 MPa to 27 MPa.

4. The fiber-metal laminate according to claim 1, wherein Each of the plurality of holes has an opening aperture of 50 μm to 90 μm.

5. The fiber-metal laminate according to claim 1, wherein The aluminum-based metal layer comprises a surface comprising a plurality of holes and a plurality of micro-holes in the plurality of holes, and the surface has a (200) crystal plane accounting for not less than 40% of the total of (111), (200), (220) and (311) crystal planes of the aluminum-based metal layer.

6. A method of manufacturing a fiber and metal composite sheet, characterized by, A chemical etching operation is performed on the surface of the aluminum-based metal layer to form a plurality of holes and a plurality of micro-holes in the plurality of holes on the surface, A unit cross section of the surface has at least 20 micro-holes in a depth range below the surface after the chemical etching operation, and the depth range is 40 μm, and the unit cross section is 1 mm. A composite material layer comprising a thermoplastic polymer and a fiber material is provided. A hot pressing process operation is performed to embed at least a portion of the composite material layer in the plurality of holes and the plurality of micro-holes of the aluminum-based metal layer. The etching time of the chemical etching operation is 15 seconds to 300 seconds. The etching solution of the chemical etching operation comprises sulfuric acid and chloride ions. The surface of the aluminum-based metal layer has a hole coverage rate of more than 70% after the chemical etching operation.

7. The method of manufacturing a fiber and metal composite sheet according to claim 6, wherein The surface of the aluminum-based metal layer has an average roughness of 15 μm to 35 μm after the chemical etching operation.

8. The method of manufacturing a fiber and metal composite sheet according to claim 6, wherein ​ 9. The method of manufacturing a fiber and metal composite sheet according to claim 6, wherein ​ 10. The method of manufacturing a fiber and metal composite sheet according to claim 6, wherein ​

Images