CN117774218A - Injection molded ultra-high strength metal-polymer joint and preparation method thereof - Google Patents
Injection molded ultra-high strength metal-polymer joint and preparation method thereof Download PDFInfo
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- CN117774218A CN117774218A CN202311820320.7A CN202311820320A CN117774218A CN 117774218 A CN117774218 A CN 117774218A CN 202311820320 A CN202311820320 A CN 202311820320A CN 117774218 A CN117774218 A CN 117774218A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 92
- 238000002347 injection Methods 0.000 title claims abstract description 20
- 239000007924 injection Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 45
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 44
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 238000011282 treatment Methods 0.000 claims abstract description 32
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 19
- 238000005260 corrosion Methods 0.000 claims abstract description 18
- 230000007797 corrosion Effects 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 238000003486 chemical etching Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
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- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 abstract description 10
- 238000011160 research Methods 0.000 abstract description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 96
- 230000000052 comparative effect Effects 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
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- 238000012986 modification Methods 0.000 description 4
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- 238000004090 dissolution Methods 0.000 description 2
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 1
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Landscapes
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The invention relates to the technical field of dissimilar metal/polymer interface combination, in particular to an injection molding metal-polymer joint and a preparation method thereof, comprising the following steps: placing the metal insert to be treated in strong-oxidability metal ion saline solution, performing ultrasonic vibration treatment, and performing chemical corrosion on the metal surface; placing the metal insert subjected to chemical corrosion in a mixed solution of aminosilane and polyvinyl alcohol, and performing secondary treatment on the metal surface; placing the metal insert subjected to secondary treatment in a mold cavity, and closing a mold to mold a polymer, thereby obtaining a metal-polymer joint; wherein the aqueous solution of the strong oxidizing metal ion salt comprises FeCl 3 、CuCl 2 、NaMnO 4 And Na (Na) 2 CrO 4 Any one or more of the following. The research shows that the tensile shear strength of the metal-polymer joint prepared by the method can reach 50-54MPa, which is far higher than that of the existing metal-polymer injection joint.
Description
Technical Field
The invention relates to the technical field of dissimilar metal-polymer interface bonding, in particular to an injection molding ultrahigh-strength metal-polymer joint and a preparation method thereof.
Background
Based on environmental protection and sustainable development requirements, metal-polymer composites are receiving increasing attention in the aerospace and rail traffic fields due to their excellent specific strength, specific stiffness and recyclability characteristics. The metal-polymer composite material is usually formed by compounding a light alloy and a polymer, the polarity difference between the two materials is extremely large, and the interface bonding strength of the metal-polymer is low.
In order to improve the interface bonding strength of the metal-polymer, researchers have developed a series of researches on interface bonding by adopting processes such as mechanical connection, adhesive bonding, hot-press connection, friction stir welding, laser welding and the like. And the bonding strength of the metal/polymer is improved by the methods of metal surface pretreatment, polymer modification, interlayer insertion and the like.
However, in the metal-polymer bonding process, the mechanical connection joint is prone to stress concentration and has a low service life; the adhesive joint has poor water absorption performance and is easy to produce environmental pollution; the hot-press connection process has the problems of overlong combination time, serious energy waste and the like; the dimensional stability of various welded joints is poor, and the polymer is easy to burn. The injection molding has the advantages of high molding efficiency, diversified product shapes, extremely high energy utilization rate and the like, but the bonding strength of a metal-polymer interface in the actual production process is far lower than that of the process introduced above. Therefore, how to enhance the bonding strength of injection molded metal-polymer joints is a technical challenge for researchers in this field.
In order to improve the strength of the injection molded metal-polymer joint, researchers have developed a series of research methods, which can be summarized as two methods of metal surface topography treatment and metal-polymer interface modification. The metal surface morphology treatment can improve the roughness of the metal surface and realize the mechanical interlocking of metal and polymer, and mainly comprises the steps of metal surface sand blasting, micro-nanosecond laser etching, chemical corrosion, anodic oxidation, micro-arc oxidation and the like. The metal-polymer interface modification realizes the synthesis bond of the metal-polymer by inserting an intermediate active body, and mainly comprises the steps of active chemical reagent coating, chemical vapor deposition, plasma treatment, hot water bath and the like. The combination pretreatment in the above manner can realize remarkable improvement of the bonding strength of the metal-polymer joint, but the combination pretreatment fails to break through 40MPa.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of an injection molding metal-polymer joint, and the tensile shear strength of the metal-polymer joint prepared by the method can reach 50-54MPa, which is far higher than that of the existing metal-polymer injection joint.
In a first aspect, the present invention provides a method of making an injection molded metal-polymer joint comprising the steps of:
s1, placing an aluminum alloy insert to be treated in strong-oxidability metal ion saline solution, performing ultrasonic vibration treatment, and performing chemical corrosion on the surface of the aluminum alloy;
s2, placing the aluminum alloy insert subjected to chemical corrosion in a mixed solution of aminosilane and polyvinyl alcohol, and performing secondary treatment on the surface of the aluminum alloy;
s3, placing the aluminum alloy insert subjected to secondary treatment in a mold cavity, and closing a mold to mold a polymer, so as to obtain a metal-polymer joint;
wherein the aqueous solution of the strong oxidizing metal ion salt comprises FeCl 3 、CuCl 2 、NaMnO 4 And Na (Na) 2 CrO 4 Any one or more of the following.
The invention is to promote the joint strength of injection molding metal-polymer, firstly, the metal insert to be treated is placed in the strong oxidizing metal ion salt water solution, and simultaneously ultrasonic vibration treatment is assisted to generate micro-nano structure on the metal surface, so as to enhance the mechanical interlocking effect of metal-polymer; then, the metal insert subjected to chemical corrosion is placed in a mixed solution of aminosilane and polyvinyl alcohol, the surface is subjected to secondary treatment, under the action of the aminosilane and the polyvinyl alcohol, the chemical combination of metal and polymer can be realized, the wettability of the metal surface can be improved, the injection molding time is shortened, the injection molding efficiency is improved, and the super-strong connection of the injection molding joint is realized.
The preparation method of the invention is suitable for metal-polymer joints bonded in injection-molded form, where the metal is preferably an aluminum alloy. Researches show that the tensile shear strength of the aluminum alloy-polymer joint prepared by the method can reach 50-54MPa, which is far higher than that of the existing metal-polymer injection joint.
Based on the above technical solution, it is further preferred that in step S1, the concentration of the strong oxidizing metal ion salt aqueous solution is 10-20wt.%, and the concentration thereof is selected according to the oxidizing property of the metal ion salt aqueous solution, and for the metal ion salt with low oxidizing property, a solution with slightly higher concentration is selected, and for the metal ion salt with high oxidizing property, a solution with lower concentration is selected; and the final use concentration needs to be determined according to the metal surface area to ensure that the metal corrosion surface morphology is not affected by the reduced concentration of metal ions.
Specifically, in the step S1, the temperature is controlled to be 40-80 ℃ and the time is controlled to be 10-20min during the chemical corrosion.
At the temperature, ultrasonic vibration treatment is assisted on the surface of the aluminum alloy, so that the generation rate of the micro-nano structure on the surface of the aluminum alloy can be increased, the uniformity of the micro-nano structure on the surface of the aluminum alloy is ensured, the mechanical interlocking effect of metal-polymer can be enhanced, and a treatment foundation is provided for secondary treatment of the surface of the aluminum alloy.
The chemical reaction principle involved in the step S1 of the invention is as follows:
based on the above technical scheme, more preferably, in step S1, after the surface of the aluminum alloy is chemically corroded, the aluminum alloy is sequentially placed in deionized water and absolute ethyl alcohol to be ultrasonically cleaned, so as to remove the strong oxidizing metal ion salt solution remained on the surface of the aluminum alloy, and the aluminum alloy is taken out and dried by using a nitrogen gun;
preferably, the ultrasonic cleaning time is 10-20min;
preferably, during ultrasonic cleaning, the working power of the ultrasonic cleaner is 80-100W, and the frequency is 30-50KHz.
In the step S2, preferably, the concentration of the aminosilane is 1-5wt.% and the concentration of the polyvinyl alcohol is 0.1-0.5wt.% in the mixed solution of the aminosilane and the polyvinyl alcohol;
preferably, the aminosilane comprises any one or more of KH-550, KH-792 and KH-892;
preferably, the polyvinyl alcohol has a polymerization degree of 1000 to 2000 to ensure the viscosity of the aqueous solution.
Specifically, the preparation method of the mixed solution of the aminosilane and the polyvinyl alcohol comprises the following steps:
dissolving polyvinyl alcohol in deionized water, heating to 80-100 ℃ under magnetic stirring to fully swell for 1-3 hours, and preparing a polyvinyl alcohol solution with the concentration of 1-5wt.%, wherein the rotating speed of the magnetic stirring is 30-50rpm/min so as to maximally improve the dissolution rate of the polyvinyl alcohol;
then, dropwise adding aminosilane into a premixed solution of absolute ethyl alcohol and deionized water, adding a polyvinyl alcohol solution under magnetic stirring, and continuously stirring for 30-40min to reduce precipitation of a polyvinyl alcohol polymer, so as to obtain a mixed solution of aminosilane and polyvinyl alcohol, wherein the volume ratio of absolute ethyl alcohol to deionized water is 5: (1-2), the rotation speed of the magnetic stirring is 10-15rpm/min.
Preferably, in the technical scheme, during the dissolution process of the polyvinyl alcohol, the polyvinyl alcohol is placed in deionized water, the temperature is slowly increased at a speed lower than 10 ℃/min, when the temperature reaches 80-100 ℃, the temperature is kept for 1-3h, and then the temperature is slowly reduced at a speed lower than 5 ℃/min.
As the technical scheme, in the step S2, the dried aluminum alloy insert is preferably placed in a mixed solution of aminosilane and polyvinyl alcohol for 10-20min, and the aluminum alloy is usually placed for no more than 12H after the soaking, so that the aluminum alloy insert is placed in an oven as soon as possible after the soaking is finished, and baked for 10-20min at 80-110 ℃ to enable Si-OH in aminosilane (such as KH-892) and AlOOH on the surface of the aluminum alloy to generate Si-O-Al and H by chemical bonding 2 O, KH-892 nmThe network is combined to the surface of the aluminum alloy to finish the secondary treatment of the surface of the aluminum alloy.
In the step S1, the working power and frequency of the ultrasonic vibrator during the ultrasonic vibration are not strictly limited, wherein the working power is preferably 110-130W, and the frequency is preferably 30-50KHz.
In the second aspect, the invention also discloses a metal-polymer joint in injection molding prepared by the method, which also belongs to the protection scope of the invention, and specifically, the tensile shear strength of the metal-polymer joint is 50-54MPa.
The preparation method of the injection molded metal-polymer joint has at least the following technical effects:
in the preparation method of the injection molding metal-polymer joint, firstly, an aluminum alloy insert to be treated is placed in strong-oxidability metal ion saline solution, and simultaneously ultrasonic vibration treatment is assisted to generate a micro-nano structure on the surface of the aluminum alloy, so that the mechanical interlocking effect of metal-polymer is enhanced; then, placing the aluminum alloy insert subjected to chemical corrosion in a mixed solution of aminosilane and polyvinyl alcohol, carrying out secondary treatment on the surface, and under the action of the aminosilane and the polyvinyl alcohol, on one hand, realizing the transition of the wettability of the aluminum alloy surface, improving the flow rate of the polymer on the aluminum alloy surface, and realizing the full combination of the polymer and a metal interface in an extremely short time; on the other hand, the aminosilane and the aluminum alloy surface can generate Si-O-Al bond, and the-NH in the aminosilane 2 and-OH in the polyvinyl alcohol can generate strong hydrogen bond with-O-in the polymer, so that the aluminum alloy and the polymer are chemically combined, and the ultra-strong connection of the injection joint is realized. The research shows that the tensile shear strength of the metal-polymer joint prepared by the method can reach 50-54MPa, which is far higher than that of the existing metal-polymer injection joint.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an electron microscope image of aluminum alloy surface corrosion and ultrasonic vibration corrosion according to the invention;
FIG. 2 is a graph showing the interfacial bond strength comparison of examples 1-3 and comparative examples 1-10 of the present invention;
FIG. 3 shows XPS spectra of chemical bonds generated under different processing conditions according to the present invention;
FIG. 4 is a FTIR spectrum showing chemical bond formation under different processing conditions according to the present invention;
FIG. 5 is a graph showing the roughness of the surface of an aluminum alloy under various processing conditions in accordance with the present invention;
FIG. 6 shows the wettability of aluminum alloy surfaces under various treatment conditions according to the present invention.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular forms also include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
S11, placing the aluminum alloy insert to be treated in FeCl with concentration of 15 wt% 3 In the aqueous solution, under the vibration of an ultrasonic vibrator with the working power of 120W and the frequency of 4KHz, treating for 15min at 45 ℃ to chemically corrode the surface of the aluminum alloy;
after chemical corrosion is carried out on the surface of the aluminum alloy, immersing the aluminum alloy into a container containing deionized water, carrying out ultrasonic cleaning for 15min, then immersing the aluminum alloy into absolute ethyl alcohol, carrying out ultrasonic cleaning for 15min, taking out the aluminum alloy, and drying the aluminum alloy by using a nitrogen gun, wherein during ultrasonic cleaning, the working power of an ultrasonic cleaner is 90W, and the frequency is 40KHz.
S12, placing the dried aluminum alloy insert in a mixed solution with the concentration of aminosilane (KH-892) of 3wt.% and the concentration of polyvinyl alcohol (the polymerization degree of 2000) of 0.3wt.%, fully soaking for 15min, and then placing the aluminum alloy in an oven, and baking at 90 ℃ for 15min to finish secondary treatment of the surface of the aluminum alloy;
s13, placing the aluminum alloy insert subjected to secondary treatment in a mold cavity, and closing a mold to mold a polymer, so as to obtain a metal-polymer joint, wherein the injection parameters are shown in Table 1.
Table 1 injection parameters
Example 2
S21, placing the aluminum alloy insert to be treated in FeCl with concentration of 20 wt% 3 In the aqueous solution, under the vibration of an ultrasonic vibrator with the working power of 120W and the frequency of 40KHz, treating for 10min at 50 ℃ to chemically corrode the surface of the aluminum alloy;
after chemical corrosion is carried out on the surface of the aluminum alloy, immersing the aluminum alloy into a container containing deionized water, carrying out ultrasonic cleaning for 20min, then immersing the aluminum alloy into absolute ethyl alcohol, carrying out ultrasonic cleaning for 20min, taking out the aluminum alloy, and drying the aluminum alloy by using a nitrogen gun, wherein during ultrasonic cleaning, the working power of an ultrasonic cleaner is 100W, and the frequency is 30KHz.
S22, placing the dried aluminum alloy insert in a mixed solution with the concentration of aminosilane (KH-892) of 5wt.% and the concentration of polyvinyl alcohol (the polymerization degree of 2000) of 0.5wt.%, fully soaking for 20min, and then placing the aluminum alloy in an oven, and baking at 80 ℃ for 20min to finish secondary treatment of the surface of the aluminum alloy;
s23, placing the aluminum alloy insert subjected to the secondary treatment in a die cavity, and closing the die to mold the polymer, so as to obtain the metal-polymer joint.
Example 3
S31, placing the aluminum alloy insert to be treated in FeCl with concentration of 10 wt% 3 In the aqueous solution, under the vibration of an ultrasonic vibrator with the working power of 120W and the frequency of 40KHz, treating for 10min at 50 ℃ to chemically corrode the surface of the aluminum alloy;
after chemical corrosion is carried out on the surface of the aluminum alloy, immersing the aluminum alloy into a container containing deionized water, carrying out ultrasonic cleaning for 10min, then immersing the aluminum alloy into absolute ethyl alcohol, carrying out ultrasonic cleaning for 10min, taking out the aluminum alloy, and drying the aluminum alloy by using a nitrogen gun, wherein during ultrasonic cleaning, the working power of an ultrasonic cleaner is 90W, and the frequency is 40KHz.
S32, placing the dried aluminum alloy insert in a mixed solution with the concentration of aminosilane (KH-892) of 5wt.% and the concentration of polyvinyl alcohol (the polymerization degree of 2000) of 0.5wt.%, fully soaking for 15min, and then placing the aluminum alloy in an oven, and baking at 100 ℃ for 15min to finish secondary treatment of the surface of the aluminum alloy;
s33, placing the aluminum alloy insert subjected to the secondary treatment in a die cavity, and closing the die to mold the polymer, so as to obtain the metal-polymer joint.
Comparative example 1
And (3) grinding the metal insert by sand paper and cleaning by alcohol, then placing the aluminum alloy insert into a die cavity, and closing the die to mold the polymer, thereby obtaining the metal-polymer joint.
Comparative example 2
Grinding the aluminum alloy insert by sand paper, then immersing the aluminum alloy insert in an aminosilane solution with the concentration of 3wt.% and finally placing the aluminum alloy insert in a die cavity, and closing the die to mold the polymer, thereby obtaining the metal-polymer joint.
Comparative example 3
Grinding the aluminum alloy insert by sand paper, then immersing the aluminum alloy insert in a mixed solution with the aminosilane concentration of 3wt.% and the polyvinyl alcohol concentration of 0.3wt.%, and finally placing the aluminum alloy insert in a die cavity, and closing the die to mold the polymer, thereby obtaining the metal-polymer joint.
Comparative example 4
Chemical etching of the aluminum alloy insert using a strong oxidizing metal ion aqueous salt solution (the difference is that ultrasonic vibration is not performed as in step S11 in example 1);
and (3) after alcohol cleaning and drying, placing the aluminum alloy insert in a die cavity, and closing the die to inject the polymer to obtain the metal-polymer joint.
Comparative example 5
Chemical etching of the aluminum alloy insert using a strong oxidizing metal ion aqueous salt solution (the difference is that ultrasonic vibration is not performed as in step S11 in example 1);
then soaking in an aminosilane solution with the concentration of 3wt.% and finally placing the aluminum alloy insert in a die cavity, and closing the die to mold the polymer, thereby obtaining the metal-polymer joint.
Comparative example 6
Chemical etching of the aluminum alloy insert using a strong oxidizing metal ion aqueous salt solution (the difference is that ultrasonic vibration is not performed as in step S11 in example 1);
then immersing in a mixed solution with the concentration of aminosilane of 3wt.% and the concentration of polyvinyl alcohol of 0.3wt.%, and finally placing the aluminum alloy insert in a die cavity, and closing the die to mold the polymer, thus obtaining the metal-polymer joint.
Comparative example 7
Chemically etching the aluminum alloy insert using a strong oxidizing metal ion aqueous salt solution (same as step S11 in example 1);
and (3) after alcohol cleaning and drying, placing the aluminum alloy insert in a die cavity, and closing the die to inject the polymer to obtain the metal-polymer joint.
Comparative example 8
Chemically etching the aluminum alloy insert using a strong oxidizing metal ion aqueous salt solution (same as step S11 in example 1);
then soaking in an aminosilane solution with the concentration of 3wt.% and finally placing the aluminum alloy insert in a die cavity, and closing the die to mold the polymer, thereby obtaining the metal-polymer joint.
Comparative example 9
NaOH was used instead of the strongly oxidizing metal ion aqueous salt solution in example 1,
other steps and parameters were substantially the same as in example 1.
Comparative example 10
The mixed solution of aminosilane and polyvinyl alcohol in example 1 was replaced with gamma-glycidoxypropyl trimethoxysilane KH-560;
other steps and parameters were substantially the same as in example 1.
FIG. 1 shows the effect of chemical etching on the microstructure of an aluminum alloy surface by chemical etching alone and ultrasonic vibration in accordance with the present invention.
As can be seen from FIG. 1, the surface of the aluminum alloy can only generate a micro-structure after being treated by the strong oxidizing metal ion brine solution, and the surface of the aluminum alloy can generate an obvious micro-nano-structure after being treated by the strong oxidizing metal ion brine solution and assisted by ultrasonic vibration.
To further investigate the effect of different treatments on the tensile shear strength of metal-polymer joints, the tensile shear strength of the metal-polymer joints obtained in examples 1-3 and comparative examples 1-10 was measured according to the present invention, and the test results are shown in Table 1 and FIG. 2.
TABLE 1 tensile shear Strength test results
| Sequence number | Tensile shear Strength (MPa) |
| Example 1 | 53.9 |
| Example 2 | 51.2 |
| Example 3 | 50.6 |
| Comparative example 1 | 2.96 |
| Comparative example 2 | 4.39 |
| Comparative example 3 | 9.74 |
| Comparative example 4 | 20.6 |
| Comparative example 5 | 26.9 |
| Comparative example 6 | 36.7 |
| Comparative example 7 | 31.8 |
| Comparative example 8 | 35.5 |
| Comparative example 9 | 22.5 |
| Comparative example 10 | 28.4 |
As can be seen from the combination of the table 1 and the figure 2, the method for corroding the surface of the aluminum alloy by sequentially using the mixed solution of the strong-oxidability metal ion salt water solution, the aminosilane and the polyvinyl alcohol can obviously improve the bonding strength of a metal-polymer interface, and the tensile shear strength of the aluminum alloy can reach 50-54MPa, which is far higher than the strength of the existing metal-polymer injection joint.
Comparative example 8 use of an ethanol solution of aminosilane instead of the mixed solution of aminosilane and polyvinyl alcohol of example 1, the strength of the resulting metal-polymer injection molded joint may be relatively poor compared to example 1 because of the absence of PVA effect, KH-892 nanonetwork and polymer-generated O … H 2 N hydrogen bond strength ratio KH-892 and OH … O … produced by PVA combined nanonetworks and polymers
NH 2 The strength of the composite hydrogen bond is lower.
Comparative example 9 using NaOH instead of the strongly oxidizing aqueous metal ion salt solution of example 1, the strength of the resulting metal-polymer injection molded joint was somewhat improved, but the tensile shear strength was still to be improved as compared to example 1, probably because NaOH corrosion resulted in a surface roughness that was too low and did not produce a cross-scale network surface structure, the mechanical interlocking was less, and the metal-polymer interfacial bonding strength was lower than that of ultrasonic FeCl 3 A treated joint.
Comparative example 10 using gamma-glycidoxypropyl trimethoxysilane KH-560 instead of the mixed solution of aminosilane and polyvinyl alcohol of example 1, the strength of the resulting metal-polymer injection molded joint may be relatively poor compared to example 1 because KH-560 forms Si-O-Al bonds with Al surface, fixing KH-560 nanonetwork on aluminum alloy surface, but epoxy groups inside KH-560 cannot chemically bond with C-O-C and c=o in polymer, and the strength is low.
Meanwhile, the design principle of the treatment method is analyzed, wherein FIG. 3 is an XPS spectrum of the aluminum alloy surface under different treatment conditions of the invention, and FIG. 4 is a FTIR spectrum of the aluminum alloy surface under different treatment conditions of the invention.
As can be seen in conjunction with FIGS. 3-6, the present invention uses a strongly oxidizing metal ion salt FeCl 3 After the ultrasonic chemical corrosion of the aluminum alloy surface by the aqueous solution, compared with the surface before the treatment, the surface roughness is obviously improved, and AlOOH is generated on the surface, and compared with the prior art, the method for treating the aluminum alloy surface by using the mixed solution of the aminosilane and the polyvinyl alcohol for the second time, the method for treating the aluminum alloy surface by using the aqueous solution not only can promote the chemical combination of the aluminum alloy and the polymer (for example, si-O-Al bonds can be generated on the surface of the aminosilane and the aluminum alloy), but also can promote the-NH of the aminosilane 2 and-OH of the polyvinyl alcohol may create complex hydrogen bonds with-O-and c=o in the polymer. In addition, under the combined action of the aminosilane and the polyvinyl alcohol, the wettability of the surface of the aluminum alloy is changed, the flow rate of the polymer on the surface of the aluminum alloy is improved, the full combination of the polymer and the aluminum alloy interface can be realized in a very short time, the metal and the polymer are chemically combined, and the super-strong connection of the injection joint is realized.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A method of making an injection molded metal-polymer joint comprising the steps of:
s1, placing a metal insert to be treated in strong-oxidability metal ion saline solution, performing ultrasonic vibration treatment, and performing chemical corrosion on the metal surface;
s2, placing the metal insert subjected to chemical corrosion in a mixed solution of aminosilane and polyvinyl alcohol, and performing secondary treatment on the metal surface;
s3, placing the metal insert subjected to the secondary treatment in a mold cavity, and closing a mold to mold a polymer, so as to obtain a metal-polymer joint;
wherein the aqueous solution of the strong oxidizing metal ion salt comprises FeCl 3 、CuCl 2 、NaMnO 4 And Na (Na) 2 CrO 4 Any one or more of the following.
2. The method according to claim 1, wherein in step S1, the concentration of the strong oxidizing metal ion aqueous salt solution is 10 to 20wt.%.
3. The method according to claim 1, wherein in step S1, the chemical etching is performed at a temperature of 40 to 80 ℃ for 10 to 20 minutes.
4. The preparation method according to claim 1, wherein in step S1, after the metal surface is chemically corroded, the metal surface is sequentially placed in deionized water and absolute ethyl alcohol to be ultrasonically cleaned, and the metal surface is taken out and dried by using a nitrogen gun;
preferably, the ultrasonic cleaning time is 10-20min;
preferably, during ultrasonic cleaning, the working power of the ultrasonic cleaner is 80-100W, and the frequency is 30-50KHz.
5. The preparation method according to claim 1, wherein in step S2, the concentration of aminosilane is 1-5wt.% and the concentration of polyvinyl alcohol is 0.1-0.5wt.% in the mixed solution of aminosilane and polyvinyl alcohol;
preferably, the aminosilane comprises any one or more of KH-550, KH-792 and KH-892;
preferably, the polyvinyl alcohol has a degree of polymerization of 1000 to 2000.
6. The preparation method according to claim 1, wherein the preparation method of the mixed solution of aminosilane and polyvinyl alcohol comprises the following steps:
dissolving polyvinyl alcohol in deionized water, heating to 80-100 ℃ under magnetic stirring to fully swell for 1-3h, and preparing a polyvinyl alcohol solution with the concentration of 1-5wt.%, wherein the rotating speed of the magnetic stirring is 30-50rpm/min;
dropwise adding aminosilane into a premixed solution of absolute ethyl alcohol and deionized water, adding a polyvinyl alcohol solution under magnetic stirring, and continuously stirring for 30-40min to obtain a mixed solution of aminosilane and polyvinyl alcohol, wherein the volume ratio of absolute ethyl alcohol to deionized water is 5: (1-2), the rotation speed of the magnetic stirring is 10-15rpm/min.
7. The method according to claim 6, wherein the polyvinyl alcohol is placed in deionized water, slowly heated at a rate of less than 10 ℃/min, maintained at a temperature of 80-100 ℃ for 1-3 hours, and then slowly cooled at a rate of less than 5 ℃/min.
8. The method according to claim 4, wherein in step S2, the dried metal insert is immersed in a mixed solution of aminosilane and polyvinyl alcohol for 10 to 20 minutes, and then the metal insert is baked in an oven at 80 to 110 ℃ for 10 to 20 minutes, thereby completing the secondary treatment of the metal surface.
9. The method according to claim 1, wherein in step S1, the working power of the ultrasonic vibrator is 110-130W and the frequency is 30-50KHz during the ultrasonic vibration.
10. Injection molded metal-polymer joint, characterized in that it is produced according to the production method according to any one of claims 1 to 9, the tensile shear strength of which is 50 to 54MPa.
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