CN107471533B - Metal substrate and metal-plastic bonding member - Google Patents

Metal substrate and metal-plastic bonding member Download PDF

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CN107471533B
CN107471533B CN201710812215.7A CN201710812215A CN107471533B CN 107471533 B CN107471533 B CN 107471533B CN 201710812215 A CN201710812215 A CN 201710812215A CN 107471533 B CN107471533 B CN 107471533B
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metal
plastic
micron
honeycomb
convex surface
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CN107471533A (en
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张孟军
张法亮
刘利强
王成
董晓佳
李文涛
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Goertek Techology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C2045/1486—Details, accessories and auxiliary operations
    • B29C2045/14868—Pretreatment of the insert, e.g. etching, cleaning

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

The invention discloses a metal substrate and a combination piece of metal and plastic. The surface of the metal base material is provided with a micron-sized concave-convex surface and honeycomb-shaped pores, the average width RSm of the contour of the micron-sized concave-convex surface is 1-400 mu m, the average peak-valley depth Rz is 1-15 mu m, the honeycomb-shaped pores are formed on the micron-sized concave-convex surface, the average aperture range of the honeycomb-shaped pores is 10-500nm, and the micron-sized concave-convex surface is configured to bear an injection molding plastic material. The invention has the technical effect that the bonding acting force of the plastic material connected to the metal base material and the metal base material can be improved.

Description

Metal substrate and metal-plastic bonding member
Technical Field
The invention belongs to the technical field of material processing, and particularly relates to a metal base material and a metal and plastic combined piece.
Background
In the electronic communication industry, more and more electronic products adopt a metal and plastic composite form to form a product structure, and the structural design can realize rich functional effects. For example, a composite metal and plastic design may be used where the appearance of the product is desired to exhibit metallic features and the internal structure is desired to reduce weight and save material costs.
The traditional composite method of metal and plastic comprises the methods of adhesive bonding, snap-fit or rivet connection and the like. However, the traditional composite mode has the defects of low composite reliability, need of adding a fixed connection mechanism and the like. With the development of the technology, a composite mode of injection molding plastic on a metal surface also appears in the prior art. When plastic is injection molded, plastic is directly injection molded on a metal material using the metal material as a base material. However, the bonding force between metal and plastic is limited, and there is a risk of separation between the two, and it is difficult to improve the composite reliability.
Therefore, there is a need for an improved process for compounding metal and plastic materials, which can improve the structural reliability of the material composition, or simplify the structure of the product to be manufactured, and reduce the number of additional components added to the product.
Disclosure of Invention
It is an object of the present invention to provide an improved metal substrate.
According to a first aspect of the present invention, there is provided a metal substrate, the surface of which has a micro-scale concave-convex surface and honeycomb pores, the micro-scale concave-convex surface has an average contour width RSm of 1 to 400 μm and an average peak-to-valley depth Rz of 5 to 10 μm, the honeycomb pores are formed on the micro-scale concave-convex surface, the honeycomb pores have an average pore size ranging from 10 to 500nm, the honeycomb pores extend from the surface of the stainless steel substrate to an average depth ranging from 10 to 200nm, and the micro-scale concave-convex surface is configured to bear an injection molded plastic material.
Optionally, the honeycomb pores extend from the surface of the stainless steel substrate to an average depth ranging from 10 to 200 nm.
Optionally, the material of the metal substrate is stainless steel.
Optionally, the metal base material is subjected to a first etching treatment to form the micron-sized concave-convex surface on the surface, and then subjected to a second etching treatment to form honeycomb-shaped pores on the micron-sized concave-convex surface.
The invention also provides a combination piece of metal and plastic, which comprises the metal base material and the plastic material, wherein the plastic material is formed on the micron-sized concave-convex surface in an injection molding mode.
Optionally, the plastic material comprises a thermoplastic resin and a filler material, the mass percentage of the filler material in the plastic material is 5-40%, and the filler material comprises at least one of nylon fiber, carbon fiber, glass fiber, aramid fiber, calcium carbonate, magnesium carbonate, silica and clay.
Optionally, the plastic material comprises at least one of polyphenylene sulfide resin (PPS), polybutylene terephthalate resin (PBT), Polyamide (PA), Polycarbonate (PC) and polyolefin.
The inventor of the present invention finds that, in the prior art, although some technical solutions of injection molding and compounding of metal materials and plastic materials appear, for the compounding manner of metal and plastic materials, no improved technical solution with high compounding reliability appears in the prior art. Therefore, the technical task to be achieved or the technical problems to be solved by the present invention are never thought or anticipated by those skilled in the art, and therefore the present invention is a new technical solution.
Other features of the present invention and advantages thereof will become apparent from the following detailed description of exemplary embodiments thereof, which proceeds with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
FIG. 1 is a schematic structural view of a metal and plastic bonding member provided by the present invention;
FIG. 2 is a cross-sectional scanning electron microscope of the metal and plastic bonding member provided by the present invention;
fig. 3 is a scanning electron microscope image of the honeycomb-shaped fine pores provided by the present invention.
Detailed Description
Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that: the relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise.
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses.
Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate.
In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
The invention provides a metal substrate 1, wherein the metal substrate 1 is used for bearing a plastic material 22, and the plastic material 22 can be directly fixed on the metal substrate 1 by injection molding. Fig. 1 shows the structural configuration of the metal substrate 1 in combination with the plastic material 22. The metal base material 1 is subjected to first etching treatment to form a micron-sized concave-convex surface 11, the contour average width RSm of the concave-convex surface is 1-400 mu m, and the average peak-valley depth Rz is 1-15 mu m. And then, forming the nanometer honeycomb-shaped pores 12 on the micron-scale concave-convex surface 11 through second etching treatment. The nanometer honeycomb pores are distributed on the micron-sized concave-convex surface 11. The average pore diameter of the honeycomb-shaped fine pores 12 is in the range of 10 to 500 nm.
Further preferably, the average depth of the honeycomb-shaped fine pores 12 extending from the surface to the inside of the stainless steel substrate is in the range of 10 to 200 nm. In fig. 3, the morphology of the nano-scale honeycomb pores 12 formed on the micro-scale concavo-convex surface 11 is shown, and the nano-scale honeycomb pores 12 can be embedded with the plastic material lodged thereon, thereby improving the bonding force.
The micron-sized concave-convex surface 11 can be observed through a scanning electron microscope, the surface is in a concave-convex alternative shape, and the characteristic of a periodically distributed structure is obvious. The roughness value of the micron-sized concave-convex surface 11 can be tested by adopting a Sanfeng Mitutoyo SURFTEST SJ-310 instrument, and the surface information of the product can be effectively and comprehensively represented. The contour average width RSm of the micron-sized concave-convex surface 11 is 1-400 mu m, and the average peak-valley depth Rz is 1-15 mu m. Preferably, the average width RSm of the contour of the micro-scale convexo-concave surface 11 is 100-200 μm, and the average peak-to-valley depth Rz is 5-10 μm. Fig. 2 shows the topographical features of the micro-scale asperities 11 of the surface of the metal substrate 1 and shows the features of the injection molding of the plastic material 22 embedded in the micro-scale asperities 11. The micron-sized concave-convex surface 11 with the morphological characteristics within the range is more favorable for injection molding combination with the plastic material 22, and has reasonable structure distribution and moderate depth. The corrosion effect can be better obtained on the premise of ensuring the structural reliability of the final combination product. According to theoretical analysis and calculation, the smaller the RSm value of the profile plane width is, the more densely and uniformly distributed the concave structures on the metal surface. If the mean width RSm of the profile is too large, the concave spacing will be too large, resulting in unstable bonding between the metal substrate and the plastic.
Further, the average peak-valley depth Rz can represent the undulation degree condition of the micron-sized concave-convex surface, and the larger the value is, the larger the undulation degree is, and the larger the difference value between the peak and the valley is. In the prior art, the Rz value of the surface of the metal base material is often less than 5 μm, and the drawing force of the plastic material formed on the metal base material is weak and is often 30MPa or less. In the invention, the adopted corrosion process is that the average peak-valley depth Rz value of the micron-sized concave-convex surface reaches more than 5 mu m. Larger waviness enables more plastic material to be embedded, resulting in greater pullout force. The plastic material is injected on the metal base material provided by the invention, and the plastic material can be pulled out of the metal base material only when the pulling acting force of more than 30MPa is exerted.
Alternatively, the material of the metal substrate is preferably stainless steel, which can be widely used in electronic products. Of course, other metal materials such as aluminum alloy and the like may be used as the material of the metal base material.
The metal substrate of the present invention is preferably subjected to two etching processes to form a predetermined surface topography. Firstly, the micron-sized concave-convex surface is formed on the surface of the metal base material through the first etching treatment. And then, forming honeycomb-shaped pores on the micron-sized concave-convex surface of the metal base material through second etching treatment.
The metal substrate provided by the invention has the following technical effects that firstly, the technical scheme etches and etches a micron-scale concave-convex structure with a larger outline on the metal substrate. The large average peak-valley depth Rz enables the micron-sized concave-convex surface to have a remarkable undulating surface, the area of combination of plastic and a metal base material is increased, and more plastic materials can be contained in the concave-convex surface.
Secondly, the surface roughness of the micron-sized concave-convex surface is increased by the honeycomb-shaped pores, and the bonding effect of the plastic and the metal base material is improved. After one or more times of corrosion by the corrosive liquid, the surface of the metal base material is seriously pitting and is respectively corroded in the longitudinal direction and the transverse direction, finally, honeycomb-shaped pores are formed on the micron-sized concave-convex surface, and the pore walls and the metal base material are integrated. This enables a stronger connection to be made with the plastics material than with a metal substrate surface covered with an oxide film or particulate build-up. Therefore, the plastic material is combined with the metal base material in an injection molding mode to form the combined piece, and the metal base material and the plastic material are not easy to separate and damage in the drawing or shearing process. The reliability of the plastic material injected on the metal base material is ensured, and the conditions of corrosion cracking, mechanical fracture and the like are prevented.
Further, the present invention also provides a combination of metal and plastic, as shown in fig. 1, comprising the above metal substrate 1 and plastic material 22. The plastic material 22 is injection molded on the micron-sized concave-convex surface 11 of the metal base material 1.
Preferably, the plastic material comprises a thermoplastic resin and a filler material. The filler material is doped in the thermoplastic resin. The filling material is at least one of nylon fiber, carbon fiber, glass fiber, aramid fiber, calcium carbonate, magnesium carbonate, silica and clay, and accounts for 5-40 wt% of the plastic material. The filler material may be intermingled and filled in the thermoplastic resin before the injection molding process is performed.
The linear expansion coefficient of stainless steel as the metal substrate was 1.5 × 10-5/° C, and the linear expansion coefficient of the plastic material is 6-8 × 10-5The linear expansion coefficient of stainless steel and plastic materials with a large difference per DEG C is not favorable for the curing process of the plastic materials. Other metallic materials also have this problem as a metal substrate. Therefore, it is necessary to dope the thermoplastic resin with a filler for modificationMaterials to reduce the linear expansion coefficient of plastic materials, for example, fiberglass materials have a linear expansion coefficient of only 3.8 × 10-5Glass fiber, etc., can be incorporated into the thermoplastic resin to bring the linear expansion coefficient of the plastic material composition as close as possible to that of stainless steel and other metal materials.
Optionally, the thermoplastic material comprises at least one of polyphenylene sulfide resin (PPS), polybutylene terephthalate resin (PBT), Polyamide (PA), Polycarbonate (PC) and polyolefin.
In one embodiment of the present invention, a conventional 304 stainless steel plate with a thickness of 1.5mm is used as a metal substrate, and the metal substrate is punched into a rectangular shape of 18mm by 44mm, polished, and then degreased and cleaned. Then soaking the fabric in alkalescent cleaning solution for 300s, and then putting the fabric into deionized water for cleaning and drying. By regulating and controlling parameters such as temperature, concentration, time and the like of the corrosive liquid for the first corrosion and combining a roughness tester, the average width RSm of the micron-sized concave-convex surface profile of the product is 200 mu m, and the average peak-valley depth Rz of the product is 10 mu m. Therefore, the surface of the metal base material can have larger undulation degree through the adjustment of the process parameters. And then, etching by secondary corrosive liquid to form holes, drying and injection molding. The 304 stainless steel sheet test piece after the etching treatment was placed in an injection molding mold, and a polybutylene terephthalate (PBT) resin composition containing 20% of glass fiber was injection-molded. Then fixing the combination piece made of 304 stainless steel and plastic on a universal material testing machine for product tensile test, and respectively testing 6 groups of test pieces, wherein the average drawing force value of the test pieces is 1767N and is about 35 MPa. The test results are shown in table 1 below. The force required to pull the plastic material off the stainless steel substrate is significantly increased compared to the prior art.
Figure GDA0002379371600000061
Figure GDA0002379371600000071
TABLE 1
The combined piece provided by the invention has the technical effects, and the drawing force of the combined piece is obviously improved. Wherein, the honeycomb-shaped fine pores have obvious effect on improving the drawing force. In particular, through, vertically distributed pores can be more conducive to the filling of molten plastic material.
Another important technical effect of the present invention is that the product combining member has more excellent air tightness. The air tightness and the water resistance are used as the purposes of the technical application and are mainly applied to the electronic information industry. The honeycomb pores prepared by the technical scheme are an important condition for obtaining air tightness, and the plastic and the metal matrix are tightly combined together. In the prior art, the surface state of the product is mostly micron-sized holes, but the diameter of the holes is larger. After the plastic material is injected, the plastic material is cooled and shrunk, and a slight peeling phenomenon is generated between the plastic material and the metal base material, so that the air tightness is reduced.
In one embodiment of the present invention, a conventional 1.5mm thick 304 stainless steel plate is used as a metal substrate, and is polished and then degreased and cleaned. Then soaking the fabric in alkalescent cleaning solution for 300s, and then putting the fabric into deionized water for cleaning and drying. By regulating and controlling parameters such as temperature, concentration, time and the like of the primary corrosion liquid and combining a roughness tester, the average width RSm of the micron-sized concave-convex surface profile of the product is 180 mu m, and the average peak-valley depth Rz of the product is 8 mu m. Therefore, the surface of the metal base material can have larger undulation degree through the adjustment of the process parameters. And then, etching by secondary corrosive liquid to form holes, drying and injection molding. The 304 stainless steel sheet test piece after the etching treatment was placed in an injection molding mold, and a polybutylene terephthalate (PBT) resin composition containing 20% of glass fiber was injection-molded. In order to further represent the combination effect of the plastic and the stainless steel, the pressure-placing type detection is adopted, after the combination piece is filled with gas, the gas leakage amount of the combination piece is directly measured by a pressure gauge, and the combination effect of the plastic material and the stainless steel substrate is truly reflected. The results are shown in Table 2.
Sample (I) Number of samples Fraction defective Yield of
Air tightness test article 100 0％ 100％
TABLE 2
As can be seen from table 2, the airtightness of the 100 batches of the bonded parts was all acceptable, which is directly related to the hole-forming structure of the present solution.
Although some specific embodiments of the present invention have been described in detail by way of examples, it should be understood by those skilled in the art that the above examples are for illustrative purposes only and are not intended to limit the scope of the present invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.

Claims (6)

1. The metal base material is characterized in that the surface of the metal base material is provided with a micron-sized concave-convex surface and honeycomb-shaped pores, the average width RSm of the micron-sized concave-convex surface is 1-400 mu m, the average peak-valley depth Rz is 5-10 mu m, the honeycomb-shaped pores are formed on the micron-sized concave-convex surface, the average pore size range of the honeycomb-shaped pores is 10-500nm, the average depth range of the honeycomb-shaped pores extending from the surface of the stainless steel base material to the inside is 10-200nm, and the micron-sized concave-convex surface is configured for bearing an injection molding plastic material.
2. The metal substrate according to claim 1, wherein the material of the metal substrate is stainless steel.
3. The metal substrate according to claim 1, wherein the metal substrate is subjected to a first etching process to form the micro-scale convexo-concave surface on the surface, and then subjected to a second etching process to form the honeycomb pores on the micro-scale convexo-concave surface.
4. A combination of metal and plastic, comprising a metal substrate according to any one of claims 1-3 and a plastic material injection molded onto said micro-scale relief.
5. The metal and plastic combination of claim 4, wherein the plastic material comprises a thermoplastic resin and a filler material, the filler material is present in the plastic material in an amount of 5-40% by weight, and the filler material comprises at least one of nylon fibers, carbon fibers, glass fibers, aramid fibers, calcium carbonate, magnesium carbonate, silica, and clay.
6. A metal and plastic combination according to claim 4, wherein the thermoplastic material comprises at least one of polyphenylene sulfide resin (PPS), polybutylene terephthalate resin (PBT), Polyamide (PA), Polycarbonate (PC) and polyolefin.
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CN109280920B (en) * 2018-10-31 2021-07-02 南京中和至诚信息技术有限公司 Aluminum alloy with micro-nano structure on surface and preparation method and application thereof
CN114474793A (en) * 2021-12-31 2022-05-13 歌尔股份有限公司 Carbon fiber metal composite material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103582329A (en) * 2012-07-24 2014-02-12 富泰华工业（深圳）有限公司 Shell and manufacturing method thereof
CN207465724U (en) * 2017-09-11 2018-06-08 歌尔股份有限公司 The engaging member of metal base and metal and plastics

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103582329A (en) * 2012-07-24 2014-02-12 富泰华工业（深圳）有限公司 Shell and manufacturing method thereof
CN207465724U (en) * 2017-09-11 2018-06-08 歌尔股份有限公司 The engaging member of metal base and metal and plastics

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