CN104325597B - A kind of metal-resin composite and preparation method thereof - Google Patents
A kind of metal-resin composite and preparation method thereof Download PDFInfo
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- CN104325597B CN104325597B CN201310531002.9A CN201310531002A CN104325597B CN 104325597 B CN104325597 B CN 104325597B CN 201310531002 A CN201310531002 A CN 201310531002A CN 104325597 B CN104325597 B CN 104325597B
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Abstract
The invention discloses the preparation method of a kind of metal-resin composite, the method comprises the following steps: (1) carries out laser ablation to metallic matrix, forms surface and has the metallic matrix of micron order hole；(2) metallic matrix that described surface has micron order hole is put in acid solution and carries out electrochemical corrosion；(3) metallic matrix obtained after step (2) processes is put in mould, be molded with thermoplastic resin composition, form the metal-resin composite of integration.The adhesion of metallic matrix resin composite body prepared by the method for the employing present invention is excellent；And using in the preparation process of method of the present invention, described acid solution is without heating, and described acid solution concentration is low, and nontoxic, the volatility of solution is low, and the pollution to environment is little, energy-conserving and environment-protective.
Description
Technical field
The present invention relates to a kind of metal-resin composite and preparation method thereof.
Background technology
At present, the method that metal (titanium or titanium alloy) is combined with resin-phase mainly there are three kinds: one is to utilize adhesive,
By chemical adhesive respectively with titanium or titanium alloy and molded resin effect, thus both are combined；Another kind is
Carry out chemical etching at titanium or titanium alloy surface, produce superminiature male and fomale(M&F), then carry out injection combination；The third is by sun
Mode or the electrochemical cathode of pole oxidation process, and produce nano level hole at titanium or titanium alloy surface, by this hole with
Plastic injection combines.
But, the method using adhesive, adhesion is poor, not acid and alkali-resistance, and adhesive has certain thickness, affects
The size of finished product；The method using chemical etching, for ensureing adhesion, it is necessary to needs with concentrated acid heating or uses fluorine-containing
Corrosive liquid, owing to the mode of concentrated acid heating is the longest, energy consumption is high, and acid solution evaporative emission environment, and according to fluorine-containing corrosion
Liquid, owing to the toxicity of fluorine is big, requires height to production environment, belongs to the high-risk material of high pollution；Further, anodic oxidation or electrification are used
Learning the mode of cathode treatment, obtained nano aperture is little, and oxide-film is the thinnest, causes the nano aperture degree of depth inadequate, obtained
Injecting products adhesion low, practicality is the highest.
Therefore, to how, metal is combined with resin-phase and prepares the research of metal-resin composite and increasingly come into one's own.
Summary of the invention
The invention aims to provide and realize the gold that adhesion is excellent, practicality is high and environmental pollution is little
Belong to the preparation method of resin composite body.
The invention provides the preparation method of a kind of metal-resin composite, the method comprises the following steps:
(1) metallic matrix is carried out laser ablation, form surface and there is the metallic matrix of micron order hole；
(2) metallic matrix that described surface has micron order hole is put in acid solution and carries out electrochemical corrosion；
(3) metallic matrix obtained after step (2) processes is put in mould, carry out with thermoplastic resin composition
Injection, forms the metal-resin composite of integration.
According to the preparation method of the described metal-resin composite that the present invention provides, by laser instrument will be used to process and electricity
The method that chemical attack combines prepares the metal-resin composite that adhesion is excellent, not only overcomes the single laser instrument of employing
Processing can not the face more than 180 degree, the angle of inclination inside converted products, and overcome the single electrochemical corrosion of employing and process
The defects such as speed is relatively slow, corrosion depth is inadequate, the present invention is by combining the two, at the micron order hole of laser instrument etching
Metal base surface on form more complicated, intensive hole, make surface have the metallic matrix of this structure and size favourable
In being combined with thermoplastic resin composition, and the method for the present invention uses floride-free technique, easily carries out liquid waste processing, and described
Acid solution is without heating, and the volatility of solution is low, and the pollution to environment is little, energy-conserving and environment-protective.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that described herein specifically
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides the preparation method of a kind of metal-resin composite, the method comprises the following steps:
(1) metallic matrix is carried out laser ablation, form surface and there is the metallic matrix of micron order hole；
(2) metallic matrix that described surface has micron order hole is put in acid solution and carries out electrochemical corrosion；
(3) metallic matrix obtained after step (2) processes is put in mould, carry out with thermoplastic resin composition
Injection, forms the metal-resin composite of integration.
According to the present invention, described metallic matrix can be Titanium base or titanium alloy substrate.
According to the present invention, metallic matrix is carried out laser ablation, form surface and there is the metallic matrix of micron order hole；Its
In, laser ablation can be once to etch, it is also possible to is multiple etching, and once etching can form circle at metal base surface
Hole, multiple etching can form the hole of multiple circle at metal base surface, and the hole of multiple circles may connect
Together, it is therefore also possible to groove can be formed on the surface of metallic matrix.
According to the present invention, in step (1), the width of the hole formed on metallic matrix after laser ablation is permissible
For 20-100 μm, preferably 50-80 μm；The degree of depth can be 1-100 μm, preferably 10-40 μm；The spacing of hole can be
0.05-1mm, preferably 0.1-0.3mm.In the present invention, the width of the hole formed on metallic matrix refers to this circular port
The size of the maximum gauge in hole, if multiple hole is joined together to form groove, then, in the present invention, at metallic matrix
The width of the hole of upper formation refers to the width of the groove formed on metal base surface, in like manner, is formed on metallic matrix
The degree of depth of hole refers to the degree of depth of the groove formed on metal base surface.
According to the present invention, in step (1), the laser instrument performing etching metallic matrix used the most specifically limits
Fixed, in the present invention, described laser instrument can be the model of Chinese workers' laser production be LSF20 laser-beam drilling machine, this laser instrument
Machined parameters is also not particularly limited, as long as can perform etching on metallic matrix, and the width of the hole formed is 20-
100 μm, the degree of depth is 1-100 μm.In the case of in the present invention, it is preferred to, the machined parameters of this laser instrument is: hole or separation
For 0.05-1mm, process velocity is 50-3000mm/s, and frequency is 20-80kHz, and working power is 10-20 watt；Under this parameter
This laser instrument is operated, it is possible to perform etching on metallic matrix, and can form hole described above or groove.
According to the present invention, in step (2), the metallic matrix that described surface has micron-sized hole is put into acid molten
In liquid and carry out electrochemical corrosion so that the width of this hole is widened further, and the degree of depth of this hole is added further
Deeply.In step (2), the width of the hole formed on metallic matrix after electrochemical corrosion is 20-200 μm, is preferably
50-150μm；The degree of depth is 1-200 μm, preferably 20-50 μm.
According to the present invention, in step (2), described acid solution can be ferric trichloride and the mixing of non-oxidizing acid
Solution, and on the basis of the gross weight of described acid solution, the content of described ferric trichloride can be 1-20 weight %, is preferably
5-15 weight %；The content of described non-oxidizing acid can be 0.1-20 weight %, preferably 1-15 weight %；In the present invention,
Described non-oxidizing acid can be one or more in hydrochloric acid, oxalic acid, phosphoric acid and acetic acid.
According to the present invention, in the described electrochemical corrosion course of step (2), negative electrode is not particularly limited, and can be this
In field, conventional use of material is as negative electrode, and in the present invention, negative electrode can be preferably graphite；Using described metallic matrix as
Anode, and make the region to be molded of described metallic matrix towards negative electrode.The condition of described electrochemical corrosion may include that voltage is
1.8-18V, the time is 2-24min；Under preferable case, the condition of described electrochemical corrosion may include that voltage is 2-16V, time
Between be 6-20min.
It addition, according to the present invention, in step (2), described electrochemical corrosion can also include: with alkaline solution to electrification
The metallic matrix obtained after learning corrosion treatmentCorrosion Science carries out surface process.Because metallic matrix soaks in an acidic solution for a long time, and
The hole formed on metal base surface is all micron-sized, may remain acid molten in these micron-sized holes
Liquid, therefore may can produce corrosiveness in subsequent process, therefore, obtain after electrochemical corrosion being processed with alkaline solution
Metallic matrix carries out surface process, the acid solution of residual can be neutralized effect, it is possible to avoid drawbacks described above, and,
Even if alkaline solution there may be residual, and metallic matrix also will not produce pair impact.In the present invention, this surface be processed as by
The metallic matrix that electrochemical corrosion obtains after processing is immersed in alkaline solution, even if alkaline solution is completely covered through electrochemistry rotten
The metallic matrix that erosion obtains after processing.Alkali in described alkaline solution can be in sodium carbonate, sodium acid carbonate or NaOH
One or more.Under preferable case, the alkali in described alkaline solution is sodium carbonate.After electrochemical corrosion being processed with alkaline solution
It can be 1-30min, preferably 5-20min that the metallic matrix obtained carries out the time of surface process.Described alkaline solution dense
Degree can be 1-10%.
According to the present invention, in step (3), described thermoplastic resin composition can be containing the thermoplastic of 50-100 weight %
Property resin and the fibrous material of 0-50 weight %.Under preferable case, described thermoplastic resin composition contains 80-100 weight %
Thermoplastic resin and the fibrous material of 0-20 weight %.
According to the present invention, described thermoplastic resin can be polyphenylene sulfide, polybutylene terephthalate (PBT) resin,
One or more in polyamide and Merlon；Described fibrous material can be ceramic fibre, glass fibre, alumina silicate fibre
With one or more in polyester fiber.
According to the present invention, in step (3), the consumption of described thermoplastic resin composition is not particularly limited, Ke Yigen
According to size and the size of metallic matrix of mould, as long as can metallic matrix be formed integrated with thermoplastic resin composition
Metal-resin composite.Under preferable case, the consumption of described thermoplastic resin composition and described titanium alloy substrate
The volume ratio of consumption can be 1:1.
According to the present invention, in step (1), before metallic matrix is carried out laser ablation, it is also possible to metallic matrix
Carry out pre-treatment；This pretreatment process includes the rectangle sheet that metallic matrix is cut into 15mm × 80mm, more respectively by this gold
Belong to matrix and put into polishing machine sanding and polishing, then, then carry out oil removing successively, wash and the process such as drying.In the present invention,
Described polishing machine is not particularly limited, and can be the polishing machines often known of those skilled in the art, and the preparation side to the present invention
Metal-resin composite prepared by method is polished, oil removing, wash and dry and be all not particularly limited, and can be this area skill
Technology known to art personnel.
Hereinafter by embodiment, the present invention will be described in detail.
In the following Examples and Comparative Examples, characterize according to universal testing machine (purchased from Ying Site, model is 3369)
The shearing force of metallic matrix prepared by the present invention；Described polyphenylene sulfide is purchased from Qi get engineering plastics Co., Ltd；Described poly-
Mutual-phenenyl two acid bromide two alcohol ester's resin is purchased from Qi get engineering plastics Co., Ltd；Described glass fibre is purchased from Orco glass fibre
Factory；Described ceramic fibre is purchased from Orco glass fibre factory；The trade mark used by the present invention is that the titanium alloy sheet of TA1 titanium plate and TA2 is equal
Belonging to Materials Co., Ltd purchased from port ancient sacrificial bronze ware, described polishing machine is purchased from the permanent safe polishing machine that model is 883 produced；Described laser instrument
The model produced purchased from Chinese workers' laser is LSF20 laser-beam drilling machine.
Preparation example 1
Take TA1 titanium plate and each one piece of TA2 titanium alloy sheet that thickness is 0.8mm, be cut into the rectangle sheet of 15mm × 80mm,
The most respectively this TA1 titanium plate and TA2 titanium alloy sheet are put into polishing machine sanding and polishing, then, then carry out successively oil removing, washing with
And the pretreatment process such as drying, finally, prepare TA1 Titanium base and TA2 titanium alloy substrate.
Embodiment 1
The present embodiment is used for illustrating the preparation method of the metal-resin composite of the present invention
Laser instrument is used to carry out laser ablation on the titanium alloy-based surface of TA2, shape on the titanium alloy-based surface of this TA2
Becoming width is that 50 μm, the degree of depth are 10 μm and spacing is the hole of 0.1mm；Wherein, the working power of this laser instrument is 10 watts, speed
Degree is 2200mm/s, and frequency is 60kHz；
On the basis of the gross weight of the acid solution (ferric trichloride and the mixed solution of hydrochloric acid) prepared, ferric trichloride
Content is 15 weight %, and the content of hydrochloric acid is 15 weight %, is put into by the metallic matrix that described surface has micron order hole or groove
In this acid solution, then, the titanium alloy substrate after soaking with acid solution is as anode, using graphite as negative electrode, and makes
The region to be molded of described TA2 titanium alloy substrate is towards negative electrode；Electrochemical corrosion 20min is carried out, through electrification under voltage is 16V
The width of the hole formed on this TA2 titanium alloy substrate after learning corrosion is 150 μm；The degree of depth is 50 μm；Subsequently, will be through electrochemistry
Titanium alloy substrate after corrosion takes out, and cleans and dries up, and puts into immersion 10min in the sodium carbonate liquor of 5 weight % afterwards；Again should
Titanium alloy substrate takes out, and cleans up, and puts in baking oven and dries at a temperature of 65 DEG C, the titanium alloy substrate after being processed；
Above-mentioned titanium alloy substrate obtained after electrochemical corrosion is put in mould, with containing 20 weight % glass
The thermoplastic resin composition of the polyphenylene sulfide (PPS) of fiber and 80 weight % is molded, and described thermoplastic resin group
The consumption of compound is 1:1 with the volume ratio of the consumption of described titanium alloy substrate, obtains the titanium alloy substrate resin compounded of integration
Body S1, after this metallic matrix resin composite body S1 is stood 24 hours, is fixed on universal testing machine and stretches
Test, in test result, average shear force can regard the size of the adhesion between this TA2 titanium alloy substrate and resin as, knot
Fruit is as shown in table 1.
Embodiment 2
The present embodiment is used for illustrating the preparation method of the metal-resin composite of the present invention
Laser instrument is used to carry out laser ablation on the titanium alloy-based surface of TA2, shape on the titanium alloy-based surface of this TA2
Becoming width is that 20 μm, the degree of depth are 1 μm and spacing is the hole of 0.05mm；Wherein, this laser instrument working power is 10 watts, speed
For 2200mm/s, frequency is 80kHz；
On the basis of the gross weight of the acid solution (ferric trichloride and the mixed solution of hydrochloric acid) prepared, ferric trichloride
Content is 5 weight %, and the content of hydrochloric acid is 1 weight %, and the metallic matrix that described surface has micron order hole or groove is put into this
In acid solution, then, the titanium alloy substrate after soaking with acid solution is as anode, using graphite as negative electrode, and makes institute
State the region to be molded of TA2 titanium alloy substrate towards negative electrode；Electrochemical corrosion 6min is carried out under voltage is 2V, rotten through electrochemistry
The width of the hole formed on this TA2 titanium alloy substrate after erosion is 50 μm；The degree of depth is 10 μm；Subsequently, will be through electrochemical corrosion
After titanium alloy substrate take out, clean and dry up, put in the sodium carbonate liquor of 10 weight % immersion 1min afterwards；Again this titanium is closed
Auri body takes out, and cleans up, and puts in baking oven and dries at a temperature of 65 DEG C, the titanium alloy substrate after being processed；
Above-mentioned titanium alloy substrate obtained after electrochemical corrosion is put in mould, with containing 30 weight % potteries
The thermoplastic resin composition of the polybutylene terephthalate (PBT) resin of fiber and 70 weight % is molded, and described thermoplastic
Property resin combination the volume ratio of consumption of consumption and described titanium alloy substrate be 1:1, obtain the titanium alloy substrate of integration
Resin composite body S2, after this metallic matrix resin composite body S2 is stood 24 hours, is fixed on universal testing machine
Carrying out extension test, in test result, average shear force can regard the adhesion between this TA2 titanium alloy substrate and resin as
Size, result is as shown in table 1.
Embodiment 3
The present embodiment is used for illustrating the preparation method of the metal-resin composite of the present invention
Use laser instrument to carry out laser ablation on TA2 titanium alloy substrate, the titanium alloy-based surface of this TA2 is formed width
Degree is that 100 μm, the degree of depth are 40 μm and spacing is the hole of 1mm；Wherein, the working power of this laser instrument is 20 watts, and speed is
2500mm/s, frequency is 20kHz；
On the basis of the gross weight of the acid solution (ferric trichloride and the mixed solution of hydrochloric acid) prepared, ferric trichloride
Content is 10 weight %, and the content of hydrochloric acid is 10 weight %, is put into by the metallic matrix that described surface has micron order hole or groove
In this acid solution, then, the titanium alloy substrate after soaking with acid solution is as anode, using graphite as negative electrode, and makes
The region to be molded of described TA2 titanium alloy substrate is towards minus plate；Electrochemical corrosion 12min is carried out, through electricity under voltage is 14V
The width of the hole formed on this TA2 titanium alloy substrate after chemical attack is 200 μm；The degree of depth is 100 μm；Subsequently, will be through electricity
Titanium alloy substrate after chemical attack takes out, and cleans and dries up, and puts into immersion 30min in the sodium carbonate liquor of 1 weight % afterwards；Again
Titanium alloy substrate is taken out, cleans up, put in baking oven and dry at a temperature of 65 DEG C, the titanium alloy substrate after being processed；
Above-mentioned titanium alloy substrate obtained after electrochemical corrosion is put in mould, with gathering containing 100 weight %
Diphenyl sulfide resin (PPS) is molded, and the consumption of the consumption of described polyphenylene sulfide (PPS) and described titanium alloy substrate
Volume ratio is 1:1, obtains the titanium alloy substrate resin composite body S3 of integration, and this metallic matrix resin composite body S3 is stood 24
After hour, being fixed on universal testing machine and carry out extension test, in test result, average shear force can be regarded as
The size of the adhesion between this TA2 titanium alloy substrate and resin, result is as shown in table 1.
Embodiment 4
Preparing metallic matrix resin composite body S4 according to preparation method same as in Example 1, institute's difference is:
Use laser instrument when performing etching on TA1 Titanium base, this TA1 Titanium base surface is formed width be 100 μm, the degree of depth be 40
μm and spacing are the hole of 0.3mm；Wherein, the working power of this laser instrument is 20 watts, and speed is 2500mm/s, and frequency is
20kHz；
The width of the hole formed on this TA1 Titanium base after electrochemical corrosion is 180 μm；The degree of depth is 100 μm；
After the metallic matrix resin composite body S4 of preparation is stood 24 hours, it is fixed in universal testing machine enterprising
Row extension test, in test result, average shear force can regard the size of the adhesion between this TA1 Titanium base and resin as,
Result is as shown in table 1.
Embodiment 5
Preparing metallic matrix resin composite body S5 according to preparation method same as in Example 1, difference is: adopting
When performing etching on TA1 Titanium base with laser instrument, this TA1 Titanium base surface is formed width be 50 μm, the degree of depth be 20 μm
And spacing is the hole of 0.1mm；Wherein, the working power of this laser instrument is 10 watts, and speed is 2200mm/s, and frequency is
60kHz。
The width of the hole formed on this TA1 Titanium base after electrochemical corrosion is 150 μm；The degree of depth is 60 μm；
After the metallic matrix resin composite body S5 of preparation is stood 24 hours, it is fixed in universal testing machine enterprising
Row extension test, in test result, average shear force can regard the size of the adhesion between this TA1 Titanium base and resin as,
Result is as shown in table 1.
Embodiment 6
Preparing metallic matrix resin composite body S6 according to preparation method same as in Example 1, difference is: at electricity
In chemical attack, on the basis of the gross weight of the acid solution (ferric trichloride and the mixed solution of hydrochloric acid) prepared, tri-chlorination
The content of iron is 20 weight %, and the content of hydrochloric acid is 15 weight %；Formed on this TA2 titanium alloy substrate after electrochemical corrosion
The width of hole is 200 μm；The degree of depth is 70 μm；
After the metallic matrix resin composite body S6 of preparation is stood 24 hours, it is fixed in universal testing machine enterprising
Row extension test, in test result, average shear force can regard the adhesion between this TA2 titanium alloy substrate and resin as
Size, result is as shown in table 1.
Embodiment 7
Preparing metallic matrix resin composite body S7 according to preparation method same as in Example 1, difference is to be joined
The mixture that acid solution is ferric trichloride and phosphoric acid of system.
After the metallic matrix resin composite body S7 of preparation is stood 24 hours, it is fixed in universal testing machine enterprising
Row extension test, in test result, average shear force can regard the size of the adhesion between titanium alloy substrate and resin as,
Result is as shown in table 1.
Embodiment 8
Preparing metallic matrix resin composite body S7 according to preparation method same as in Example 1, difference is to be joined
The mixture that acid solution is ferric trichloride and acetic acid of system.
After the metallic matrix resin composite body S7 of preparation is stood 24 hours, it is fixed in universal testing machine enterprising
Row extension test, in test result, average shear force can regard the size of the adhesion between titanium alloy substrate and resin as,
Result is as shown in table 1.
Comparative example 1
Preparing metallic matrix resin composite body DS1 according to preparation method same as in Example 1, difference is do not have
Use laser instrument in titanium alloy substrate enterprising row metal etching to form hole or groove on metal base surface, only at titanium alloy
Electrochemical corrosion is carried out on matrix surface.
After the metallic matrix resin composite body DS1 of preparation is stood 24 hours, it is fixed on universal testing machine
Carrying out extension test, in test result, average shear force can regard the big of the adhesion between titanium alloy substrate and resin as
Little, result is as shown in table 1.
Comparative example 2
Preparing metallic matrix resin composite body DS2 according to preparation method same as in Example 1, difference is do not have
Metallic matrix through laser ablation is proceeded electrochemical corrosion.
After the metallic matrix resin composite body DS2 of preparation is stood 24 hours, it is fixed on universal testing machine
Carrying out extension test, in test result, average shear force can regard the big of the adhesion between titanium alloy substrate and resin as
Little, result is as shown in table 1.
Comparative example 3
Metallic matrix resin composite body DS3 is prepared, except for the difference that in electrochemistry according to preparation method same as in Example 1
In corrosion, described acid solution is the ammonium hydrogen fluoride solution of 1 weight %, and reacts 24min at temperature is 25 DEG C.
After the metallic matrix resin composite body DS3 of preparation is stood 24 hours, it is fixed on universal testing machine
Carrying out extension test, in test result, average shear force can regard the big of the adhesion between titanium alloy substrate and resin as
Little, result is as shown in table 1.
Comparative example 4
Metallic matrix resin composite body DS4 is prepared, except for the difference that in electrochemistry according to preparation method same as in Example 1
In corrosion, the titanium alloy substrate after not etched by laser instrument is as anode, but configuration 500ml anodic oxidation electrolyte, its
In, electrolyte prescription is 10 weight % phosphoric acid and 20 weight % sodium gluconates, and anodic oxidation voltage is 20V, and conduction time is
10min。
After the metallic matrix resin composite body DS4 of preparation is stood 24 hours, it is fixed on universal testing machine
Carrying out extension test, in test result, average shear force can regard the big of the adhesion between titanium alloy substrate and resin as
Little, result is as shown in table 1.
Table 1
By the data of table 1 it can be seen that the titanium of preparation or averagely the cutting of titanium alloy substrate resin S1-S8 in embodiment 1-8
Shear force significantly improves than the average shear force of the titanium alloy substrate resin DS1-DS4 of preparation in comparative example 1-4, illustrates the present invention's
Titanium or titanium alloy substrate prepared by method are excellent with the adhesion of resin, say, that use titanium prepared by the method for the present invention
Or the adhesion of titanium alloy substrate resin composite body is excellent；And use in the preparation process of method of the present invention, described acidity is molten
Liquid is without heating, and described acid solution concentration is low, and nontoxic, the volatility of solution is low, and the pollution to environment is little, energy-saving ring
Protect.
Claims (12)
1. a preparation method for metal-resin composite, the method comprises the following steps:
(1) metallic matrix is carried out laser ablation, form surface and there is the metallic matrix of micron order hole；
(2) metallic matrix that described surface has micron order hole is put in acid solution and carries out electrochemical corrosion；
(3) metallic matrix obtained after step (2) processes is put in mould, note with thermoplastic resin composition
Mould, form the metal-resin composite of integration；
Wherein, in step (1), the width of the hole formed on metallic matrix after laser ablation is 20-100 μm, deeply
Degree is 1-100 μm, and the spacing of hole is 0.05-1mm；In step (2), formed on metallic matrix after electrochemical corrosion
The width of hole be 20-200 μm, the degree of depth is 1-200 μm.
Method the most according to claim 1, wherein, described metallic matrix is Titanium base or titanium alloy substrate.
Method the most according to claim 1, wherein, in step (1), is formed after laser ablation on metallic matrix
The width of hole be 50-80 μm, the degree of depth is 10-40 μm, and the spacing of hole is 0.1-0.3mm；In step (2), Jing Guo electricity
The width of the hole formed on metallic matrix after chemical attack is 50-150 μm, and the degree of depth is 20-50 μm.
Method the most according to claim 1, wherein, in step (2), described acid solution is ferric trichloride and non-oxide
Property the mixed solution of acid, and on the basis of the gross weight of described acid solution, the content of described ferric trichloride is 1-20 weight
Amount %, the content of described non-oxidizing acid is 0.1-20 weight %；Described non-oxidizing acid be hydrochloric acid, oxalic acid, phosphoric acid and
One or more in acetic acid.
Method the most according to claim 4, wherein, on the basis of the gross weight of described acid solution, described ferric trichloride
Content be 5-15 weight %, the content of described non-oxidizing acid is 1-15 weight %.
Method the most according to claim 1, wherein, in step (2), using described metallic matrix as anode, and makes institute
State the region to be molded of metallic matrix towards negative electrode；The condition of described electrochemical corrosion includes: voltage is 1.8-18V, and the time is
2-24min。
Method the most according to claim 1, wherein, in step (2), the step of described electrochemical corrosion also includes: use
The metallic matrix that alkaline solution obtains after processing electrochemical corrosion carries out surface process.
Method the most according to claim 7, wherein, the alkali in described alkaline solution is sodium carbonate, sodium acid carbonate and hydrogen-oxygen
Change one or more in sodium；The concentration of described alkaline solution is 1-10%；After electrochemical corrosion being processed with alkaline solution
To metallic matrix to carry out time of surface process be 1-30min.
Method the most according to claim 1, wherein, in step (3), described thermoplastic resin composition contains 50-100
The thermoplastic resin of weight % and the fibrous material of 0-50 weight %.
Method the most according to claim 9, wherein, described thermoplastic resin is polyphenylene sulfide, poly terephthalic acid
One or more in butanediol ester resin, polyamide and Merlon；Described fibrous material be ceramic fibre, glass fibre,
One or more in aluminium silicate fiber peacekeeping polyester fiber.
11. metal-resin composites prepared according to the preparation method described in any one in claim 1-10.
12. metal-resin composites according to claim 11, wherein, described metallic matrix is Titanium base or titanium alloy-based
Body.
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| CN107570878B (en) * | 2017-09-29 | 2019-06-28 | 深圳市长盈精密技术股份有限公司 | The laser carving method of mobile terminal antenna holder |
| CN107815686A (en) * | 2017-11-03 | 2018-03-20 | 安徽新合富力科技有限公司 | A kind of stainless steel nano method for treating |
| 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 |
| CN110587907B (en) * | 2019-08-26 | 2021-08-24 | 中广核环保产业有限公司 | Preparation method of stainless steel resin complex |
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| US20050106362A1 (en) * | 2003-11-13 | 2005-05-19 | Gene Kim | Energetic beam markable sheet |
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| CN1120078A (en) * | 1994-09-12 | 1996-04-10 | 北京科技大学 | Method of quick and deep chemical etching for stainless steel |
| CN103582329A (en) * | 2012-07-24 | 2014-02-12 | 富泰华工业（深圳）有限公司 | Shell and manufacturing method thereof |
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