CN118061618A

CN118061618A - Fiber and metal composite laminate and method for manufacturing same

Info

Publication number: CN118061618A
Application number: CN202211477303.3A
Authority: CN
Inventors: 黄彦霖; 江昀宸; 江祺璟; 吴隆佃
Original assignee: Metal Industries Research and Development Centre
Current assignee: Metal Industries Research and Development Centre
Priority date: 2022-11-23
Filing date: 2022-11-23
Publication date: 2024-05-24

Abstract

A fiber and metal composite laminate and a manufacturing method thereof are provided, wherein the fiber and metal composite laminate comprises an aluminum-based metal layer and a composite material layer. The surface of the aluminum-based metal layer comprises a plurality of holes and a plurality of micro-side holes positioned in the holes, and the surface of the aluminum-based metal layer is provided with a (200) plane with a specific content. The surface of the aluminum-based metal layer is provided with a plurality of micro-side holes, so that at least one part of the composite material layer is embedded into the holes and the micro-side holes of the aluminum-based metal layer, and the lap joint strength and the stability of the composite laminate are improved.

Description

Fiber and metal composite laminate and method for manufacturing same

Technical Field

The present disclosure relates to a hybrid material (hybrid material) manufacturing technology, and more particularly, to a fiber and metal composite laminate and a manufacturing method thereof.

Background

Lightweight materials are widely used in various industries, such as 3C, aviation, bicycle, and the like. With the increasing demand in the industry for lightweight materials, manufacturers need to optimize and improve the dissimilar metal joining of metal and composite materials to produce lighter and better performing products.

The nanofabrication treatment technique (nano molding technology; NMT) is a technique for joining nanocrystallized surface treated metal to a composite material (e.g., resin) to form a fiber and metal composite laminate. In the NMT field, metal materials and composite materials can be joined using glue to increase the lap strength of the hybrid material. However, the use of glue increases manufacturing costs and glue is susceptible to environmental factors affecting the overall properties of the composite laminate. In addition, the size and distribution of the pores in the metal surface and the nature of the composite itself can also affect the lap strength of the composite.

In view of the foregoing, there is still a need to provide a new fiber and metal composite laminate and a method for manufacturing the same to overcome the foregoing problems.

Disclosure of Invention

The present disclosure provides a fiber and metal composite laminate. The fiber and metal composite laminate comprises an aluminum-based metal layer and a composite material layer. The surface of the aluminum-based metal layer comprises a plurality of holes and a plurality of micro-side holes positioned in the holes, and the surface is provided with a (200) plane with the content of not less than 40 percent. The surface has at least 20 micro-side holes per unit section in a depth range below the surface, and the depth range is 40 μm and the unit section is 1mm. The composite material layer comprises thermoplastic polymer and fiber material, wherein at least one part of the composite material layer is embedded into a plurality of holes and a plurality of micro-side holes of the aluminum-based metal layer.

In some embodiments, the pore coverage of the surface of the aluminum-based metal layer is greater than 70%.

In some embodiments, the surface of the aluminum-based metal layer has an average roughness of 15 μm to 35 μm.

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

In some embodiments, an open pore size of each of the plurality of pores is 50 μm to 90 μm.

The present disclosure provides a method of manufacturing a fiber and 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) plane with a content of not less than 40%. And performing chemical etching operation on the surface of the aluminum-based metal layer to form a plurality of holes and a plurality of micro-side holes positioned in the holes on the surface, wherein the holes comprise the plurality of micro-side holes. Wherein after the chemical etching operation, the surface has at least 20 micro-side holes per unit section in a depth range below the surface, and the depth range is 40 μm. A composite layer is provided, wherein the composite layer comprises a thermoplastic polymer and a fibrous material. And performing hot pressing process operation to enable at least one part of the composite material layer to be embedded into the holes and the micro-side holes of the aluminum-based metal layer.

In some embodiments, the etching time of the chemical etching operation is 15 seconds to 300 seconds.

In some embodiments, the etching solution of the chemical etching operation comprises sulfuric acid and chloride ions.

In some embodiments, the pore coverage of the surface of the aluminum-based metal layer is greater than 70% after the chemical etching operation.

In some embodiments, the surface of the aluminum-based metal layer has an average roughness of 15 μm to 35 μm after the chemical etching operation.

Drawings

The various aspects of the disclosure may be best understood from the following detailed description when read with the accompanying drawing figures. It will be appreciated that the various features are not drawn to scale in accordance with standard practice in the industry. Indeed, the dimensions of the various features may be arbitrarily increased or reduced for clarity.

FIG. 1 is a partially enlarged schematic top view of an aluminum-based metal layer after chemical etching in accordance with some embodiments of the present disclosure;

FIG. 2 is an enlarged partial cross-sectional schematic view along the line of the aluminum-based metal layer of FIG. 1;

FIG. 3 is a schematic perspective view of a fiber and metal composite laminate according to some embodiments of the present disclosure;

FIG. 4 is a flow chart of a method of manufacturing a fiber and metal composite laminate according to one embodiment of the present disclosure;

FIG. 5 is an X-ray diffraction analysis chart of an aluminum-based metal layer according to comparative example, experimental example 1 and experimental example 2 of the present disclosure;

FIG. 6 is a scanning electron micrograph image of the surface of an aluminum-based metal layer of Experimental example 1 according to the present disclosure;

FIG. 7 is a scanning electron micrograph of a cross section of an aluminum-based metal layer of Experimental example 1 according to the present disclosure;

FIG. 8 is a scanning electron micrograph image of the surface of an aluminum-based metal layer of Experimental example 2 according to the present disclosure;

fig. 9 is a scanning electron micrograph of a cross section of a fiber and metal composite laminate according to experimental example 2 of the present disclosure.

[ Symbolic description ]

100 Fiber and metal composite laminate

110 Aluminum-based metal layer

110A surface

112 Holes

114 Hole area

116 Micro side hole

120 Composite material layer

122 Thermoplastic Polymer

124 Fibrous material

400 Manufacturing method

410 Step

420 Step

430 Step

440 Step

L line

D, opening aperture

X, Y, Z direction

Detailed Description

The following disclosure provides many different implementations, or examples, for implementing different features of the disclosure. Specific embodiments of components and arrangements are described below to simplify the present disclosure. These are, of course, merely examples and are not intended to be limiting. For example, in the description that follows, the formation of a first feature over or on a second feature may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which another feature may be formed between the first and second features such that the first and second features may not be in direct contact. Moreover, the present disclosure may repeat reference numerals and/or letters in the various examples. The purpose of repetition is to simplify and clearly illustrate the relationship between the various embodiments and arrangements discussed.

In addition, spatially relative terms such as "under," "below," "above," "over," and the like are used herein for convenience in describing the relationship of one element or feature to another element or feature in the figures. Spatially relative terms may be intended to encompass other orientations of the device in use or operation in addition to the orientation depicted in the figures. That is, spatially relative terms used in the present disclosure may be construed accordingly as well when the orientation of the device is different from the figures (rotated 90 degrees or at other orientations).

In this document, a range from "one value to another value" is a shorthand way of referring individually to all the values in the range, which are avoided in the specification. Thus, recitation of a particular numerical range includes any numerical value within that range, as well as the smaller numerical range bounded by any numerical value within that range, as if the any numerical value and the smaller numerical range were written in the specification in the clear. In addition, when a number or range of numbers is described as "about," "approximately," and other like terms, it is intended that the number described be a number within a reasonable range, as those skilled in the art will appreciate that the number or other number is within +/-10%.

In hybrid material joining techniques, the size, density, distribution of pores in the metal surface and the nature of the composite layer will affect the anchoring effect of the hybrid material. If the composite material cannot smoothly penetrate into the holes of the metal, the lap joint strength of the metal and the composite material cannot be increased. The fiber and metal composite laminate disclosed by the invention has the advantages that as the surface of the metal is provided with the plurality of micro-side holes, the composite material can be embedded into the micro-side holes of the metal, so that the composite laminate with high lap joint strength and stable combination is formed. The fiber and metal composite laminate disclosed by the invention does not need to use adhesive to bond different materials between aluminum-based metal and a composite material layer, so that the condition that the overall property of the composite laminate is influenced by the adhesive is avoided. In addition, the holes and micro-side holes formed by the aluminum-based metal with the preferred (200) orientation can enable the composite material to be smoothly embedded, so that the firmly combined composite laminate can be prepared without modifying the properties of the composite material, and the process steps can be reduced.

Referring to fig. 1, a partially enlarged top view of an aluminum-based metal layer 110 according to some embodiments of the present disclosure is shown after chemical etching. Prior to chemically etching the aluminum-based metal layer 110, the surface 110a of the aluminum-based metal layer 110 has a (200) planar grain preferred orientation (PREFERRED ORIENTATION). In detail, the aluminum-based metal layer 110 has a grain preferred orientation of (200) plane by a grain preferred orientation process. The grain preferred orientation process may be, for example, a cold rolling and annealing process. In some embodiments, the thickness of the aluminum-based metal layer 110 is about 0.1, 0.3, 0.8, or 1.5mm. It is understood that the aluminum-based metal layer 110 mainly has four planes (111), (200), (220), and (311). In the present embodiment, when the (200) plane ratio is 40% or more and greater than the ratio of the other planes, the aluminum-based metal layer 110 can be determined to have a preferable orientation of crystal grains in the (200) plane, based on the total of four planes. The surface 110a of the aluminum-based metal layer 110 may have a (200) plane in an amount of not less than 40%, for example, 45% or more, 50% or more, 55% or more, or 60% or more by adjusting parameters of the grain-preferred azimuthal process.

As shown in fig. 1, the surface 110a of the aluminum-based metal layer 110 has a plurality of holes 112. In some embodiments, the shape of the holes 112 may be circular, oval, rectangular, or polygonal in shape. In some embodiments, the pore coverage of the surface 110a of the aluminum-based metal layer 110 is greater than 70%. The aluminum-based metal layer 110 is etched to form unevenly distributed hole regions 114, as shown in fig. 1, having 5 hole regions 114. However, the number of hole areas 114 is not intended to limit the present disclosure, but is merely used to discuss the manner in which hole coverage is calculated. The hole coverage of the present disclosure satisfies the following equation:

Hole coverage = hole area/total area

The overall schematic boundary of fig. 1 is referred to as the "total area", and the total area of 5 hole areas 114 is referred to as the "hole area".

Please refer to fig. 2, which is a partially enlarged cross-sectional view along a line L of the aluminum-based metal layer 110 of fig. 1. As shown in fig. 1 and 2, line L passes through two holes 112. As shown in fig. 2, each hole 112 has a plurality of micro-side holes 116 therein. In some embodiments, the surface 110a of the aluminum-based metal layer 110 has at least 20 micro-side holes 116 per unit section within a depth range of 40 μm below the surface 110 a. The "unit cross section" herein is 1mm, that is, the distance of the line L is 1mm. Whereas the length of line L, the number of holes 112 spanned by line L, and the number of micro-holes 116 in fig. 1 and 2 are merely illustrative and are intended to illustrate micro-holes below line L, the size and number of which are not intended to limit the present invention. Further, the micro-holes 116 are defined herein as lateral (different from the direction Z) micro-holes under one hole 112, and the number of micro-holes 116 is an average value. In some embodiments, the microscale apertures 116 are about 2 μm to about 6 μm in length. In some embodiments, the opening aperture D of the holes 112 is 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 about 50 μm to about 90 μm, the composite material layer 120 (refer to fig. 3) of the subsequent process is easier to be embedded in the hole 112. Also, since each hole 112 has a plurality of micro-side holes 116 in the direction X and the direction Y, the overlap strength between the aluminum-based metal layer 110 and the composite material layer 120 can be increased. In some embodiments, the surface 110a of the aluminum-based metal layer 110 has an average roughness (Rz) of about 15 μm to about 35 μm, such as about 20, 25, or 30 μm.

Referring to fig. 3, a schematic perspective view of a fiber and metal composite laminate 100 according to some embodiments of the present disclosure is shown. The fiber and metal composite laminate 100 includes an aluminum-based metal layer 110 and a composite material layer 120. In detail, the composite material layer 120 is disposed over the chemically etched aluminum-based metal layer 110 (in the direction Z). In other words, the aluminum-based metal layer 110 and the composite material layer 120 are stacked on each other. The composite layer 120 includes thermoplastic polymers 122 and fibrous materials 124 dispersed in the thermoplastic polymers 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 fibers, kevlar fibers, basalt fibers, boron fibers, PE fibers, natural fibers, or carbon fibers. At least a portion of the composite material layer 120 is embedded in the plurality of holes 112 and the plurality of micro-lateral holes 116 of the aluminum-based metal layer 110 (see fig. 2). In some embodiments, the overlap strength between the aluminum-based metal layer 110 and the composite layer 120 is from about 20MPa to about 27MPa, such as about 21, 22, 23, 24, 25, or 26MPa. When the hole coverage of the surface 110a is less than 70%, the surface 110a cannot provide a sufficient number of hole locations to embed the composite layer 120, thereby reducing the overlap strength of the fiber and metal composite laminate 100.

Referring to fig. 1 and 4, fig. 4 is a flowchart of a method 400 for manufacturing a fiber and metal composite laminate 100 according to an embodiment of the present disclosure. The manufacturing method 400 includes steps 410 through 440. In step 410, an aluminum-based metal layer 110 is provided, wherein a surface 110a of the aluminum-based metal layer 110 has a (200) plane with a 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 on the surface 110 a. After the chemical etching operation, the surface 100a has at least 20 micro-side holes per unit section within a depth range below the surface 110a, and the depth range is 40 μm. In some embodiments, the etching time of the chemical etching operation is about 15 seconds to about 300 seconds, such as about 30, 60, 120, 180, or 240 seconds. In some embodiments, the etching solution of the chemical etching operation comprises sulfuric acid and chloride ions. In some embodiments, the etching solution of the chemical etching operation is composed of a solution containing sulfuric acid, chloride ions, and iron ions. In some embodiments, the etching solution of 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 may increase the etching efficiency of the aluminum-based metal layer 110. In step 430, a composite layer 120 is provided, wherein the composite layer 120 comprises thermoplastic polymer 122 and fibrous material 124. In step 440, a hot press process operation is performed to embed at least a portion of the composite material layer 120 into the plurality of holes 112 and the plurality of micro-side holes 116 of the aluminum-based metal layer 110. If the (200) plane content is less than 40%, the holes 112 can still be formed by the chemical etching operation, but the number of micro-holes 116 is greatly reduced, or the micro-holes 116 are not provided, so that the lap strength and the stability of the fiber and metal composite laminate 100 cannot be effectively improved.

Fig. 5 is an X-ray diffraction analysis chart of the aluminum-based metal layer 110 of the comparative example, experimental example 1, and experimental example 2 according to the present disclosure. As shown in fig. 2, the aluminum-based metal layer 110 mainly has four planes (111), (200), (220), and (311). In the comparative example, the (200) plane was about 10% in terms of the total of four planes. In experimental example 1, the (200) plane was about 55% in terms of the total of four planes. In experimental example 2, the (200) plane was about 64% in terms of the total of four planes.

The inventors have found that the (200) plane may create more micro-side holes than the (111), (220) and (311) planes of the aluminum-based metal layer 110, which is related to the strain energy of each plane. In detail, in the process of etching the aluminum-based metal layer by the etching solution, the aluminum oxide on the metal surface layer is weaker in the direction of larger strain energy, so that the etching solution is easier to enter, and more micro-side holes are generated. In addition, if the (200) plane is not preferable, the etching liquid will corrode in the depth direction (direction Z), and micro-side holes in the left-right direction (direction X and direction Y) will not easily occur.

Referring to fig. 6, a scanning electron microscope image of a surface 110a of an aluminum-based metal layer 110 according to experimental example 1 of the present disclosure is shown. There are about 18 hole areas 114 in fig. 6. Referring to fig. 7, a scanning electron microscope image of a cross section of an aluminum-based metal layer 110 according to experimental example 1 of the present disclosure is shown. The hole in fig. 7 has about 4 micro-side holes 116.

The technical contents and effects of the embodiments of the present invention will be described in more detail below by using the results of comparative examples, experimental examples 1 and 2, but the present invention is not limited thereto.

The properties of the etched aluminum-based metal layer 110 and the bond strength of the fiber to metal composite laminate of the examples are set forth in table 1 below.

TABLE 1

The number of micro-side holes in Table 1 is the average number per 1mm, the average roughness is in μm, the opening pore diameter is in μm, and the lap strength is in MPa. The bond strength between the aluminum-based metal layer 110 and the composite material layer 120 was tested by ASTM D1002, wherein the bond area of the test piece was (25.4 mm.+ -. 0.254 mm) X (12.7 mm.+ -. 0.010 mm).

In each of the examples in Table 1, aluminum-based metal layers were formed using aluminum alloy sheets of size AA5052-H32, 1.5mm thick. The etching solution for chemically etching the aluminum alloy sheet contained 10wt.% sulfuric acid, 15wt.% hydrochloric acid, and 75wt.% deionized water. The etching solution of this embodiment does not contain manganese ions. The etching time was about 60 seconds. The etched aluminum alloy sheet was cleaned with nitric acid, deionized water for about 300 seconds, and dried. The drying temperature was about 80 ℃ and the drying time was about 6 hours. The thermoplastic polymer of the composite layer of each example was Polycarbonate (PC). The composite layers of the examples were hot pressed with aluminum alloy sheets at a temperature of about 230 c, a hot pressing pressure of about 50kfg/cm ³, and a hot pressing time of about 300 seconds.

As is clear from Table 1, the lap strength of Experimental example 1 was 20.7MPa, and the lap strength of Experimental example 2 was 26.1MPa. Therefore, the fiber and metal composite laminates of the experimental examples 1 and 2 can provide better lap strength than the comparative examples.

Referring to fig. 8, a scanning electron microscope image of a surface 110a of an aluminum-based metal layer 110 according to experimental example 2 of the present disclosure is shown. The holes 112 of the surface 110a are polygonal in shape.

Referring to fig. 9, a scanning electron microscope image of a cross section of a fiber and metal composite laminate 100 according to experimental example 2 of the present disclosure is shown. As can be seen from fig. 9, the composite material layer 120 is embedded in the plurality of holes 112 and the plurality of micro-side holes 116 of the aluminum-based metal layer 110.

In summary, since the fiber and metal composite laminate of the present disclosure has a plurality of micro-side holes on the surface of the metal, the composite material can be embedded into the micro-side holes of the metal, thereby forming a composite laminate with high lap joint strength and stable bonding. The fiber and metal composite laminate disclosed by the invention does not need to use adhesive to bond different materials between the aluminum-based metal layer and the composite material layer, so that the condition that the overall property of the composite laminate is influenced by the adhesive is avoided. In addition, the holes and micro-side holes formed by the aluminum-based metal in the preferred (200) direction can enable the composite material to be smoothly embedded, so that the aluminum-based metal layer and the composite material layer can be directly bonded by hot pressing without modifying the properties of the composite material, a firmly-combined composite laminate is formed, and the processing steps can be reduced. The hot pressing process can reduce the cost of the die because no vacuum is required. The composite laminate formed by the aluminum-based metal layer and the composite material layer can be at least lighter than aluminum alloy by more than 15%, so that the added value of the product is improved.

The foregoing outlines features of several embodiments so that those skilled in the art may better understand the aspects of the present disclosure. Those skilled in the art should appreciate that the present disclosure may be readily utilized as a basis for designing or modifying other processes and structures for carrying out the same purposes and/or achieving the same advantages of the embodiments introduced herein. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the disclosure, and that they may make various changes, substitutions and alterations herein without departing from the spirit and scope of the disclosure.

Claims

1. A fiber and metal composite laminate comprising:

an aluminum-based metal layer, wherein a surface of the aluminum-based metal layer comprises a plurality of holes and a plurality of micro-side holes positioned in the holes, and the surface has a (200) plane with a content of not less than 40%;

Wherein a unit section of the surface has at least 20 micro-side holes in a depth range below the surface, and the depth range is 40 μm, and the unit section is 1mm; and

And the composite material layer comprises a thermoplastic polymer and a fiber material, wherein at least one part of the composite material layer is embedded into the holes and the micro-side holes of the aluminum-based metal layer.

2. The fiber and metal composite laminate according to claim 1, wherein a hole coverage of the surface of the aluminum-based metal layer is greater than 70%.

3. The fiber and metal composite laminate according to claim 1, wherein the surface of the aluminum-based metal layer has an average roughness of 15 μm to 35 μm.

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

5. The fiber and metal composite laminate according to claim 1, wherein an open pore size of each of the plurality of holes is 50 μm to 90 μm.

6. A method of manufacturing a fiber and metal composite laminate, comprising:

Providing an aluminum-based metal layer, wherein one surface of the aluminum-based metal layer has a (200) plane with a content of not less than 40%;

Performing a chemical etching operation on the surface of the aluminum-based metal layer to form a plurality of holes and a plurality of micro-side holes in the holes on the surface,

Wherein after the chemical etching operation, a unit section of the surface has at least 20 micro-side holes in a depth range below the surface, and the depth range is 40 μm;

Providing a composite material layer, wherein the composite material layer comprises a thermoplastic polymer and a fiber material; and

And performing a hot pressing process operation to embed at least a part of the composite material layer into the holes and the micro-side holes of the aluminum-based metal layer.

7. The method of claim 6, wherein the chemical etching operation has an etching time of 15 seconds to 300 seconds.

8. The method of claim 6, wherein an etching solution of the chemical etching operation comprises sulfuric acid and chloride ions.

9. The method of claim 6, wherein a hole coverage of the surface of the aluminum-based metal layer after the chemical etching operation is greater than 70%.

10. The method of claim 6, wherein an average roughness of the surface of the aluminum-based metal layer after the chemical etching operation is 15 μm to 35 μm.