CN105500601B - A kind of metallic matrix and its surface treatment method and metal-resin composite and its manufacture method - Google Patents
A kind of metallic matrix and its surface treatment method and metal-resin composite and its manufacture method Download PDFInfo
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Abstract
The invention discloses a kind of metallic matrix and its surface treatment method, and metal-resin composite and its manufacture method, wherein, the method for the surface treatment of the metallic matrix comprises the following steps：(1) metallic matrix is pre-processed using sulfuric acid solution, forming surface has the metallic matrix of irregular corrosion hole；(2) metallic matrix after pretreatment is put into alkaline solution and carries out electrochemical corrosion or be put into acid solution to carry out chemical immersion.The metallic matrix of surface treatment through the present invention is put into mould, is molded with thermoplastic resin composition, the metal-resin composite of integration is formed.Realize the manufacture method for the metal-resin composite that adhesion is excellent and manufacture method is simple and easy to apply, cost is low.
Description
Technical field
The present invention relates to a kind of metallic matrix and its surface treatment method, and a kind of metal-resin composite and its manufacture
Method.
Background technology
At present, method metal (stainless steel) and resin being combined mainly has two kinds：One kind is to utilize adhesive, is passed through
Chemical adhesive is acted on stainless steel and resin respectively, so that both be combined；Another is by chemistry or electrification
Mode, corrodes in stainless steel surfaces and hole, then combined resin with stainless steel by being molded.
However, using the method for adhesive, adhesion is poor, not acid and alkali-resistance, and adhesive has certain thickness, for multiple
Miscellaneous shape area is not applied to, and can not realize the seamless combination of stainless steel and resin；By the way of chemistry or electrochemical corrosion,
Some meetings cause the heavy corrosion of stainless steel surfaces, and subsequent treatment is difficult to remove, and is unfavorable for the incrustation of appearance；And have
Extent of corrosion is light, causes it can only be to specific resin effectively, so that limiting it uses scope.
Therefore, how to prepare metallic matrix, how metal base surface handled, and to how by metal (no
Rust steel) matrix is combined with resin and manufactures metal (stainless steel) and the research of the complex of resin is increasingly taken seriously.
The content of the invention
The invention aims to provide a kind of metallic matrix and its surface treatment method, and there is provided one kind combination
The manufacture method for the metal-resin composite that power is excellent and manufacture method is simple and easy to apply, cost is low.
To achieve these goals, the invention provides a kind of metallic matrix, wherein, the metallic matrix is stainless base steel
Oxygen element is contained on body, the stainless steel base surface, and the weight/mass percentage composition of the top layer oxygen element of the stainless steel base is 1-
10 weight %.
The invention provides a kind of surface treatment method of metallic matrix, this method comprises the following steps：
(1) metallic matrix is pre-processed using sulfuric acid solution, forming surface has the metal of irregular corrosion hole
Matrix；
(2) metallic matrix after pretreatment is put into alkaline solution and carries out electrochemical corrosion or be put into acid solution
Middle carry out chemical immersion；
Wherein, the mix acid liquor that the acid solution constitutes for two or more acid.
Present invention also offers a kind of metallic matrix prepared by the above method.
Present invention also offers a kind of metal-resin composite, the metal-resin composite include metallic matrix and with the gold
Belong to the resin bed that matrix surface is combined, wherein, the metallic matrix is metallic matrix of the present invention.
Present invention also offers a kind of manufacture method of metal-resin composite, wherein, this method is included metallic matrix
It is put into mould, is molded with thermoplastic resin composition, forms the metal-resin composite of integration.
The surface treatment method of the metallic matrix provided according to the present invention, by using sulfuric acid solution to metallic matrix
Pre-processed, irregular corrosion hole can be formed in metal base surface, hole depth is shallower, beaten easily by machinery
The method of grinding and polishing light is removed, and is conducive to the decoration of appearance, metallic matrix after pretreatment then is put into alkaline solution again
It is middle to carry out electrochemical corrosion or be put into acid solution to carry out chemical immersion, can be in metal base surface after pretreatment
Upper formation oxy radical, so as to improve both adhesions, therefore, metallic matrix prepared by the above method is put into mould,
It is molded with thermoplastic resin composition, the excellent metal-resin composite of adhesion can be obtained.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the metallic matrix handled according to the present invention, and forming surface has the irregular metallic matrix for corroding hole
The photo of metallographic microscope；
Fig. 2 is the photo of the metallographic microscope in the section of integrated metal-resin composite made according to the present invention.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of metallic matrix, wherein, the metallic matrix is stainless steel base, the stainless steel base
Oxygen element is contained on surface, according to the present invention, is swept using the Flied emission of the model JSM-7600F purchased from Jeol Ltd.
Retouch Electronic Speculum and annex energy disperse spectroscopy and energy spectrum analysis is carried out to the surface of stainless steel produced by the present invention and the complex of resin, test is each
Main composition such as Fe, Si, Ni, O content, wherein, measure the weight/mass percentage composition of the top layer oxygen element of the metallic matrix
Substantially increase, can be 1-10 weight %.
According to the present invention, containing corrosion hole on the surface of the stainless steel base, the width of the corrosion hole can be with
For 100-50000nm, depth can be 100-50000nm；In the present invention, the corrosion hole is not of uniform size, and shape is multiple
Miscellaneous, size distribution ranges are wide；In the present invention, the width of the hole on metallic matrix (stainless steel base) refers in Metal Substrate
The width of the groove formed on body surface face, similarly, the depth of the hole on metallic matrix refer to be formed on metal base surface
Groove depth；And in the present invention, the width and depth of the corrosion hole on metallic matrix are referred respectively in gold
Belong to the width for corroding hole on matrix and the scope of depth, i.e. so-called width refers to the width and maximum width of minimum
Scope between degree, so-called depth refers to the depth and the maximum scope obtained between depth of minimum.
The invention provides a kind of surface treatment method of metallic matrix, this method comprises the following steps：
(1) metallic matrix is pre-processed using sulfuric acid solution, forming surface has the metal of irregular corrosion hole
Matrix；
(2) metallic matrix after pretreatment is put into alkaline solution and carries out electrochemical corrosion or be put into acid solution
Middle carry out chemical immersion；
Wherein, the mix acid liquor that the acid solution constitutes for two or more acid.
According to the present invention, the metallic matrix can be stainless steel base.
According to the present invention, in step (1), the condition pre-processed to metallic matrix includes：Temperature can be 20-90
DEG C, the time can be 20-180min；Preferably, in step (1), the condition of the pretreatment includes：Temperature is 30-80 DEG C,
Time is 30-120min.
According to the present invention, in step (1), the concentration of the sulfuric acid can be 5-50 weight %；Preferably, the sulfuric acid
Concentration be 10-45 weight %.
According to the present invention, in step (2), the concentration of the alkaline solution can be 1-40 weight %, it is preferable that described
The concentration of alkaline solution is 5-30 weight %.
According to the present invention, in step (2), the alkaline solution can be sodium hydroxide, potassium hydroxide, sodium phosphate and lemon
One or more solution in lemon acid sodium；In the present invention, the sodium hydroxide, the potassium hydroxide, the sodium phosphate and
The specific concentration of the sodium citrate is not limited, as long as meeting by the sodium hydroxide, the potassium hydroxide, the sodium phosphate
Concentration with the alkaline solution of one or more compositions in the sodium citrate is 1-40 weight %, preferably 5-30 weight %
.
According to the present invention, in step (2), electrification is carried out to the metallic matrix obtained after pretreatment with the alkaline solution
Learn corrosion process in, negative electrode is not particularly limited, can be this area in conventional use of material as negative electrode, in the present invention
In, negative electrode can be preferably carbon plate, and the metallic matrix obtained using after pretreatment is used as anode.With the alkaline solution to pretreatment
The condition that the metallic matrix obtained afterwards carries out electrochemical corrosion includes：The voltage of application can be 1-10V, and processing time can be
0.5-30min。
According to the present invention, in step (2), the concentration of the acid solution can be 1-40 weight %, it is preferable that described
The concentration of acid solution is 5-30 weight %.
According to the present invention, in step (2), the acid solution can be two in phosphoric acid, sulfuric acid, nitric acid and citric acid
Plant or two or more solution；In the present invention, the phosphoric acid, the sulfuric acid, the nitric acid and the respective tool of the citric acid
Bulk concentration is not limited, as long as meeting by two kinds in the phosphoric acid, the sulfuric acid, the nitric acid and the citric acid or two kinds
The concentration of the acid solution of composition described above is 1-40 weight %, preferably 5-30 weight %.
According to the present invention, in step (2), chemistry is carried out to the metallic matrix obtained after pretreatment with the acid solution
The condition of immersion can include：Temperature is 20-90 DEG C, and soak time is 3-180min.
Present invention also offers a kind of metallic matrix prepared by the above method.
Present invention also offers a kind of metal matrix composite, the metal-resin composite include metallic matrix and with the gold
Belong to the resin bed that matrix surface is combined, wherein, the metallic matrix is metallic matrix of the present invention.
According to the present invention, wherein, containing corrosion hole on the surface of the metallic matrix, form the resin of the resin bed
Composition is filled in the corrosion hole.
According to the present invention, the resin combination for forming the resin bed is thermoplastic resin composition, the thermoplastic resin
Oil/fat composition can the thermoplastic resin containing 50-95 weight % and 5-50 weight % fibrous material；
According to the present invention, the thermoplastic resin can be polyphenylene sulfide (PPS), polybutylene terephthalate (PBT)
One or more in resin, polyamide and makrolon；The fibrous material is ceramic fibre, glass fibre, aluminium silicate fiber
One or more in peacekeeping polyester fiber.
Present invention also offers a kind of manufacture method of metal-resin composite, this method includes prepare the above method
Metallic matrix is put into mould, is molded with thermoplastic resin composition, forms the metal-resin composite of integration.
According to the present invention, the injection molding is not particularly limited, and can use skill known in those skilled in the art
Art is molded；Under preferable case, injection parameterses are：Injection temperature is 300-320 DEG C, and injection pressure is 2000-
2200bar, dwell pressure is 1600-1800bar, and the dwell time is 1.5-2s.
According to the present invention, the consumption of the thermoplastic resin composition is not particularly limited, can be according to the size of mould
And the size of metallic matrix, it is combined as long as metallic matrix can be formed into integrated metal-resin with thermoplastic resin composition
Body.Under preferable case, the volume ratio of the consumption of the consumption of the thermoplastic resin composition and the metallic matrix can be with
For 1：1.
According to the present invention, before being pre-processed to metallic matrix, pre-treatment can also be carried out to metallic matrix；Before this
Processing procedure includes being cut into metallic matrix into 15mm × 80mm rectangle sheet, then the metallic matrix is put into polishing machine respectively
Interior sanding and polishing, then, then carries out the processes such as oil removing, washing, sandblasting, washing and drying successively.In the present invention, it is described to throw
Ray machine is not particularly limited, the polishing machine that can often know for those skilled in the art, and the manufacture method of the present invention is manufactured
Metal-resin composite be polished, oil removing, washing, sandblasting and drying be all not particularly limited, can be this area skill
Technology known to art personnel.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, according to field emission scanning electron microscope and annex energy disperse spectroscopy (purchased from JEOL's strain
Formula commercial firm, model JSM-7600F) energy spectrum analysis is carried out to the surface of stainless steel produced by the present invention and the complex of resin,
Test each main component content；Present invention manufacture is characterized according to universal testing machine (being purchased from Ying Site, model 3369)
Stainless steel and resin complex shearing force；The polyphenylene sulfide is purchased from Qi get engineering plastics Co., Ltd；It is described
Polybutylene terephthalate (PBT) resin is purchased from Qi get engineering plastics Co., Ltd；The glass fibre is purchased from Orco glass fibre
Factory；The ceramic fibre is purchased from Orco glass fibre factory；The trade mark used in the present invention is purchased from Shenzhen for SUS304 stainless steel plates
Japan-US high industrial Science and Technology Ltd., the polishing machine is purchased from the polishing machine of the model 883 of permanent safe production.
Preparation example 1
The SUS304 stainless steel plates for taking thickness to be 1mm, are cut into 15mm × 80mm rectangular pieces, put it into polishing machine
Sanding and polishing, then, then carries out oil removing, washing, sandblasting, washing, dries at 80 DEG C, manufacture obtains stainless steel base successively.
Embodiment 1
The present embodiment is used for illustrating the surface treatment method of the metallic matrix of the present invention, the Metal Substrate prepared by this method
Body, and metal-resin composite and its manufacture method.
Stainless steel base prepared by preparation example 1 is put into the sulfuric acid solution that percentage by weight is 20 weight %, at 40 DEG C
Lower immersion 120min is pre-processed, and irregular corrosion hole is formed on stainless steel base；Then, by the stainless steel base
Take out, washing, in the sodium hydroxide solution for placing into 30 weight %, using carbon plate as negative electrode, the stainless steel base is anode, in 3V
Lower energization 3min carries out electrochemical corrosion, to remove the layer of the grey black on metal base surface after pretreatment, takes out through electrification
Learn after corrosion obtained stainless steel base and clean drying, obtain surface have irregular corrosion hole (after surface treated
The scope of the width of the corrosion hole formed on metallic matrix is 100-50000nm, and the scope of depth is 100-50000nm) and
It is attached with metal (stainless steel) the matrix A1 of oxy radical；
Energy spectrum analysis is carried out to stainless steel base A1 surfaces using ESEM, each Contents of Main Components, test is tested
It the results are shown in Table 1.
Finally, above-mentioned gained stainless steel base A1 is put into mould, with containing 20 weight % glass fibres and 80 weights
The thermoplastic resin composition for measuring % polyphenylene sulfide (PPS) is molded, wherein, the thermoplastic resin composition's
The volume ratio of consumption and the consumption of the stainless steel base is 1：1, injection temperature is 310 DEG C, and injection pressure is 2100bar, is protected
Pressure pressure is 1700bar, and the dwell time is 2s, obtains the stainless steel of integration and the complex S1 of resin；
After the complex S1 of the stainless steel and resin is stood into 24 hours, it is fixed on universal testing machine and carries out
Average shear force can regard the size of the adhesion between the stainless steel base and resin as in extension test, test result,
Test result is as shown in table 2.
Embodiment 2
The present embodiment is used for illustrating the surface treatment method of the metallic matrix of the present invention, the Metal Substrate prepared by this method
Body, and metal-resin composite and its manufacture method.
Stainless steel base prepared by preparation example 1 is put into the sulfuric acid solution that percentage by weight is 20%, is soaked at 40 DEG C
Bubble 120min is pre-processed, and irregular corrosion hole is formed on stainless steel base；Then, the stainless steel base is taken
Go out, wash, place into and 60min is soaked in mix acid liquor, wherein, the mix acid liquor is the mix acid liquor of phosphoric acid and nitric acid, and institute
The concentration for stating mix acid liquor is 25 weight %, to remove the layer of the grey black on metal base surface after pretreatment, is taken out through changing
Learn after immersion obtained stainless steel base and clean drying, obtain surface have irregular corrosion hole (after surface treated
The scope of the width of the corrosion hole formed on metallic matrix is 100-50000nm, and the scope of depth is 100-50000nm) and
It is attached with metal (stainless steel) the matrix A2 of oxy radical；
Finally, above-mentioned gained stainless steel base A2 is put into mould, with containing 20 weight % glass fibres and 80 weights
The thermoplastic resin composition for measuring % polyphenylene sulfide (PPS) is molded, wherein, the thermoplastic resin composition's
The volume ratio of consumption and the consumption of the stainless steel base is 1：1, injection temperature is 310 DEG C, and injection pressure is 2100bar, is protected
Pressure pressure is 1700bar, and the dwell time is 2s, obtains the stainless steel of integration and the complex S2 of resin；
After the complex S2 of the stainless steel and resin is stood into 24 hours, it is fixed on universal testing machine and carries out
Average shear force can regard the size of the adhesion between the stainless steel base and resin as in extension test, test result,
Test result is as shown in table 2.
Embodiment 3
The present embodiment is used for illustrating the surface treatment method of the metallic matrix of the present invention, the Metal Substrate prepared by this method
Body, and metal-resin composite and its manufacture method.
According to the complex S3 of manufacture method manufacture stainless steel and resin same as Example 1, difference is：Will
Stainless steel base prepared by preparation example 1 is put into the sulfuric acid solution that percentage by weight is 50%, and 20min is soaked at 60 DEG C and is carried out
Pretreatment；Obtaining surface has the irregular corrosion hole (width of the corrosion hole formed after surface treated on metallic matrix
The scope of degree is 100-50000nm, and the scope of depth is 100-50000nm) and it is attached with the metal (stainless steel) of oxy radical
Matrix A3；
Injection, obtains the stainless steel of integration and the complex S3 of resin；
It is fixed on universal testing machine and carries out extension test, average shear force can be regarded as in test result
The size of adhesion between the stainless steel base and resin, test result is as shown in table 2.
Embodiment 4
The present embodiment is used for illustrating the surface treatment method of the metallic matrix of the present invention, the Metal Substrate prepared by this method
Body, and metal-resin composite and its manufacture method.
According to the complex S4 of manufacture method manufacture stainless steel and resin same as Example 1, difference is：Will
Stainless steel base prepared by preparation example 1 is put into the sulfuric acid solution that percentage by weight is 5%, and 180min is soaked at 80 DEG C and is carried out
Pretreatment；Obtaining surface has the irregular corrosion hole (width of the corrosion hole formed after surface treated on metallic matrix
The scope of degree is 100-50000nm, and the scope of depth is 100-50000nm) and it is attached with the metal (stainless steel) of oxy radical
Matrix A4；
Injection, obtains the stainless steel of integration and the complex S4 of resin；
It is fixed on universal testing machine and carries out extension test, average shear force can be regarded as in test result
The size of adhesion between the stainless steel base and resin, test result is as shown in table 2.
Embodiment 5
The present embodiment is used for illustrating the surface treatment method of the metallic matrix of the present invention, the Metal Substrate prepared by this method
Body, and metal-resin composite and its manufacture method.
According to the complex S5 of manufacture method manufacture stainless steel and resin same as Example 1, difference is：Will
Stainless steel base after sulfur acid pretreatment is placed into 1 weight % sodium hydroxide solution, using carbon plate as negative electrode, the stainless steel
Matrix is anode, and energization 30min carries out electrochemical corrosion under 1V, and obtaining surface has irregular corrosion hole (at surface
The scope of the width of the corrosion hole formed after reason on metallic matrix is 100-50000nm, and the scope of depth is 100-
50000nm) and it is attached with metal (stainless steel) the matrix A5 of oxy radical；
Injection, obtains the stainless steel of integration and the complex S5 of resin；
It is fixed on universal testing machine and carries out extension test, average shear force can be regarded as in test result
The size of adhesion between the stainless steel base and resin, test result is as shown in table 2.
Embodiment 6
The present embodiment is used for illustrating the surface treatment method of the metallic matrix of the present invention, the Metal Substrate prepared by this method
Body, and metal-resin composite and its manufacture method.
According to the complex S6 of manufacture method manufacture stainless steel and resin same as Example 1, difference is：Will
Stainless steel base after sulfur acid pretreatment is placed into 40 weight % sodium hydroxide solution, and using carbon plate as negative electrode, this is stainless
Steel matrix is anode, and energization 0.5min carries out electrochemical corrosion under 10V, and obtaining surface has irregular corrosion hole (through table
The scope of the width of the corrosion hole formed after the processing of face on metallic matrix is 100-50000nm, and the scope of depth is 100-
50000nm) and it is attached with metal (stainless steel) the matrix A6 of oxy radical；
Injection, obtains the stainless steel of integration and the complex S6 of resin；
It is fixed on universal testing machine and carries out extension test, average shear force can be regarded as in test result
The size of adhesion between the stainless steel base and resin, test result is as shown in table 2.
Embodiment 7
The present embodiment is used for illustrating the surface treatment method of the metallic matrix of the present invention, the Metal Substrate prepared by this method
Body, and metal-resin composite and its manufacture method.
According to the complex S8 of manufacture method manufacture stainless steel and resin same as Example 2, difference is：Will
Stainless steel base after sulfur acid pretreatment, which is placed into, soaks 50min in mix acid liquor, wherein, the mix acid liquor is phosphoric acid and nitre
The mix acid liquor of acid, and the concentration of the mix acid liquor is 40 weight %, obtaining surface has irregular corrosion hole (through surface
The scope of the width of the corrosion hole formed after processing on metallic matrix is 100-50000nm, and the scope of depth is 100-
50000nm) and it is attached with metal (stainless steel) the matrix A7 of oxy radical；
Injection, obtains the stainless steel of integration and the complex S7 of resin；
It is fixed on universal testing machine and carries out extension test, average shear force can be regarded as in test result
The size of adhesion between the stainless steel base and resin, test result is as shown in table 2.
Embodiment 8
The present embodiment is used for illustrating the surface treatment method of the metallic matrix of the present invention, the Metal Substrate prepared by this method
Body, and metal-resin composite and its manufacture method.
According to the complex S8 of manufacture method manufacture stainless steel and resin same as Example 2, difference is：Will
Stainless steel base after sulfur acid pretreatment, which is placed into, soaks 70min in mix acid liquor, wherein, the mix acid liquor is phosphoric acid and nitre
The mix acid liquor of acid, and the concentration of the mix acid liquor is 6 weight %, obtaining surface has irregular corrosion hole (through surface
The scope of the width of the corrosion hole formed after processing on metallic matrix is 100-50000nm, and the scope of depth is 100-
50000nm) and it is attached with metal (stainless steel) the matrix A8 of oxy radical；
Injection, obtains the stainless steel of integration and the complex S8 of resin；
It is fixed on universal testing machine and carries out extension test, average shear force can be regarded as in test result
The size of adhesion between the stainless steel base and resin, test result is as shown in table 2.
Embodiment 9
The present embodiment is used for illustrating the surface treatment method of the metallic matrix of the present invention, the Metal Substrate prepared by this method
Body, and metal-resin composite and its manufacture method.
According to the complex S8 of manufacture method manufacture stainless steel and resin same as Example 1, difference is：With
The thermoplastic resin composition of PBT containing 50 weight % ceramic fibres and 50 weight % is molded, and the thermoplastic resin
The volume ratio of the consumption of oil/fat composition and the consumption of the stainless steel base is 1：1, obtain the stainless steel and resin of integration
Complex S9；
It is fixed on universal testing machine and carries out extension test, average shear force can be regarded as in test result
The size of adhesion between the stainless steel base and resin, test result is as shown in table 2.
Embodiment 10
The present embodiment is used for illustrating the surface treatment method of the metallic matrix of the present invention, the Metal Substrate prepared by this method
Body, and metal-resin composite and its manufacture method.
According to the complex S8 of manufacture method manufacture stainless steel and resin same as Example 2, difference is：With
The thermoplastic resin composition of PBT containing 50 weight % ceramic fibres and 50 weight % is molded, and the thermoplastic resin
The volume ratio of the consumption of oil/fat composition and the consumption of the stainless steel base is 1：1, obtain the stainless steel and resin of integration
Complex S10；
It is fixed on universal testing machine and carries out extension test, average shear force can be regarded as in test result
The size of adhesion between the stainless steel base and resin, test result is as shown in table 2.
Comparative example 1
The direct injection molding of stainless steel base prepared by preparation example 1, obtains the complex DS1 of stainless steel and resin；
It is fixed on universal testing machine and carries out extension test, average shear force can be regarded as in test result
The size of adhesion between the stainless steel base and resin, test result is as shown in table 2.
Comparative example 2
Stainless steel base prepared by preparation example 1 is put into the sulfuric acid solution that percentage by weight is 10 weight %, at 70 DEG C
Lower immersion 6min, obtains stainless steel base DS2；
Finally, above-mentioned gained stainless steel base A2 is put into mould, with containing 20 weight % glass fibres and 80 weights
The thermoplastic resin composition for measuring % polyphenylene sulfide (PPS) is molded, and the use of the thermoplastic resin composition
The volume ratio of the consumption of amount and the stainless steel base is 1：1, obtain the stainless steel of integration and the complex DS2 of resin；
It is fixed on universal testing machine and carries out extension test, average shear force can be regarded as in test result
The size of adhesion between the stainless steel base and resin, test result is as shown in table 2.
Table 1
It can also be seen that from the result of table 1 after being handled using the method for the present invention the surface of metallic matrix, the gold
The content for belonging to the oxygen element on the surface of matrix is dramatically increased, and illustrates have oxy radical to be attached on the surface of the metallic matrix,
The oxy radical be conducive to and plastics combination.
Stainless steel base A1 prepared by embodiment 1 is placed in the corrosion condition on metallography microscope Microscopic observation surface, such as accompanying drawing 1
It is shown, it is seen that surface has irregular corrosion hole, and should be 100-50000nm with the width of irregular corrosion hole,
Depth is 100-50000nm；After the complex S1 cutting polishings of stainless steel resin prepared by embodiment 1, metallography microscope is placed in
Microscopic observation is molded the section corrosion condition in region, as shown in Figure 2, wherein, white portion is stainless steel substrates matrix, grey mould
Paste region is plastics, it is seen that stainless steel substrates and hole on plastics faying face are densely distributed, and shape and size are not of uniform size.
The complex of integrated stainless steel resin manufactured in embodiment 1-10 and comparative example 1-2 is fixed on ten thousand
Maximum load can be considered the adhesion between stainless steel and resin in energy Material Testing Machine progress product extension test, test result
Size.Test result is as shown in subordinate list 2：
Table 2
| Average shear force (MPa) | |
| Embodiment 1 | 24.14 |
| Embodiment 2 | 23.35 |
| Embodiment 3 | 21.19 |
| Embodiment 4 | 20.65 |
| Embodiment 5 | 18.37 |
| Embodiment 6 | 18.26 |
| Embodiment 7 | 19.23 |
| Embodiment 8 | 17.72 |
| Embodiment 9 | 18.46 |
| Embodiment 10 | 18.07 |
| Comparative example 1 | 0 |
| Comparative example 2 | 12.31 |
Result above shows that the average shear force of the stainless steel resin composite body obtained by embodiment 1-10 is substantially better than contrast
Example 1-2, that is to say, that the adhesion using the stainless steel base resin composite body of the method manufacture of the present invention is excellent；And use
In the manufacturing process of the method for the present invention, the reagent is cheap, and toxicity is low, and the volatility of solution is low, the dirt to environment
Dye is small.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (17)
1. a kind of metallic matrix, it is characterised in that the metallic matrix is stainless steel base, and the stainless steel base surface is contained
Oxygen element, the weight/mass percentage composition of the top layer oxygen element of the stainless steel base is 1-10 weight %, the presence of the oxygen element
Form is the oxy radical for being attached to the stainless steel base surface.
2. metallic matrix according to claim 1, wherein, corrosion hole, institute are contained on the surface of the stainless steel base
The width for stating corrosion hole is 100-50000nm, and depth is 100-50000nm.
3. a kind of surface treatment method of metallic matrix, this method comprises the following steps：
(1) metallic matrix is pre-processed using sulfuric acid solution, forming surface has the metallic matrix of irregular corrosion hole,
The mode of the pretreatment is immersion；
(2) metallic matrix after pretreatment is put into alkaline solution and carries out electrochemical corrosion or be put into acid solution
Row chemical immersion；
Wherein, the mix acid liquor that the acid solution constitutes for two or more acid；
The metallic matrix is stainless steel base.
4. method according to claim 3, wherein, in step (1), the condition of the pretreatment includes：Temperature is 20-
90 DEG C, the time is 20-180min.
5. method according to claim 3, wherein, in step (1), the concentration of the sulfuric acid solution is 5-50 weights
Measure %.
6. method according to claim 3, wherein, in step (2), the concentration of the alkaline solution is 1-40 weights
Measure %.
7. the method according to claim 3 or 6, wherein, in step (2), the alkaline solution is sodium hydroxide, hydrogen-oxygen
Change one or more solution in potassium, sodium phosphate and sodium citrate.
8. method according to claim 7, wherein, the metallic matrix obtained after pretreatment is carried out with the alkaline solution
The condition of electrochemical corrosion includes：The voltage of application is 1-10V, and processing time is 0.5-30min.
9. method according to claim 3, wherein, in step (2), the concentration of the acid solution is 1-40 weights
Measure %.
10. the method according to claim 3 or 9, wherein, in step (2), the acid solution is phosphoric acid, nitric acid, sulphur
Two or more mixed solution in acid and citric acid.
11. method according to claim 10, wherein, the metallic matrix obtained after pretreatment is entered with the acid solution
The condition of row chemical immersion includes：Temperature is 20-90 DEG C, and soak time is 3-180min.
12. the metallic matrix prepared as the method described in any one in claim 3-11.
13. a kind of metal-resin composite, the metal-resin composite includes metallic matrix and combined with the metal base surface
Resin bed, it is characterised in that the metallic matrix is the metallic matrix described in any one in claim 1-2 and 12.
14. metal-resin composite according to claim 13, wherein, contain etch pit on the surface of the metallic matrix
Hole, the resin combination for forming the resin bed is filled in the corrosion hole.
15. metal-resin composite according to claim 13, wherein, it is heat to form the resin combination of the resin bed
Thermoplastic resin composition, the thermoplastic resin composition contains 50-95 weight % thermoplastic resin and 5-50 weight %
Fibrous material.
16. metal-resin composite according to claim 15, wherein, the thermoplastic resin be polyphenylene sulfide,
One or more in polybutylene terephthalate (PBT) resin, polyamide and makrolon；The fibrous material is fine for ceramics
One or more in dimension, glass fibre, aluminium silicate fiber peacekeeping polyester fiber.
17. the manufacture method of the metal-resin composite in claim 13-16 described in any one, it is characterised in that the party
Method includes metallic matrix being put into mould, is molded with thermoplastic resin composition, and the metal-resin for forming integration is answered
It is fit.
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| US11312048B2 (en) | 2017-01-10 | 2022-04-26 | Guangdong Everwin Precision Technology Co., Ltd. | Surface treatment method of material, material product and composite material |
| CN106835139B (en) * | 2017-01-10 | 2019-05-14 | 广东长盈精密技术有限公司 | Surface treatment method, stainless steel products and the stainless steel-plastics compounded body of stainless steel |
| CN106965374A (en) * | 2017-03-20 | 2017-07-21 | 歌尔股份有限公司 | The engaging member and its processing method of a kind of stainless steel and plastics |
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| CN110561678A (en) * | 2018-06-05 | 2019-12-13 | 深圳市裕展精密科技有限公司 | composite of titanium-based material and resin and preparation method thereof |
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