Patent Publication Number: US-2019193370-A1

Title: Metal-and-resin composite and method for making the same

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a Division Application of the U.S. patent application Ser. No. 14/610,154 filed on Jan. 30, 2015, the contents of which are incorporated by reference herein. 
    
    
     FIELD 
     The present disclosure generally relates to a metal-and-resin composite and a method for making the metal-and-resin composite. 
     BACKGROUND 
     Metal-and-resin composites are used in a wide range of industrial fields including the production of parts for automobiles, domestic appliances, industrial machinery, and the like. Generally, metal and resin are joined together by an adhesive. However, this method cannot supply a high strength composite of metal and resin. There is a need to combine metal and resin together. 
    
    
     
       BRIEF DESCRIPTION OF THE FIGURES 
       Implementations of the present technology will now be described, by way of example only, with reference to the attached figures. 
         FIG. 1  is a cross-sectional view of an exemplary embodiment of a metal-and-resin composite. 
         FIG. 2  is a scanning electron microscope (SEM) image of a metal substrate having an intermediate layer. 
         FIG. 3  is a flow chart of a method for making a metal-and-resin composite in accordance with an exemplary embodiment. 
     
    
    
     DETAILED DESCRIPTION 
     It will be appreciated that for simplicity and clarity of illustration, where appropriate, reference numerals have been repeated among the different figures to indicate corresponding or analogous elements. In addition, numerous specific details are set forth in order to provide a thorough understanding of the embodiments described herein. However, it will be understood by those of ordinary skill in the art that the embodiments described herein can be practiced without these specific details. In other instances, methods, procedures and components have not been described in detail so as not to obscure the related relevant feature being described. Also, the description is not to be considered as limiting the scope of the embodiments described herein. The drawings are not necessarily to scale and the proportions of certain parts may be exaggerated to better illustrate details and features of the present disclosure. 
     The term “comprising” when utilized, means “including, but not necessarily limited to”; it specifically indicates open-ended inclusion or membership in the so-described combination, group, series and the like. 
       FIG. 1  illustrates a metal-and-resin composite  100  according to an exemplary embodiment. The composite  100  includes a metal substrate  10 , an intermediate layer  30  formed on the metal substrate  10 , and a resin member  50  covering the intermediate layer  30 , to bond with the metal substrate  10 . 
     The metal substrate  10  can be made of stainless steel, aluminum alloy, titanium alloy, aluminum-magnesium alloy, or zinc alloy. The metal substrate  10  has a plurality of nano pores  11  through a chemical etching process. The nano pores  11  have a diameter of about 10 nm to about 1000 nm, and a depth of about 0.1 μm to about 20 μm. 
     The intermediate layer  30  comprises coupling agent. The coupling agent can be a titanate coupling agent, a zirconate coupling agent, a silane coupling agent, a boric acid ester coupling agent, or a sulfonic acid coupling agent. The intermediate layer  30  fills at least a portion of each nano pore  11  and covers the metal substrate  10 . The intermediate layer  30  has a thickness of about 0.5 nm to about 10 nm. In at least one exemplary embodiment, a portion of each nano pore  11  is unfilled with the intermediate layer  30 . 
     An energy dispersive spectroscopy (EDS) test indicates that surfaces of the intermediate layer  30  includes carbon having a mass percentage of about 2.58-2.87%, oxygen having a mass percentage of about 1.29-2.08%, silicon having a mass percentage of about 0.59-0.72%, chromium having a mass percentage of about 17.78-18.08%, manganese having a mass percentage of about 0.66-0.75%, iron having a mass percentage of about 67.73-69.23%, and nickel having a mass of about 7.79-7.88%. 
     A scanning electron microscope (SEM) test indicates that the intermediate layer  30  covers the metal substrate  10 , and fills at least portion of each nano pore  11 , a portion of each nano pore  11  is unfilled with the intermediate layer  30 . The portion of each nano pore  11  unfilled with the intermediate layer  30  has a diameter of about 10 nm to about 990 nm. 
     The resin member  50  can cover and bond with the intermediate layer  30 , and fill the portion of each nano pore  11  unfilled with the intermediate layer  30 , such to bond with the metal substrate  10 . 
     The resin member  50  can be made of polybutylene terephthalate (PBT), polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polyetheretherketone (PEEK), polycarbonate (PC), or polyvinyl chloride (PVC). The bond between the resin member  50  and the intermediate layer  30  includes chemical bonds, such that the resin member  50  can bond with the metal substrate  10  through the chemical bonds. The tensile strength of the composite  100  is about 10 KgF/cm 2  to about 100 KgF/cm 2 , and the shear strength of the composite  100  is about 10 KgF/cm 2  to about 260 KgF/cm 2 . 
     Referring to  FIG. 3 , a flowchart is presented in accordance with an example embodiment. The method  300  is provided by way of example, as there are a variety of ways to carry out the method. The method  300  described below can be carried out using the configurations illustrated in  FIGS. 1-2 , for example, and various elements of these figures are referenced in explaining method  300 . Each block shown in  FIG. 3  represents one or more processes, methods or subroutines, carried out in the example method  300 . Furthermore, the order of blocks is illustrative only and the order of the blocks can change according to the present disclosure. Additional blocks can be added or fewer blocks can be utilized, without departing from this disclosure. The example method  300  can begin at block  301 . 
     At block  301 , a metal substrate  10  is provided. The metal substrate  10  can be made of stainless steel, aluminum alloy, titanium alloy, aluminum-magnesium alloy, or zinc alloy. 
     At block  302 , the metal substrate  10  is degreased by dipping the metal substrate  10  into a metal degreaser solution having a concentration of about 5-20 g/L. The dipping process can last for about 3 minutes to about 10 minutes. The temperature of the degreaser solution can be about 40° C. to about 75° C. In at least one exemplary embodiment, the degreaser solution can be a conventional degreaser solution. 
     At block  303 , the degreased metal substrate  10  is then etched through an acid treatment to remove a metal oxide film which may naturally form on the metal substrate  10  when the metal substrate  10  is exposed to air. This acid treatment can be carried out by dipping the metal substrate  10  in an acid solution for about 0.5 minutes to about 5 minutes. The acid solution can have a temperature of about 50° C. to about 60° C., and a concentration of about 5-20 g/L. The acid solution can be selected from at least one of a group consisting of hydrochloric acid, phosphoric acid, sulphuric acid, nitric acid and hydrofluoric acid. It is to be understood that the metal substrate  10  has not been etched during the acid treatment. The metal substrate  10  is then cleaned to remove etch-resulting impurities. 
     At block  304 , the metal substrate  10  is chemical etched to form a plurality of nano pores  11  on a surface of the metal substrate  10 . The chemical etching can be carried out by dipping the metal substrate  10  into a chemical etching solution at a temperature of about 10° C. to about 120° C. The chemical etching process can last for about 1 minute to about 120 minutes. The chemical etching solution can be a sulphuric acid solution having a concentration of about 100-980 ml/L. The nano pores  11  have a diameter of about 10 nm to about 1000 nm, and a depth of about 0.1 μm to about 20 μm. 
     At block  305 , an intermediate layer  30  is formed on the metal substrate  10  and filled at least portion of each nano pore  11  through a surface coupling treatment. The intermediate layer  30  has a thickness of about 0.5 nm to about 10 nm. The surface coupling treatment can be carried out by dipping the metal substrate  10  into a coupling solution at a temperature of about 25° C. to about 100° C. The surface coupling treatment can last for 1 second to about 5 minutes. The coupling solution can include solvent and coupling agent having a concentration of about 10 ml/L to about 100 ml/L. The coupling agent can be a titanate coupling agent, a zirconate coupling agent, a silane compound coupling agent, a boric acid ester coupling agent, or a sulfonic acid coupling agent. The solvent can be water or methanol. The intermediate layer  30  has a thickness of about 0.5 nm to about 10 nm. In at least one exemplary embodiment, a portion of each nano pore  11  is unfilled with the intermediate layer  30 . 
     At block  306 , the metal substrate  10  is dried at a temperature of about 25° C. to about 140° C. The metal substrate  10  can be dried naturally, or dried in an oven. 
     An energy dispersive spectroscopy (EDS) test indicates that a surface of the intermediate layer  30  formed in EXAMPLE 3 includes carbon having a mass percentage of about 2.58-2.87%, oxygen having a mass percentage of about 1.29-2.08%, silicon having a mass percentage of about 0.59-0.72%, chromium having a mass percentage of about 17.78-18.08%, manganese having a mass percentage of about 0.66-0.75%, iron having a mass percentage of about 67.73-69.23%, and nickel having a mass of about 7.79-7.88%. 
     A scanning electron microscope (SEM) test indicates that the intermediate layer  30  covers the metal substrate  10 , and fills at least portion of each nano pore  11 , a portion of each nano pore  11  is unfilled with the intermediate layer  30 . The portion of each nano pore  11  unfilled with the intermediate layer  30  has a diameter of about 10 nm to about 990 nm. 
     At block  307 , a resin member  50  is formed on the intermediate layer  30  to bond with the metal substrate  10  through an injection process. The injection process can be carried out by placing the metal substrate  10  into an injection mold (not shown), and molten resin is injected into the mold, and covers and bonds a surface of the intermediate layer  30  and fills the portion of each nano pore  11  unfilled with the intermediate layer  30 , forming the resin member  50 . The composite  100  is thus formed. During the injection process, the molten resin is kept at a temperature of about 220° C. to about 320° C. The resin member  40  can be made of polybutylene terephthalate (PBT), polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polyetheretherketone (PEEK), polycarbonate (PC), or polyvinyl chloride (PVC). The bond between the resin member  50  and the intermediate layer  30  includes chemical bondings, such the resin member  50  can bond with the metal substrate  10  through the chemical bondings. The tensile strength of the composite  100  is about 10 KgF/cm 2  to about 100 KgF/cm 2 , and the shear strength of the composite  100  is about 10 KgF/cm 2  to about 260 KgF/cm 2 . 
     EXAMPLE 1 
     In this example, the metal substrate  10  was made of stainless steel SUS304, and the resin member  50  was made of PBT. 
     The metal substrate  10  was degreased by dipping in a degreaser solution having a concentration of 20 g/L and a temperature of 75° C., allowing the metal substrate  10  to be ultrasonically cleaned, for 5 min. 
     The degreased metal substrate  10  was etched by dipping in a hydrochloric acid solution having a concentration of 200 g/L and a temperature of 50° C., allowing the metal substrate  10  to be etched for 0.5 min. 
     The etched metal substrate  10  was chemical etched by dipping in a sulphuric acid solution having a concentration of 300 ml/L and a temperature of 70° C., allowing the metal substrate  10  to be chemical etched for 10 min. 
     The chemical etched metal substrate  10  was surface coupling treated by dipping in a coupling solution having a temperature of 25° C., allowing the metal substrate  10  to be surface coupling treated for 10 seconds to form an intermediate layer  30  on the metal substrate  10 . The coupling solution includes methanol and zirconate coupling agent having a concentration of 30 ml/L. 
     The metal substrate  10  was dried in an oven having an interior temperature of 60° C. for 15 min. 
     Molten PBT resin having a temperature of 285° C. was injected to a surface of intermediate layer  30 , and finally formed the resin member  50 . 
     EXAMPLE 2 
     In this example, the metal substrate  10  was made of stainless steel SUS306, and the resin member  50  was made of PPS. 
     The metal substrate  10  was degreased by dipping in a degreaser solution having a concentration of 5 g/L and a temperature of 75° C., allowing the metal substrate  10  to be ultrasonically cleaned, for 10 min. 
     The degreased metal substrate  10  was etched by dipping in a hydrochloric acid solution having a concentration of 200 g/L and a room temperature, allowing the metal substrate  10  to be etched for 5 min. 
     The etched metal substrate  10  was chemical etched by dipping in a hydrochloric acid solution having a concentration of 980 ml/L and a temperature of 120° C., allowing the metal substrate  10  to be chemical etched for 10 min. 
     The chemical etched metal substrate  10  was surface coupling treated by dipping in a coupling solution having a temperature of 40° C., allowing the metal substrate  10  to be surface coupling treated for 60 seconds to form an intermediate layer  30  on the metal substrate  10 . The coupling solution includes water and zirconate coupling agent having a concentration of 20 ml/L. 
     The metal substrate  10  was dried in an oven having an interior temperature of 60° C. for 15 min. 
     Molten PPS resin having a temperature of 320° C. was injected to a surface of intermediate layer  30 , and finally formed the resin member  50 . 
     EXAMPLE 3 
     In this example, the metal substrate  10  was made of stainless steel SUS316, and the resin member  50  was made of PA. 
     The metal substrate  10  was degreased by dipping in a degreaser solution having a concentration of 15 g/L and a temperature of 60° C., allowing the metal substrate  10  to be ultrasonically cleaned, for 3 min. 
     The degreased metal substrate  10  was etched by dipping in a hydrochloric acid solution having a concentration of 150 g/L and a room temperature, allowing the metal substrate  10  to be etched for 3 min. 
     The etched metal substrate  10  was chemical etched by dipping in a sulphuric acid solution having a concentration of 900 ml/L and a temperature of 10° C., allowing the metal substrate  10  to be chemical etched for 120 min. 
     The chemical etched metal substrate  10  was surface coupling treated by dipping in a coupling solution having a temperature of 25° C., allowing the metal substrate  10  to be surface coupling treated for 15 seconds to form an intermediate layer  30  on the metal substrate  10 . The coupling solution includes water and silane coupling agent having a concentration of 30 ml/L. 
     The metal substrate  10  was dried in an oven having an interior temperature of 120° C. for 5 min. 
     Molten PA resin having a temperature of 220° C. was injected to a surface of intermediate layer  30 , and finally formed the resin member  50 . 
     It is to be understood, however, that even through numerous characteristics and advantages of the present disclosure have been set forth in the foregoing description, together with details of assembly and function, the disclosure is illustrative only, and changes may be made in detail, especially in the matters of shape, size, and arrangement of parts within the principles of the disclosure to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.