CN108018555A - A kind of metallic surface processing method, metal product and metallo-plastic complex - Google Patents
A kind of metallic surface processing method, metal product and metallo-plastic complex Download PDFInfo
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- CN108018555A CN108018555A CN201710976683.8A CN201710976683A CN108018555A CN 108018555 A CN108018555 A CN 108018555A CN 201710976683 A CN201710976683 A CN 201710976683A CN 108018555 A CN108018555 A CN 108018555A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
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Abstract
The invention discloses a kind of metallic surface processing method, metal product and metallo-plastic complex, this method to include：The present invention carries out roughened surface etching process using acid sand reagent to pending metal, to obtain the metal that surface produces nanoscale hole hole.Since the property for the acid sand reagent prepared in advance is suitable, and act directly on the pending metal surface, larger-size nano aperture can be produced in the pending metal surface by a roughened surface etching process, through the above way, the larger nano aperture of the aperture size can make the even closer combination of the plastics of the metal after processing and follow-up injection moulding process, be conducive to improve the quality of injecting products.
Description
Technical field
The present invention relates to a kind of metallic surface processing method, metal product and metallo-plastic complex.
Background technology
With the continuous development of intelligent terminal technology, while the intelligent terminal function is enriched constantly, user is to institute
It is also higher and higher to state the requirement of the appearance and feel of intelligent terminal, and plastic-metal complex material is obtained by Shooting Technique
Because appearance is exquisite, uses the comfortable hot spot for becoming intelligent terminal area research.
Existing plastic-metal complex material usually requires first to need to form nano aperture in metal surface, afterwards, leads to
Certain pressure is crossed, plastic melt is entered in the nano aperture of metal surface, so as to form a kind of composite construction.And have preparing
When having the metal of nano aperture, there is the metal and modeling with nano aperture that prepare in the technology being commonly used
The problem of combination force difference of material, the quality of plastic-metal composite material is unqualified.
The content of the invention
The invention mainly solves the technical problem of providing the modeling of a kind of metallic surface processing method, metal product and metal
Expect complex, the metal with larger nano aperture structure can be prepared, and after injection molding, the combination power of product
By force.
In order to solve the above technical problems, one aspect of the present invention is：A kind of metallic surface processing is provided
Method, the described method includes：Roughened surface etching process is carried out to pending metal using acid sand reagent, to obtain table
Face produces the metal of nanoscale hole hole.
In order to solve the above technical problems, another technical solution used in the present invention is：A kind of metal product is provided, it is described
Metal product is obtained after being handled using method as described above.
In order to solve the above technical problems, another technical solution that the present invention uses is：It is compound to provide a kind of metallo-plastic
Body, the metallo-plastic complex include：Metal product as described above and the plastics for being moulded in the surface of metal product.
The beneficial effects of the invention are as follows：The situation of the prior art is different from, the present invention treats place using acid sand reagent
Manage metal and carry out roughened surface etching process, to obtain the metal that surface produces nanoscale hole hole.By the institute prepared in advance
It is suitable to state the property of acid sand reagent, and acts directly on the pending metal surface, can be by being once roughened table
Facet etch processing produces larger-size nano aperture in the pending metal surface, by the above-mentioned means, the aperture ruler
Very little larger nano aperture can make the even closer combination of the plastics of the metal after processing and follow-up injection moulding process, be conducive to carry
The quality of high injecting products.
Brief description of the drawings
Fig. 1 is the flow chart of one embodiment of metallic surface processing method of the present invention；
Fig. 2 is the scanning electron microscope signal of the metal that surface produces nanoscale hole hole in metallic surface processing method of the present invention
Figure；
Fig. 3 is that the scanning electron microscope of the metal that surface produces nanoscale hole hole in prior art metallic surface processing method is shown
It is intended to.
Embodiment
The present invention is described in detail with embodiment below in conjunction with the accompanying drawings.
The invention discloses a kind of metallic surface processing method, wherein, the described method includes：
Roughened surface etching process is carried out to pending metal using acid sand reagent, nanometer is produced to obtain surface
The metal of level hole.Since the acid in the acid sand reagent can be reacted with metal, reach coarse to metal progress
Change the purpose of surface etching, and then in the pending metal surface generation nanoscale hole hole.Optionally, the metal for magnesium,
The metal that aluminium etc. can be chemically reacted with acid.
Optionally, the acid sand reagent includes：One in ferric trichloride, hydrochloric acid, hydrogen fluoride ammonia, copper chloride or sulfuric acid
Kind or it is a variety of, such as described acid sand reagent is hydrochloric acid and the mixed solution of sulfuric acid, the acidity sand reagent is ferric trichloride,
Hydrochloric acid and hydrogen fluoride ammonia mixed solution, the acidity sand reagent is ferric trichloride, hydrochloric acid, hydrogen fluoride ammonia, copper chloride and sulfuric acid
Mixed solution.Using different types of sour mutual cooperation, acid can be made to be carried out with metal reaction more abundant, be conducive to increase
The size for the nanoscale hole hole that the big metal surface produces；Optionally, select ferric trichloride, hydrogen fluoride ammonia and copper chloride this kind of
Strong acid weak base salt, on the one hand can increase the acidity of solution, carry out the roughened surface etching process more abundant；Separately
On the one hand, chlorion and fluorine ion have preferable permeability, can be penetrated into from the hole of metal, so as to accelerate described coarse
Change the progress of surface etching process.
Optionally, in the acid sand reagent, the concentration of the ferric trichloride is 30-300g/L, as 30g/L,
100g/L, 170g/L, 240g/L and 300g/L etc.；The concentration of the hydrochloric acid is 30-300g/L, as 30g/L, 90g/L,
150g/L, 210g/L and 300g/L etc.；The concentration of the hydrogen fluoride ammonia is 20-200g/L, as 20g/L, 70g/L, 120g/L,
170g/L and 200g/L etc.；The concentration of the copper chloride is 5-50g/L, such as 5g/L, 15g/L, 25g/L, 35g/L and 50g/L
Etc.；The concentration of the sulfuric acid is 30-300g/L, such as 30g/L, 100g/L, 160g/L, 250g/L and 300g/L.
Further, the temperature of the acid sand reagent is 20-60 DEG C, such as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C
Deng；Processing time is 1-10min, such as 1min, 3min, 5min, 7min, 10min.Usually, similar institute is obtained
The aperture size of metal surface generation nanoscale hole hole is stated, the temperature of the acidity sand reagent is higher, and processing time is corresponding
Reduce；Meanwhile the influence in view of acid concentration, when the temperature of acid sand reagent and processing time are to the metal surface
When the aperture size influence amplitude of the nanoscale hole hole of generation is similar, acid concentration is higher, and the metal surface generates nano grade pore
The aperture size in hole is bigger.In short, the concentration of the acidity sand reagent is high, temperature is high, processing time length is conducive in metal
The nanoscale hole hole of Surface Creation aperture size bigger.
Optionally, before the acid sand reagent of the use carries out roughened surface etching process to pending metal, also
Including：The pending metal is pre-processed, the pretreatment includes ungrease treatment and sour neutralisation treatment.
Optionally, after the acid sand reagent of the use carries out roughened surface etching process to pending metal, also
Including：Surface is carried out to the metal after roughened surface etching process and removes Slag treatment；The metal after Slag treatment is removed to surface to carry out
Coating film treatment.
Please refer to Fig.1, Fig. 1 is metallic surface processing method of the present invention with the flow chart of embodiment, the method bag
Include step：
S100, pre-process the pending metal；
In the step S100, the preprocessing process can include ungrease treatment and sour neutralisation treatment；This is because
The surface of metal product would generally scribble protection oil, oxide and dust etc., to make the follow-up roughening table carried out to metal
Surface treatment obtains preferable effect, carries out coarse surface treatment before processing in the metal, waits to locate to described using degreasing agent
Manage metal surface and carry out ungrease treatment.The degreasing agent can be in alkaline defatting agent, lotion degreasing agent or solution degreasing agent
It is one or more.In one embodiment, the degreasing agent is the alkaline defatting agents such as VR6332-3, ELC409 or GT-TZ102,
The alkaline defatting agent is not only nontoxic, cheap, and degreasing effect is relatively good.During carrying out the ungrease treatment again, institute
The concentration for stating degreasing agent is 30-50g/L, such as 30g/L, 35g/L, 40g/L, 45g/L or 50g/L；The ungrease treatment
Temperature is 50-80 DEG C, such as 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C；The time of the ungrease treatment is 3-10min, as 3min,
5min, 7min, 9min, 10min etc.；Certainly, the higher degreasing agent concentration, the higher ungrease treatment temperature and compared with
The long ungrease treatment time is conducive to obtain more preferable degreasing effect.In addition, after skimming processes, the one of the metal surface
Some degreasing agents can be also remained in a little sightless small holes of naked eyes, to avoid influence of the degreasing agent to subsequent operation, into
One step cleans the metal surface after ungrease treatment with water or alcohol etc., and the mode of the cleaning is clear for flushing or ultrasound
Wash.
To avoid the residual of the alkaline defatting agent from having a negative impact the coarse surface treatment effect of acid reagent,
Optionally, sour neutralisation treatment is carried out to the metal after the ungrease treatment, and in the sour neutralisation treatment, sour neutralisation treatment agent
For nitric acid, the concentration of the nitric acid is 100-300g/L, such as 100g/L, 150g/L, 200g/L, 250g/L or 300g/L；
The temperature of the acid neutralisation treatment is 25-50 DEG C, such as 25 DEG C, 30 DEG C, 35 DEG C, 45 DEG C or 50 DEG C；The acid neutralisation treatment
Time be 1-5min, such as 1min, 2min, 3min, 4min or 5min.Certainly, higher acid concentration, the higher acid
Neutralisation treatment temperature and the longer sour neutralisation treatment time are conducive to obtain preferable sour neutralisation treatment effect.
S200, carry out roughened surface etching process to the pretreated metal；
In the step S200, roughened surface is carried out to the pretreated metal with the acid sand reagent
Etching process,, can be according to treating before the acidity sand reagent is prepared since the acid sand reagent is prepared in advance
Handle the species of metal, thickness and required surface and produce the size of nanoscale hole hole and determine the composition of the acid sand reagent
And concentration, and the condition of coarse surface treatment is combined, such as the roughened surface etching process temperature, the roughened surface
Etch processes time etc., obtains the more suitable acid sand reagent, and then controls the metal-surface nano level hole
Size.
In addition, a roughened surface etching process only is carried out with regard to that can make gold to the pending metal in present embodiment
Metal surface produces larger-sized nanoscale hole hole, reduces operating procedure, shortens the production cycle；Meanwhile decreasing
The dosage of medicine is learned, while reducing cost, reduces sewage discharge, more energy conservation and environmental protection.
S300, remove Slag treatment to the metal progress surface after the roughened surface etching process；
In the step S300, to remained in after the roughened surface etching process impurity of the metal surface into
Row removes Slag treatment；Specifically, carrying out surface to the metal after roughened surface etching process removes Slag treatment, including：
First subsurface slagging-off processing carries out the metal after roughened surface etching process using alkaline solution；Described
In first subsurface slagging-off processing procedure, the alkaline solution is piece aqueous slkali, and the concentration of described aqueous slkali is 10-150g/
L, such as 10g/L, 50g/L, 90g/L, 130g/L or 150g/L；The temperature of the first subsurface slagging-off processing is 25-50
DEG C, such as 25 DEG C, 35 DEG C, 40 DEG C, 45 DEG C or 50 DEG C；The time of the first subsurface slagging-off processing is 1-5min, such as
1min, 2min, 3min, 4min or 5min etc.；Certainly, higher alkali concn, higher the first subsurface slagging-off processing
Treatment temperature and longer first subsurface slagging-off processing processing time are conducive to obtain preferable first subsurface
Remove the gred treatment effect.
Optionally, the metal after being handled using the first acid solution the first subsurface slagging-off is carried out at final surface slagging-off
Reason；To remove the lye residual in the first subsurface slagging-off processing, using the principle of acid-base neutralization, carry out final surface and remove
Slag treatment；First acid solution is salpeter solution, and the concentration of the salpeter solution is 100-300g/L, as 100g/L,
150g/L, 200g/L, 250g/L or 300g/L etc.；The final surface is 25-50 DEG C except the temperature of Slag treatment, such as 25 DEG C,
30 DEG C, 35 DEG C, 45 DEG C or 50 DEG C etc.；The final surface is 1-5min except the time of Slag treatment, as 1min, 2min, 3min,
4min or 5min etc.；Certainly, Slag treatment is removed on the acid concentration of higher first acid solution, the higher final surface
Temperature and the longer final surface slagging-off processing time are conducive to obtain the preferable final surface slagging-off treatment effect.
S400, remove the surface metal progress coating film treatment after Slag treatment；
In the step S400, coating film treatment refers to plate last layer metal on some metal surfaces using electrolysis principle
The process of oxide, metal or alloy, with play prevent metal aoxidize (such as corrosion), improve wearability, electric conductivity, reflective,
Corrosion resistance and having improved aesthetic appearance etc. act on.Specifically, the present embodiment uses graphite as cathode, the gold after Slag treatment is removed on the surface
Category does anode (by taking metallic aluminium as an example), and acid does electrolyte, then can produce pellumina in anode metal aluminium surface after being powered, reach
Protect the surface except the purpose of the metal after Slag treatment.In the reaction process, the electrolyte is the second acid solution,
Second acid solution includes the one or more in sulfuric acid solution, phosphoric acid solution or oxalic acid solution, and e.g., described second is acid
Solution is sulfuric acid solution, and second acid solution is the mixed solution of sulfuric acid, phosphoric acid and oxalic acid；When second acid solution
For sulfuric acid solution, phosphoric acid solution and oxalic acid solution mixed solution when, wherein, the concentration of the sulfuric acid is 100-400g/L, such as
100g/L, 180g/L, 260g/L, 340g/L or 400g/L etc.；The concentration of the phosphoric acid is 100-400g/L, as 100g/L,
180g/L, 260g/L, 340g/L or 400g/L etc.；The concentration of the oxalic acid is 100-400g/L, as 100g/L, 180g/L,
260g/L, 340g/L or 400g/L etc.；And the coating film treatment temperature be 10-25 DEG C, such as 10 DEG C, 14 DEG C, 18 DEG C, 22 DEG C or
25 DEG C etc.；The coating film treatment time is 8-30min, such as 8min, 13min, 18min, 23min or 30min.Certainly,
The concentration of sour second acid solution is higher in electrolyte, and the coating film treatment temperature is higher, can be within a short period of time
Produce certain thickness oxidation film.
In addition, the coating film treatment process of present embodiment is carried out after roughened surface etching process is carried out to metal
, that is to say, that oxide-film can be also coated with the nanoscale hole hole that the roughened surface etching process produces, it is so favourable
In the anticorrosive and wear-resisting property for the metal for improving the surface generation nanoscale hole hole.And in the prior art, typically plating
Multiple lye etching is carried out again after film, and therefore, lye needs first to go out the oxide-film of the metal surface, could be to metal sheet
Body is etched, and the resistance of the etching process is very big；Therefore, it is necessary to carry out multiple lye etching, and the nano grade pore produced
The size in hole is smaller, is unfavorable for the combination of plastics in the metal after coarse surface treatment and follow-up injection moulding process, obtained production
Quality is poor.
S500, carry out drying and processing to the metal after the coating film treatment.
In the step S500, drying and processing is carried out to the metal after the coating film treatment, can effectively prevent product
Bacterium is grown in the residual water on surface or chemical reaction occurs and corrodes the product, influences product quality.Specifically, according to described
The factors such as the residual volume of product surface moisture, environment temperature determine the temperature and time of drying and processing, and usual treatment temperature is 50-
80 DEG C, such as 50 DEG C, 60 DEG C, 70 DEG C or 80 DEG C；Processing time is 20-50min, such as 20min, 30min, 40min or 50min
Etc..Certainly, treatment temperature is higher, and required processing time is shorter.
In addition, in the step S100-S400, metal surface can all be cleaned after each step, it is described clear
Wash journey to clean the metal surface after processing using water or alcohol etc., the mode of the cleaning is clear for flushing or ultrasound
Wash.
Further, please refer to Fig.2, Fig. 2 is that surface produces nanoscale hole hole in metallic surface processing method of the present invention
Metal scanning electron microscope schematic diagram, from figure 2 it can be seen that after being handled using the above method, the surface produces nanoscale
The metal of hole, the pore diameter range of the nanoscale hole hole is 20-150nm, and the pore diameter range of the nanoscale hole hole is main
Concentrate on 50-120nm；And surface produces the metal of nanoscale hole hole in prior art metallic surface processing method in Fig. 3
In scanning electron microscope schematic diagram, the pore diameter range of the nanoscale hole hole is concentrated mainly on 20-40nm；As it can be seen that using acid sand
Reagent, which carries out pending metal roughened surface etching process mode, to produce larger-sized nanoscale in metal surface
Hole, and 2-3 times that the size of the nanoscale hole hole is the prior art, are conducive to improve metal and modeling in follow-up injection moulding process
The combination power of material；It is with short production cycle and technique is simple, it is easy to utilize.
Based on the above method, the invention also discloses a kind of metal product, wherein, the metal product uses the above method
Obtained after processing.
Based on the above method, the invention also discloses a kind of metallo-plastic complex, wherein, the metallo-plastic complex
Including：Above-mentioned metal product and the plastics for being moulded in the surface of metal product.Due to the nanoscale of the surface of metal product
Bore hole size is larger, can combine closely with the plastics in the injection moulding process, improves the knot of the metallo-plastic complex
Structure stability.
Illustrate that surface that the above-mentioned method of the application is obtained has the gold of nano aperture below with specific embodiment
Category and metallo-plastic complex.
Embodiment 1：
Pretreatment：The ungrease treatment temperature be 70 DEG C at, by the pending immersion metal in concentration be 40g/L
Degreasing agent ELC409 in 7min, ungrease treatment is carried out to the pending metal, and the metal of the ungrease treatment is carried out
Washing, obtains the metal after ungrease treatment；Afterwards, in the case where the temperature of the ungrease treatment is 35 DEG C, after the ungrease treatment
Immersion metal in the nitric acid of 200g/L 3min, sour neutralisation treatment is carried out to the metal after the ungrease treatment, and to described
After the metal of sour neutralisation treatment is washed, pretreated metal is obtained；
Roughened surface etching process：, will be described pretreated in the case where the coarse surface treatment temperature is 20 DEG C
Immersion metal in the concentration containing ferric trichloride be 170g/L, the concentration of hydrochloric acid is 150g/L, the concentration of hydrogen fluoride ammonia is 120g/
L, 5min in the acid sand reagent that the concentration of copper chloride is 25g/L and the concentration of sulfuric acid is 160g/L compositions, to the pre- place
Metal after reason carries out roughened surface etching process, and after being washed to the metal of the coarse surface treatment, obtains
Metal after roughened surface etching process；
Remove Slag treatment in surface：Remove the gred in first subsurface at 40 DEG C of temperature, by the roughened surface etching process
The 3min in the piece aqueous slkali of 90g/L of immersion metal afterwards, first is carried out to the metal after the roughened surface etching process
Subsurface removes Slag treatment, and after being washed to the metal of first subsurface slagging-off processing, obtains the first subsurface and remove
Metal after Slag treatment；At final 35 DEG C of the temperature of surface slagging-off, the immersion metal after the first time is surface-treated
The 3min in the salpeter solution of 200g/L, the metal after being surface-treated to the first time carry out final slagging-off surface treatment, and
After being washed to the final surface except the metal of Slag treatment, surface is obtained except the metal after Slag treatment；
Coating film treatment：Using graphite as cathode, anode is done in the surface except the metallic aluminium after Slag treatment, is containing the dense of sulfuric acid
It is 18 DEG C in coating temperature in the electrolyte that the concentration spent for 260g/L, phosphoric acid is 260g/L and the concentration of oxalic acid is 260g/L,
Under conditions of plated film time is 18min, the metal after removing the gred to the surface carries out coating film treatment, and to the coating film treatment
Metal washed after, obtain the metal after coating film treatment；
Drying and processing：In the case where drying and processing temperature is 60 DEG C, to the metal drying and processing 30min after the coating film treatment,
Drying and processing is carried out to the metal after the coating film treatment, obtains metal product.
Injection process:Metal product after the drying is cooled to room temperature, then by it by way of injection molding
It is combined together with plastics, forms metallo-plastic complex；
Tested with reference to power：Pulling force survey is carried out to the metallo-plastic complex of injection molding using push-pull effort machine HM-6605C
Examination, the results are shown in Table 1.
Embodiment 2：
Pretreatment：The ungrease treatment temperature be 30 DEG C at, by the pending immersion metal in concentration be 80g/L
Degreasing agent ELC409 in 9min, ungrease treatment is carried out to the pending metal, and the metal of the ungrease treatment is carried out
Washing, obtains the metal after ungrease treatment；Afterwards, in the case where the temperature of the ungrease treatment is 25 DEG C, after the ungrease treatment
Immersion metal in the nitric acid of 300g/L 4min, sour neutralisation treatment is carried out to the metal after the ungrease treatment, and to described
After the metal of sour neutralisation treatment is washed, pretreated metal is obtained；
Roughened surface etching process：, will be described pretreated in the case where the coarse surface treatment temperature is 20 DEG C
Immersion metal 7min in the acid sand reagent that the concentration containing hydrochloric acid is 210g/L and the concentration of sulfuric acid is 100g/L compositions,
Roughened surface etching process is carried out to the pretreated metal, and water is carried out to the metal of the coarse surface treatment
After washing, the metal after roughened surface etching process is obtained；
Remove Slag treatment in surface：Remove the gred in first subsurface under temperature 50 C, by the roughened surface etching process
The 5min in the piece aqueous slkali of 10g/L of immersion metal afterwards, first is carried out to the metal after the roughened surface etching process
Subsurface removes Slag treatment, and after being washed to the metal of first subsurface slagging-off processing, obtains the first subsurface and remove
Metal after Slag treatment；Under the final surface slagging-off temperature 50 C, the immersion metal after the first time is surface-treated
The 5min in the salpeter solution of 100g/L, the metal after being surface-treated to the first time carry out final slagging-off surface treatment, and
After being washed to the final surface except the metal of Slag treatment, surface is obtained except the metal after Slag treatment；
Coating film treatment：Using graphite as cathode, anode is done in the surface except the metallic aluminium after Slag treatment, is in the concentration of phosphoric acid
It it is 14 DEG C in coating temperature, under conditions of plated film time is 23min, after removing the gred to the surface in the electrolyte of 400g/L
Metal carries out coating film treatment, and after being washed to the metal of the coating film treatment, obtains the metal after coating film treatment；
Drying and processing：In the case where drying and processing temperature is 60 DEG C, to the metal drying and processing 40min after the coating film treatment,
Drying and processing is carried out to the metal after the coating film treatment, obtains metal product.
Injection process:Metal product after the drying is cooled to room temperature, then by it by way of injection molding
It is combined together with plastics, forms metallo-plastic complex；
Tested with reference to power：Pulling force survey is carried out to the metallo-plastic complex of injection molding using push-pull effort machine HM-6605C
Examination, the results are shown in Table 1.
Embodiment 3：
Pretreatment：The ungrease treatment temperature be 35 DEG C at, by the pending immersion metal in concentration be 80g/L
Degreasing agent ELC409 in 3min, ungrease treatment is carried out to the pending metal, and the metal of the ungrease treatment is carried out
Washing, obtains the metal after ungrease treatment；Afterwards, in the case where the temperature of the ungrease treatment is 30 DEG C, after the ungrease treatment
Immersion metal in the nitric acid of 250g/L 1min, sour neutralisation treatment is carried out to the metal after the ungrease treatment, and to described
After the metal of sour neutralisation treatment is washed, pretreated metal is obtained；
Roughened surface etching process：, will be described pretreated in the case where the coarse surface treatment temperature is 30 DEG C
Immersion metal is in the concentration containing hydrochloric acid is 100g/L, the concentration of hydrogen fluoride ammonia is 200g/L and the concentration of sulfuric acid is 250g/L groups
Into acid sand reagent in 7min, roughened surface etching process is carried out to the pretreated metal, and to described thick
After the metal of roughened surface processing is washed, the metal after roughened surface etching process is obtained；
Remove Slag treatment in surface：Remove the gred in first subsurface under temperature 45 C, by the roughened surface etching process
The 2min in the piece aqueous slkali of 50g/L of immersion metal afterwards, first is carried out to the metal after the roughened surface etching process
Subsurface removes Slag treatment, and after being washed to the metal of first subsurface slagging-off processing, obtains the first subsurface and remove
Metal after Slag treatment；Under the final surface slagging-off temperature 45 C, the immersion metal after the first time is surface-treated
The 2min in the salpeter solution of 150g/L, the metal after being surface-treated to the first time carry out final slagging-off surface treatment, and
After being washed to the final surface except the metal of Slag treatment, surface is obtained except the metal after Slag treatment；
Coating film treatment：Using graphite as cathode, anode is done in the surface except the metallic aluminium after Slag treatment, is containing the dense of sulfuric acid
The concentration spent for 180g/L and oxalic acid is in the electrolyte of 340g/L, is 22 DEG C in coating temperature, plated film time is the bar of 13min
Under part, the metal after removing the gred to the surface carries out coating film treatment, and after being washed to the metal of the coating film treatment, obtains
Metal after to coating film treatment；
Drying and processing：In the case where drying and processing temperature is 70 DEG C, to the metal drying and processing 30min after the coating film treatment,
Drying and processing is carried out to the metal after the coating film treatment, obtains metal product.
Injection process:Metal product after the drying is cooled to room temperature, then by it by way of injection molding
It is combined together with plastics, forms metallo-plastic complex；
Tested with reference to power：Pulling force survey is carried out to the metallo-plastic complex of injection molding using push-pull effort machine HM-6605C
Examination, the results are shown in Table 1.
Embodiment 4：
Pretreatment：The ungrease treatment temperature be 40 DEG C at, by the pending immersion metal in concentration be 60g/L
Degreasing agent GT-TZ102 in 5min, carry out ungrease treatment to the pending metal, and to the metal of the ungrease treatment into
Row washing, obtains the metal after ungrease treatment；Afterwards, in the case where the temperature of the ungrease treatment is 45 DEG C, by the ungrease treatment
The 2min in the nitric acid of 150g/L of immersion metal afterwards, carries out the metal after the ungrease treatment sour neutralisation treatment, and to institute
State sour neutralisation treatment metal washed after, obtain pretreated metal；
Roughened surface etching process：, will be described pretreated in the case where the coarse surface treatment temperature is 50 DEG C
Immersion metal in the concentration containing ferric trichloride be 300g/L, the concentration of hydrochloric acid is 300g/L, the concentration of hydrogen fluoride ammonia is 200g/
L, 3min in the acid sand reagent that the concentration of copper chloride is 50g/L and the concentration of sulfuric acid is 300g/L compositions, to the pre- place
Metal after reason carries out roughened surface etching process, and after being washed to the metal of the coarse surface treatment, obtains
Metal after roughened surface etching process；
Remove Slag treatment in surface：Remove the gred in first subsurface at 35 DEG C of temperature, by the roughened surface etching process
The 1min in the piece aqueous slkali of 130g/L of immersion metal afterwards, first is carried out to the metal after the roughened surface etching process
Subsurface removes Slag treatment, and after being washed to the metal of first subsurface slagging-off processing, obtains the first subsurface and remove
Metal after Slag treatment；At final 30 DEG C of the temperature of surface slagging-off, the immersion metal after the first time is surface-treated
The 1min in the salpeter solution of 250g/L, the metal after being surface-treated to the first time carry out final slagging-off surface treatment, and
After being washed to the final surface except the metal of Slag treatment, surface is obtained except the metal after Slag treatment；
Coating film treatment：Using graphite as cathode, anode is done in the surface except the metallic aluminium after Slag treatment, is containing the dense of sulfuric acid
It is 25 DEG C in coating temperature in the electrolyte that the concentration spent for 100g/L, phosphoric acid is 100g/L and the concentration of oxalic acid is 100g/L,
Under conditions of plated film time is 8min, the metal after removing the gred to the surface carries out coating film treatment, and to the coating film treatment
Metal washed after, obtain the metal after coating film treatment；
Drying and processing：In the case where drying and processing temperature is 50 DEG C, to the metal drying and processing 50min after the coating film treatment,
Drying and processing is carried out to the metal after the coating film treatment, obtains metal product.
Injection process:Metal product after the drying is cooled to room temperature, then by it by way of injection molding
It is combined together with plastics, forms metallo-plastic complex；
Tested with reference to power：Pulling force survey is carried out to the metallo-plastic complex of injection molding using push-pull effort machine HM-6605C
Examination, the results are shown in Table 1.
Embodiment 5：
Pretreatment：The ungrease treatment temperature be 25 DEG C at, by the pending immersion metal in concentration be 50g/L
Degreasing agent VR6332-3 in 10min, carry out ungrease treatment to the pending metal, and to the metal of the ungrease treatment into
Row washing, obtains the metal after ungrease treatment；Afterwards, in the case where the temperature of the ungrease treatment is 50 DEG C, by the ungrease treatment
The 5min in the nitric acid of 100g/L of immersion metal afterwards, carries out the metal after the ungrease treatment sour neutralisation treatment, and to institute
State sour neutralisation treatment metal washed after, obtain pretreated metal；
Roughened surface etching process：, will be described pretreated in the case where the coarse surface treatment temperature is 60 DEG C
Immersion metal in the concentration containing ferric trichloride is 30g/L, the concentration of hydrochloric acid is 30g/L, the concentration of hydrogen fluoride ammonia be 20g/L,
10min in the acid sand reagent that the concentration of copper chloride is 5g/L and the concentration of sulfuric acid is 30g/L compositions, after the pretreatment
Metal carry out roughened surface etching process, and after being washed to the metal of the coarse surface treatment, obtain coarse
Change the metal after the etching process of surface；
Remove Slag treatment in surface：Remove the gred in first subsurface at 25 DEG C of temperature, by the roughened surface etching process
The 4min in the piece aqueous slkali of 150g/L of immersion metal afterwards, first is carried out to the metal after the roughened surface etching process
Subsurface removes Slag treatment, and after being washed to the metal of first subsurface slagging-off processing, obtains the first subsurface and remove
Metal after Slag treatment；At final 25 DEG C of the temperature of surface slagging-off, the immersion metal after the first time is surface-treated
The 4min in the salpeter solution of 300g/L, the metal after being surface-treated to the first time carry out final slagging-off surface treatment, and
After being washed to the final surface except the metal of Slag treatment, surface is obtained except the metal after Slag treatment；
Coating film treatment：Using graphite as cathode, anode is done in the surface except the metallic aluminium after Slag treatment, is containing the dense of sulfuric acid
It is 10 DEG C in coating temperature in the electrolyte that the concentration spent for 300g/L, phosphoric acid is 300g/L and the concentration of oxalic acid is 300g/L,
Under conditions of plated film time is 30min, the metal after removing the gred to the surface carries out coating film treatment, and to the coating film treatment
Metal washed after, obtain the metal after coating film treatment；
Drying and processing：In the case where drying and processing temperature is 80 DEG C, to the metal drying and processing 20min after the coating film treatment,
Drying and processing is carried out to the metal after the coating film treatment, obtains metal product.
Injection process:Metal product after the drying is cooled to room temperature, then by it by way of injection molding
It is combined together with plastics, forms metallo-plastic complex；
Tested with reference to power：Pulling force survey is carried out to the metallo-plastic complex of injection molding using push-pull effort machine HM-6605C
Examination, the results are shown in Table 1.
Comparative example：
Pretreatment：The ungrease treatment temperature be 70 DEG C at, by the pending immersion metal in concentration be 40g/L
Degreasing agent ELC409 in 7min, ungrease treatment is carried out to the pending metal, and the metal of the ungrease treatment is carried out
Washing, obtains the metal after ungrease treatment；Afterwards, in the case where the temperature of the ungrease treatment is 35 DEG C, after the ungrease treatment
Immersion metal in the nitric acid of 200g/L 3min, sour neutralisation treatment is carried out to the metal after the ungrease treatment, and to described
After the metal of sour neutralisation treatment is washed, pretreated metal is obtained；
Remove Slag treatment in surface：Remove the gred in first subsurface at 40 DEG C of temperature, by the roughened surface etching process
The 3min in the piece aqueous slkali of 90g/L of immersion metal afterwards, first is carried out to the metal after the roughened surface etching process
Subsurface removes Slag treatment, and after being washed to the metal of first subsurface slagging-off processing, obtains the first subsurface and remove
Metal after Slag treatment；At final 35 DEG C of the temperature of surface slagging-off, the immersion metal after the first time is surface-treated
The 3min in the salpeter solution of 200g/L, the metal after being surface-treated to the first time carry out final slagging-off surface treatment, and
After being washed to the final surface except the metal of Slag treatment, surface is obtained except the metal after Slag treatment；
Coating film treatment：Using graphite as cathode, anode is done in the surface except the metallic aluminium after Slag treatment, is containing the dense of sulfuric acid
It is 18 DEG C in coating temperature in the electrolyte that the concentration spent for 260g/L, phosphoric acid is 260g/L and the concentration of oxalic acid is 260g/L,
Under conditions of plated film time is 18min, the metal after removing the gred to the surface carries out coating film treatment, and to the coating film treatment
Metal washed after, obtain the metal after coating film treatment；
First time expanding treatment：In the case where the first time expanding treatment temperature is 30 DEG C, will be obtained after the coating film treatment
Technology be immersed in 5min in the sodium carbonate liquor of 30g/L, to after the coating film treatment metal carry out first time expanding treatment,
And after being washed to the metal of the first time expanding treatment, obtain the metal after first time expanding treatment；
Second of expanding treatment：In the case where second of expanding treatment temperature is 60 DEG C, by the first time expanding treatment
The 8min in the sodium carbonate liquor using 50g/L of immersion metal afterwards, the is carried out to the metal after the first time expanding treatment
Second reaming processing, and after being washed to the metal of second of expanding treatment, after obtaining second of expanding treatment
Metal；
Third time expanding treatment：In the case where the third time expanding treatment temperature is 25 DEG C, after second of reaming
Immersion metal 5min in the sodium carbonate liquor of 10g/L, third time reaming is carried out to the metal after second of expanding treatment
Processing, and after being washed to the metal of the third time expanding treatment, obtain the metal after third time expanding treatment；
Drying and processing：In the case where drying and processing temperature is 60 DEG C, to the metal drying and processing 30min after the coating film treatment,
Drying and processing is carried out to the metal after the coating film treatment, obtains metal product.
Injection process:Metal product after the drying is cooled to room temperature, then by it by way of injection molding
It is combined together with plastics, forms metallo-plastic complex；
Tested with reference to power：Pulling force survey is carried out to the metallo-plastic complex of injection molding using push-pull effort machine HM-6605C
Examination, the results are shown in Table 1.
Table 1
| Project | Tensile test result/KGF |
| Embodiment 1 | 141.50 |
| Embodiment 2 | 143.20 |
| Embodiment 3 | 148.60 |
| Embodiment 4 | 146.30 |
| Embodiment 5 | 143.70 |
| Comparative example | 121.22 |
It was found from the test result of table 1, to be significantly greater than and contrasted using the pulling force size of the embodiment 1-5 of the method for the present invention
The pulling force size of example, therefore, after the metal and injection molding after this method is handled, the combination power of product is strong, quality
It is good.
In addition, embodiment 1 and the production cycle contrast of comparative example are as shown in table 2；
Table 2
| Project | Production cycle/min |
| Embodiment 1 | 69 |
| Comparative example | 82 |
As can be known from the results of Table 2, the production week of comparative example is less than using the production cycle of the embodiment 1 of the method for the present invention
Phase, this is because, when other steps take essentially identical, technical scheme only needs a roughened surface etching
Processing, just can produce larger-size nanoscale hole hole in metal surface, and, it is necessary to repeatedly carry out reaming in the method for comparative example
Processing could produce nanoscale hole hole in technical face, and therefore, the metal surface treating method of this reverse side is with short production cycle, production
It is efficient.
The foregoing is merely embodiments of the present invention, are not intended to limit the scope of the invention, every to utilize this
The equivalent structure or equivalent flow shift that description of the invention and accompanying drawing content are made, it is relevant to be directly or indirectly used in other
Technical field, is included within the scope of the present invention.
Claims (12)
- A kind of 1. metallic surface processing method, it is characterised in that the described method includes：Roughened surface etching process is carried out to pending metal using acid sand reagent, nano grade pore is produced to obtain surface The metal in hole.
- 2. according to the method described in claim 1, it is characterized in that, the acidity sand reagent includes：Ferric trichloride, hydrochloric acid, One or more in hydrogen fluoride ammonia, copper chloride or sulfuric acid.
- 3. according to the method described in claim 2, it is characterized in that, in the acid sand reagent：The ferric trichloride Concentration is 30-300g/L；The concentration of the hydrochloric acid is 30-300g/L；The concentration of the hydrogen fluoride ammonia is 20-200g/L；It is described The concentration of copper chloride is 5-50g/L；The concentration of the sulfuric acid is 30-300g/L.
- 4. according to the method described in claim 3, it is characterized in that, during the roughened surface etching process, institute The temperature for stating acid sand reagent is 20-60 DEG C, processing time 1-10min.
- 5. according to the method described in claim 1, it is characterized in that, described carry out pending metal using acid sand reagent Before roughened surface etching process, further include：The pending metal is pre-processed, the pretreatment includes ungrease treatment and sour neutralisation treatment；The concentration of the degreasing agent is 30-50g/L, and the temperature of ungrease treatment is 50-80 DEG C, and the time of ungrease treatment is 3- 10min；In the sour neutralisation treatment, the concentration of nitric acid is 100-300g/L, and the temperature of sour neutralisation treatment is 25-50 DEG C, in acid Time with processing is 1-5min.
- 6. according to the method described in claim 1, it is characterized in that, described carry out pending metal using acid sand reagent After roughened surface etching process, further include：Surface is carried out to the metal after roughened surface etching process and removes Slag treatment；The metal after Slag treatment is removed to surface and carries out coating film treatment.
- 7. according to the method described in claim 6, it is characterized in that, surface is carried out to the metal after roughened surface etching process Except Slag treatment, including：First subsurface slagging-off processing carries out the metal after roughened surface etching process using alkaline solution；Metal after being handled using the first acid solution the first subsurface slagging-off is carried out final surface and removes Slag treatment；The alkaline solution is piece aqueous slkali, and the concentration of described aqueous slkali is 10-150g/L, the slagging-off processing of the first subsurface Temperature is 25-50 DEG C, and the time of the first subsurface slagging-off processing is 1-5min；First acid solution is salpeter solution, and the concentration of the salpeter solution is 100-300g/L, at final surface slagging-off The temperature of reason is 25-50 DEG C, and final surface is 1-5min except the time of Slag treatment.
- 8. according to the method described in claim 6, it is characterized in that, it is described to surface remove Slag treatment after metal carry out plated film at Reason, including：The metal after Slag treatment is removed to surface using the second acid solution and carries out coating film treatment.
- 9. according to the method described in claim 8, it is characterized in that, second acid solution is molten including sulfuric acid solution, phosphoric acid One or more in liquid or oxalic acid solution；When second acid solution is sulfuric acid solution, phosphoric acid solution or oxalic acid solution During mixed solution, wherein, the concentration of the sulfuric acid is 100-400g/L, and the concentration of the phosphoric acid is 100-400g/L, the grass The concentration of acid is 100-400g/L, and treatment temperature is 10-25 DEG C, processing time 8-30min.
- 10. according to claim 1-9 any one of them methods, it is characterised in that produce nanoscale hole hole for the surface Metal, the pore diameter range of the nanoscale hole hole is 20-150nm.
- 11. a kind of metal product, it is characterised in that the metal product is using the processing of any one of claim 1-10 the method Obtain afterwards.
- 12. a kind of metallo-plastic complex, it is characterised in that the metallo-plastic complex includes：The metal of claim 11 Product and the plastics for being moulded in the surface of metal product.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105500601A (en) * | 2014-09-24 | 2016-04-20 | 比亚迪股份有限公司 | Metal substrate, surface treatment method thereof, and metal-resin composite and production method therefor |
| CN105506703A (en) * | 2015-11-25 | 2016-04-20 | 广东长盈精密技术有限公司 | Preparation method of metal plastic compound |
| CN105729717A (en) * | 2014-12-09 | 2016-07-06 | 深圳富泰宏精密工业有限公司 | Metal-resin compound and preparation method thereof |
| CN105908185A (en) * | 2016-04-20 | 2016-08-31 | 东莞劲胜精密组件股份有限公司 | Stainless steel surface treatment method and preparation method of stainless steel plastic composite |
| CN106835139A (en) * | 2017-01-10 | 2017-06-13 | 广东长盈精密技术有限公司 | The surface treatment method of stainless steel, stainless steel products and stainless steel-plastics compounded body |
-
2017
- 2017-10-17 CN CN201710976683.8A patent/CN108018555A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105500601A (en) * | 2014-09-24 | 2016-04-20 | 比亚迪股份有限公司 | Metal substrate, surface treatment method thereof, and metal-resin composite and production method therefor |
| CN105729717A (en) * | 2014-12-09 | 2016-07-06 | 深圳富泰宏精密工业有限公司 | Metal-resin compound and preparation method thereof |
| CN105506703A (en) * | 2015-11-25 | 2016-04-20 | 广东长盈精密技术有限公司 | Preparation method of metal plastic compound |
| CN105908185A (en) * | 2016-04-20 | 2016-08-31 | 东莞劲胜精密组件股份有限公司 | Stainless steel surface treatment method and preparation method of stainless steel plastic composite |
| CN106835139A (en) * | 2017-01-10 | 2017-06-13 | 广东长盈精密技术有限公司 | The surface treatment method of stainless steel, stainless steel products and stainless steel-plastics compounded body |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109112542A (en) * | 2018-08-08 | 2019-01-01 | 广东长盈精密技术有限公司 | Sand agent, aluminium alloy surface treatment method and aluminium alloy and plastic composite articles |
| CN109082694A (en) * | 2018-08-23 | 2018-12-25 | 歌尔股份有限公司 | A kind of aluminum alloy materials and preparation method thereof and composite material |
| CN109392296A (en) * | 2018-09-10 | 2019-02-26 | 深圳科诺桥科技股份有限公司 | The preparation method of electromagnetic shielding film |
| CN109392296B (en) * | 2018-09-10 | 2019-11-15 | 深圳科诺桥科技股份有限公司 | The preparation method of electromagnetic shielding film |
| CN111549348A (en) * | 2020-05-15 | 2020-08-18 | 计锋 | Metal part surface treatment method and metal part plastic complex |
| CN111926330A (en) * | 2020-08-17 | 2020-11-13 | 无锡卡仕精密科技有限公司 | Corrosive agent and corrosion method suitable for CoCrMo high-temperature alloy of artificial joint |
| CN112708423A (en) * | 2020-12-15 | 2021-04-27 | 河北中瓷电子科技股份有限公司 | Acidic microetching reagent and method for treating metal lead |
| CN112779540A (en) * | 2020-12-15 | 2021-05-11 | 河北中瓷电子科技股份有限公司 | Metal surface treatment method and preparation method of plastic packaging shell |
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