CN109554741B - Titanium metal and plastic integrated surface treatment method and composite product thereof - Google Patents
Titanium metal and plastic integrated surface treatment method and composite product thereof Download PDFInfo
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Abstract
A titanium metal and plastic integrated surface treatment method comprises the following steps: degreasing; acid corrosion; removing ash; activating, namely removing an oxide film layer generated on the surface of the titanium workpiece in the former process, delaying the occurrence of secondary oxidation and ensuring the binding force between a binding layer prepared in the latter process and the titanium substrate; putting a titanium workpiece as an anode into an electrolytic working solution, wherein the electrolytic working solution comprises: electrifying and electrolyzing phosphoric acid and electrolytic adjusting liquid to obtain a bonding layer which is well bonded with the substrate and has a micropore structure with the diameter of 30-60nm on the surface of the titanium workpiece; first immersion cleaning; performing second immersion cleaning to form a layer of adsorption filling film in the micropores of the bonding layer; and (5) drying. The invention overcomes the defects of strong surface activity and easy oxidation of titanium metal during pretreatment, and forms an ideal porous bonding layer on the surface of the titanium metal through special electrolytic oxidation and post-treatment, thereby not only ensuring the bonding strength of the bonding layer and the titanium substrate, but also meeting the integration requirement of heat flow plastic and the bonding layer during injection molding.
Description
Technical Field
The invention belongs to a surface treatment process of titanium metal, and relates to an innovative surface treatment method for finally forming a titanium-plastic composite product by integrating titanium, a titanium alloy material and plastic.
Background
The metal and plastic integrated combination technology is relatively mature in application to metal materials such as aluminum, copper, iron, stainless steel and the like, and is widely applied to parts of automobiles, household appliances and electronic products. Titanium metal is a preferred material of high-end products due to the characteristics of high specific strength, high corrosion resistance and light weight, but at present, no mature treatment process for titanium and titanium alloy materials can realize the integrated combination with plastic, so the industrial application of the titanium and titanium alloy materials is greatly limited.
The key of the metal and plastic combining technology lies in two points:
(1) specific structure on the metal surface microscopical:
the metal is formed into a nano-micron porous or gully surface with bearing strength by a certain method, the surface layer is called as an active bonding layer (hereinafter referred to as bonding layer) of the metal, the bonding layer can be formed on the metal surface by a physical method or chemical corrosion, or a metal conversion film is formed by a certain chemical or electrochemical reaction, and the conversion film has good bonding strength with a base metal.
(2) Chemical activity of the bonding layer:
including strong adsorption characteristics due to the surface energy of the microstructure of the bonding layer and bonding characteristics between non-metallic or organic functional groups generated by chemical bonding or physical filling and the heat flow plastic.
The conventional surface treatment methods for titanium and titanium alloy materials cannot realize the two points at the same time, so that the titanium and titanium alloy materials are difficult to realize integrated molding with plastic, and the practical application of a titanium-plastic composite structure meeting the requirements is not available at present.
The surface treatment process aiming at the relatively close titanium and titanium alloy materials comprises the following steps:
(1) titanium alloy conversion coating (zinc-based or manganese-based): the method is characterized in that a microscopic gully surface can be formed, can be used as a common film coating surface for bearing, and has certain binding force, but the binding force between a conversion film and a base material is poor, so that the strength requirement of forming an integrated structure with engineering plastic cannot be met.
(2) Anodizing the titanium alloy: the method is characterized in that a nano-scale porous bonding layer cannot be generated during anodic oxidation like aluminum alloy, the surface activity is poor, and the generated oxidizing bonding layer is not firmly bonded with a titanium metal substrate due to extremely active surface chemical properties of titanium metal, so that the titanium plastic basically has no bonding force after injection molding and is easy to degum and separate.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide an integrated surface treatment method of titanium metal and plastic and a composite product thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: a titanium metal and plastic integrated surface treatment method comprises the following steps:
(I) pretreatment:
1. degreasing, namely removing oil stains on the surface of the titanium workpiece;
2. acid corrosion, namely removing oxide skin and pollutants on the surface layer of the titanium workpiece to obtain a uniform and consistent surface;
3. removing ash, namely removing a layer of floating ash remained on the surface of the titanium workpiece;
4. activating, namely removing an oxide film layer generated on the surface of the titanium workpiece in the former process, delaying the occurrence of secondary oxidation and ensuring the binding force between a binding layer prepared in the latter process and the titanium substrate;
(II) electrolytic oxidation:
5. putting a titanium workpiece as an anode into an electrolytic working solution, wherein the electrolytic working solution comprises: 150-200g/L phosphoric acid and 100-150ml/L electrolytic adjusting liquid, wherein the electrolytic adjusting liquid comprises: electrifying and electrolyzing a strong oxidizing substance to obtain a bonding layer which is well bonded with the substrate and has a micropore structure with the diameter of 30-60nm on the surface of the titanium workpiece;
(III) post-treatment:
6. the first immersion cleaning is carried out, and residues of the titanium workpiece bonding layer are cleaned out;
7. performing second immersion cleaning to form a layer of adsorption filling film in the micropores of the bonding layer;
8. and (4) drying, namely putting the titanium workpiece into a dust-free hot air oven for drying.
In the 4 th step, the activating working solution comprises: 20-40ml/L of phosphoric acid, 3-8g/L of sodium fluoride and 180ml/L of activation protective solution, the treatment temperature is normal temperature, and the treatment time is 30-60S.
The activation protection solution comprises: glycerol, sodium xylene sulfonate and water.
In the 7 th step, the second time immersion cleaning working solution comprises: the dosage of the absolute ethyl alcohol, EDTA, the coupling agent and the water is 180-250ml/L, the treatment temperature is normal temperature, and the treatment time is 2-3 min.
In the step 5, the treatment temperature is 25 ℃, the voltage is 10-15V, the electrolysis is carried out for 10min, and the cathode material adopts an SUS316 stainless steel plate or a pressed activated carbon plate.
In the 6 th step, the first-time immersion cleaning working solution comprises: triethanolamine, anhydrous sodium carbonate, EDTA and water, the dosage is 180 plus 250ml/L, the treatment temperature is normal temperature, and the treatment time is 2-3 min.
In step 3, the ash removal working solution comprises: 30-50ml/L of hydrofluoric acid and 60-100ml/L of nitric acid, and the treatment temperature is normal temperature and the treatment time is 1-2 min.
In the step 2, the acid etching working solution comprises: 60-100ml/L of hydrofluoric acid, 350ml/L of phosphoric acid and 10-20ml/L of ethylene glycol, the treatment temperature is normal temperature, and the treatment time is 30 s.
Water washing treatment is carried out between each step.
A composite product prepared by a titanium metal and plastic integrated surface treatment method comprises the following steps: the titanium workpiece and the plastic integrally formed on the surface of the titanium workpiece are prepared by the surface treatment method.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to an innovative electrolytic oxidation surface treatment process for titanium and titanium alloy materials, which is different from a common anodic oxidation process.
The invention overcomes the defects of strong surface activity and easy oxidation of titanium metal during pretreatment, and forms an ideal porous bonding layer on the surface of the titanium metal through special electrolytic oxidation and post-treatment, thereby not only ensuring the bonding strength of the bonding layer and the titanium substrate, but also meeting the integration requirement of heat flow plastic and the bonding layer during injection molding.
Drawings
In order to more clearly illustrate the technical solution in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced, wherein:
FIG. 1 is a 3W magnification of the microporous bonding layer of titanium metal of the present invention;
FIG. 2 is an enlarged view of the microporous titanium bonding layer of the present invention taken at 10W times;
FIG. 3 is an enlarged view of the microporous titanium bonding layer of the present invention taken at 20W times;
FIG. 4 is a structural diagram of a composite product of titanium metal and plastic according to embodiment 2 of the present invention;
fig. 5 is a structural diagram of a composite product of titanium metal and plastic according to embodiment 3 of the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments. In the preferred embodiments, the terms "upper", "lower", "left", "right", "middle" and "a" are used for clarity of description only, and are not used to limit the scope of the invention, and the relative relationship between the terms and the terms is not changed or modified substantially without changing the technical content of the invention.
Example 1
The invention relates to a titanium metal and plastic integrated surface treatment method, which mainly comprises the following process flows of: degreasing, washing, acid etching, ash removal and activation are pre-treatment processes, the first soaking, the second soaking and the drying are post-treatment processes, the operation of each flow step is described in detail below.
(I) pretreatment:
1. degreasing and removing oil stains on the surface of the titanium workpiece. Because a very thin compact oxide film is easily generated on the surface of titanium metal, and the titanium metal has very high stability in air and acid, alkali and salt solutions, the titanium metal is basically suitable for all treatment processes such as mechanical cleaning, solvent cleaning, chemical degreasing and the like. The invention does not make a key explanation, and only provides a more conventional alkaline degreasing process, wherein the degreasing agent comprises: 80g/L sodium hydroxide, 30g/L sodium carbonate, 40g/L sodium phosphate, 10g/L sodium silicate and 0P-102g/L sodium silicate, the treatment temperature is 60-70 ℃, the treatment time is 5-10min, and ultrasonic wave can be adopted for auxiliary cleaning.
2. Acid corrosion, the titanium work piece is basically processed and formed through processes such as forging, CNC (computer numerical control) processing or heat treatment, so that the titanium work piece generates thicker oxide skin and residual metal pollutants which are firmly adsorbed on the surface, the surface condition is complex and uneven, the oxide skin and the pollutants on the surface layer of the titanium work piece can be effectively removed through acid corrosion, not only can a uniform surface be obtained, but also a certain roughness can be formed on the surface, the specific surface area of subsequent titanium-plastic integrated forming is increased, and the bonding strength of titanium-plastic combination is facilitated.
The acid corrosion working solution comprises: 60-100ml/L of 40% hydrofluoric acid, 350ml/L of 85% phosphoric acid and 10-20ml/L of ethylene glycol, the treatment temperature is normal temperature, the treatment time is 30s, and the titanium workpiece slightly swings at the same time. Hydrofluoric acid is used for reacting titanium in the acid corrosion process, and can be replaced by acidic ammonium fluoride generally; phosphoric acid can improve the viscosity of the working solution, effectively reduce the escape speed of reaction gas, not only enable hydrogen to linger on the surface of titanium to play a role in corrosion inhibition, but also reduce the volatilization of hydrogen fluoride, enable the working solution to be more stable, and weaken the pungent smell generated during treatment; the ethylene glycol plays a certain auxiliary role, can enhance the interface dispersibility in the working solution, enables the corrosion of the titanium surface to be more uniform, and has the function of improving the viscosity.
3. Except for ash, common industrial titanium products are all alloy materials except metal pure titanium, contain a small amount of other metal and nonmetal components, and after the acid corrosion treatment, a layer of ash black floating ash is always remained on the surface of a titanium workpiece, so that the titanium workpiece needs to be further removed.
The ash removal working solution comprises: 30-50ml/L of hydrofluoric acid with the concentration of 40% and 60-100ml/L of nitric acid with the concentration of 65%, the treatment temperature is normal temperature, the treatment time is 1-2min, and the titanium workpiece slightly swings at the same time. After the ash removal treatment, the titanium workpiece can obtain a clean silver white surface with certain degree of matte.
4. Since activation is extremely chemically active, titanium metal itself is very clean after ash removal treatment, but instantaneous oxidation is likely to occur in water or air, and therefore, special activation treatment is required to ensure the adhesion between the bonding layer formed in the subsequent step and the surface of the titanium substrate.
The activation working solution comprises: 20-40ml/L of phosphoric acid with the concentration of 85%, 3-8g/L of sodium fluoride and 120-180ml/L of activation protective solution, the treatment temperature is normal temperature, the treatment time is 30-60S, and the titanium workpiece slightly swings at the same time, wherein the activation protective solution comprises: 30 percent of glycerol (namely glycerol), 10 percent of sodium xylene sulfonate and the balance of water. The working solution effectively delays the occurrence of secondary oxidation while removing an oxide film layer generated on the surface of the titanium metal in the former process, thereby ensuring the binding force between a binding layer prepared in the later process and the titanium substrate.
In order to ensure the binding force between the micropore binding layer generated by the next step of electrolytic oxidation and the titanium substrate, the chemical activity of the titanium metal surface when the electrolytic oxidation is carried out must be ensured, namely, the advanced oxidation is avoided. In the ash removal of the previous step, the titanium metal surface is very easily oxidized after the ash removal and during washing because of the activity of the titanium metal itself and the fact that the ash removal liquid contains nitric acid with strong oxidizing property. The activation aims to ensure the activity of the titanium metal surface before electrolytic oxidation, wherein the mechanism is that hydrogen ions and fluorine ions provided by phosphoric acid and sodium fluoride can remove an oxide film layer on the surface of a titanium workpiece, so that an active titanium substrate is exposed to play a main activation role, the form and the components of titanium oxide are complex, only titanium dioxide is taken as an example, and the reaction formula is as follows:
TiO2+6HF＝＝H2TiF6+2H2O
the activating protection solution is used for protecting the surface of the activated titanium substrate and delaying the secondary oxidation of the activated titanium substrate, and the mechanism is that a small amount of oxygen can be dissolved in the working solution, glycerol is dispersed on the surface of the titanium metal and has a certain isolation effect to weaken the contact chance of the oxygen and the surface of the titanium metal, and when a titanium workpiece leaves the working solution and contacts with air, the glycerol can be remained on the surface of the titanium metal to form a liquid film, the liquid film is thicker than a common water film and has a slow falling and breaking speed, so that the contact with the oxygen in the air is effectively blocked and delayed, and sodium xylene sulfonate is a surfactant with solubility, and can be beneficial to the uniform dispersion of the liquid film on the surface of the titanium metal.
(II) electrolytic oxidation:
5. putting a pretreated titanium workpiece serving as an anode into an electrolytic working solution, wherein the electrolytic working solution comprises: the concentration of 85 percent phosphoric acid is 150-. Wherein the cathode material adopts SUS316 stainless steel plate or pressed active carbon plate. The electrolysis regulating solution is the key for promoting the formation of micropores on the surface of the titanium metal.
Similar to aluminum alloy anodic oxidation, anodic oxidation of titanium metal in an acidic medium is a very complex electrochemical reaction process, and the mechanism of the anodic oxidation cannot be explained by a single chemical reaction formula at present, but basically understood as an equilibrium reaction process of anodic reaction on the surface of titanium metal to generate a dense oxide film (forward reaction) and dissolution of the oxide film (reverse reaction). Unlike anodic oxidation of aluminum alloys, in a single phosphoric acid, sulfuric acid or hydrochloric acid solution, the formation of a titanium oxide film is absolutely dominant, the dissolution of the oxide film is almost negligible, i.e., the forward reaction rate is much greater than the reverse reaction rate, and anodic oxidation is completed and nearly terminated in a short time. The aluminum anodic oxide film has a microporous structure because the dissolution rate of the oxide film is only lower than the generation rate of the oxide film, but the forward reaction ratio is still large, and the equilibrium of the reaction is continuous and changes continuously with time. Therefore, in a single acidic solution, although a dense anodic oxide film can be formed on the surface of the titanium metal, a porous structure similar to an aluminum anodic oxide film cannot be formed.
The invention has the original point that the related electrolytic conditioning solution can improve the reverse reaction speed of the dissolution of the titanium anodic oxide film, so that the oxide film is corroded in the vertical direction to form micropores. The electrolytic conditioning fluid is a solution of strong oxidizing substances, the proportioning mass concentration of the strong oxidizing substances is 30-35%, and the strong oxidizing substances comprise hydrogen peroxide, potassium permanganate, ammonium persulfate, sodium perchlorate and the like. The titanium anode oxide film can be chemically corroded under acidic conditions. The phosphoric acid is selected as the acidic medium, because the formation of the micropores of the oxide film is accompanied with the gasification reaction on the surface of the anode workpiece, the generated microbubbles have a barrier effect, can assist the selective dissolution of the oxide film, and are beneficial to the formation of the micropores, and compared with media such as sulfuric acid, hydrochloric acid and the like, the phosphoric acid solution has higher viscosity, so that the microbubbles are easy to linger on a reaction interface and are beneficial to the reaction.
(III) post-treatment:
6. in the first time of immersion cleaning, a micropore combined layer is formed on the surface of the titanium metal after electrolytic oxidation, acid liquor, electrolytic conditioning solution and other metal residues are in micropores, and the residues need to be cleaned in an acid-base neutralization, infiltration and replacement mode.
The first immersion cleaning working solution comprises: triethanolamine with the mass percentage of 5 percent, anhydrous sodium carbonate with the mass percentage of 15 percent, EDTA with the mass percentage of 15 percent and the balance of water, the dosage is 180ml/L, the treatment temperature is normal temperature, and the treatment time is 2-3 min. Through the first immersion cleaning, micropores of the bonding layer are cleaned, so that the specific surface area is greatly increased, the surface energy is obviously improved, and the bonding layer has a good active adsorption effect.
7. And (4) secondary soaking, wherein after primary cleaning of the primary soaking, the micropore binding layer on the surface of the titanium metal has an active adsorption characteristic. The second time of soaking and washing makes and carries out further washing to the bonding layer, can form very thin absorption filling film in the micropore of bonding layer, and this kind of filling film can not only play the guard action to the surface activity of bonding layer, can also take place crosslinking reaction between the plastic with the heat current when injection moulding to greatly increased the cohesion of titanium metal and plastic.
The second time immersion cleaning working solution comprises: 5 percent of absolute ethyl alcohol, 10 percent of EDTA, 10 percent of coupling agent and the balance of water by mass percent, the dosage is 180-250ml/L, the treatment temperature is normal temperature, and the treatment time is 2-3 min. At present, silane coupling agents such as 3-aminopropyltrimethoxysilane and 3-isocyanate propyltrimethoxysilane are widely applied. In the second immersion cleaning, the coupling agent can be dispersed into the microporous structure of the titanium metal surface binding layer and adsorbed on the inner wall of the micropores, alkoxy connected with silicon atoms in the coupling agent can be partially hydrolyzed into silanol, part of the silanol still remains after water washing, and a coupling agent molecular membrane is formed after drying and water loss. During integral injection molding, on one hand, silanol formed after hydrolysis of the silane coupling agent can perform condensation reaction with hydroxyl on the surface of the glass fiber material of the plastic reinforcement body to generate stable silicon-oxygen bonds, and in addition, organic groups of the coupling agent can form hydrogen bonds or chemical bonds with plastic resin, so that the coupling agent filling film can play a good role in connection between a titanium metal surface bonding layer and heat flow plastic to enhance the bonding between the titanium and the plastic.
8. And (4) drying, namely, putting the titanium workpiece washed by the pure water after the second soaking into a dust-free hot air oven for drying, wherein the drying temperature is 80-100 ℃, and the drying time is 10-20 min.
Water washing treatment is required between each step, so as to ensure that the treatment process of each step is fully completed.
The concentration percentages used in the present example are mass fraction percentages commonly used for chemical preparations, and are in accordance with the general industry standards.
Example 2
Referring to fig. 4, the composite product manufactured by the titanium metal and plastic integrated surface treatment method of the present invention includes: a titanium alloy test piece 1 and a plastic layer 2 integrally formed on the surface of the test piece.
The preparation process of the composite product comprises the following steps:
(2) processing an industrial titanium alloy plate into a test piece with the length of 50mm, the width of 15mm and the thickness of 1mm, wherein the processing mode can be any one of forging, stamping, linear cutting and CNC;
(1) preparing a micropore binding layer on the surface of a test piece, namely fixing the test piece by using a titanium wire or a special titanium hanger, and forming the micropore binding layer on the surface of the test piece after the pretreatment, electrolytic oxidation and post-treatment processes included in embodiment 1 of the invention;
(2) and (3) carrying out titanium-plastic integrated injection molding, namely putting the processed test piece into a customized test piece injection molding machine, and carrying out in-mold molding on the test piece and the heat flow plastic, so as to prepare an integrated composite product. The injection molding machine is a special nano injection molding machine, and the plastic can be polybutylene terephthalate (PBT), polyphenylene sulfide (PPS) resin, Polyamide (PA) resin or any one of glass fiber reinforced plastics of the three materials.
Aiming at the composite product, the bonding strength of the titanium metal and the plastic can be embodied by the drawing force value when the titanium plastic is reversely stretched and separated, a tension tester is used for testing, an induction device is connected with a digital display, and the data displayed when the test piece is separated from the plastic layer is the drawing force value.
In this embodiment, the test piece and three engineering plastics, namely PBT, PPS, and PA, are used to prepare corresponding composite products, and the drawing force test is performed respectively, and the results are as follows, it can be shown that the two are combined very firmly:
| type of plastic | PBT | PPS | PA |
| Numerical value of drawing force (kgf) | 120-160 | 160-200 | 180-240 |
Specifically, the following description is provided: in the embodiment, only three engineering plastics commonly used for nano injection molding are listed, but not limited thereto; in addition, the drawing force value has a certain difference due to the difference of the composition of the plastic material and the tensile strength of the plastic material.
Example 3
The invention relates to a composite product prepared by a titanium metal and plastic integrated surface treatment method, which comprises the following steps: a titanium alloy mobile phone middle frame 3 and a plastic part 4 integrally formed on the mobile phone middle frame.
The preparation process of the composite product comprises the following steps:
(2) forging, stamping or CNC (computer numerical control) processing an industrial titanium alloy plate, polishing, trimming and cleaning to obtain a semi-finished blank of the middle frame of the mobile phone;
(1) the preparation of the micropore binding layer on the surface of the titanium alloy mobile phone middle frame is characterized in that the mobile phone middle frame is fixed by a special titanium hanger, and the micropore binding layer is formed on the surface of the mobile phone middle frame after the pretreatment, electrolytic oxidation and post-treatment processes included in embodiment 1 of the invention;
(2) and (3) carrying out titanium-plastic integrated injection molding, namely putting the processed mobile phone middle frame into a customized mold in an injection molding machine, and carrying out in-mold molding with the heat flow plastic, so as to prepare an integrated composite product. The injection molding machine is a special nano injection molding machine, and the plastic can be polybutylene terephthalate (PBT), polyphenylene sulfide (PPS) resin, Polyamide (PA) resin or any one of glass fiber reinforced plastics of the three materials.
In practical application, after a composite product is prepared, redundant parts on a middle frame and a plastic part of a titanium alloy mobile phone are removed through multiple CNC (computerized numerical control) machining, the appearance of the surface is modified through procedures such as grinding and polishing, related appearance decoration surface treatment is carried out at the rear section, and multiple times of cleaning and high-temperature baking are needed in the whole process. According to the requirement of products, the titanium metal and the plastic must be combined very firmly, and the titanium and the plastic cannot be separated after the series of processing and treatment. The composite product prepared by the invention can ensure the bonding strength between titanium and plastic and meet the performance requirements.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any brief modifications, equivalent changes and modifications made by the technical spirit of the present invention to the above embodiments are within the technical scope of the present invention.
Claims (10)
1. A titanium metal and plastic integrated surface treatment method is characterized by comprising the following steps:
(I) pretreatment:
1. degreasing, namely removing oil stains on the surface of the titanium workpiece;
2. acid corrosion, namely removing oxide skin and pollutants on the surface layer of the titanium workpiece to obtain a uniform and consistent surface;
3. removing ash, namely removing a layer of floating ash remained on the surface of the titanium workpiece;
4. activating, namely removing an oxide film layer generated on the surface of the titanium workpiece in the former process, delaying the occurrence of secondary oxidation and ensuring the binding force between a binding layer prepared in the latter process and a substrate;
(II) electrolytic oxidation:
5. putting a titanium workpiece as an anode into an electrolytic working solution, wherein the electrolytic working solution comprises: 150-200g/L phosphoric acid and 100-150ml/L electrolytic adjusting liquid, wherein the electrolytic adjusting liquid comprises: electrifying and electrolyzing the solution containing 30-35% of strong oxidizing substances in proportion by mass concentration to obtain a bonding layer which is well bonded with the substrate and has a microporous structure on the surface of the titanium workpiece;
(III) post-treatment:
6. the first immersion cleaning is carried out, and residues of the titanium workpiece bonding layer are cleaned out;
7. performing second immersion cleaning to form a layer of adsorption filling film in the micropores of the bonding layer;
8. and (4) drying, namely putting the titanium workpiece into a dust-free hot air oven for drying.
2. The method for integrally treating the surface of the plastic and the titanium metal as claimed in claim 1, wherein in the step 4, the activating the working solution comprises: 20-40ml/L of phosphoric acid, 3-8g/L of sodium fluoride and 180ml/L of activation protective solution, the treatment temperature is normal temperature, and the treatment time is 30-60 s.
3. The titanium metal and plastic integrated surface treatment method according to claim 2, wherein the activation protection solution comprises: glycerol and sodium xylene sulfonate.
4. The titanium metal and plastic integrated surface treatment method according to claim 1, wherein in the step 7, the second immersion cleaning working solution comprises: absolute ethyl alcohol, EDTA and coupling agent, the treatment temperature is normal temperature, and the treatment time is 2-3 min.
5. The integrated surface treatment method for titanium metal and plastic cement as claimed in claim 1, wherein in the step 5, the treatment temperature is 25 ℃, the voltage is 10-15V, the electrolysis is carried out for 10min, and the cathode material is SUS316 stainless steel plate or pressed activated carbon plate; the strong oxidizing substance is hydrogen peroxide, potassium permanganate, ammonium persulfate or sodium perchlorate.
6. The titanium metal and plastic integrated surface treatment method according to claim 1, wherein in the step 6, the first immersion cleaning working solution comprises: triethanolamine, anhydrous sodium carbonate and EDTA, and the treatment temperature is normal temperature and the treatment time is 2-3 min.
7. The titanium metal and plastic integrated surface treatment method according to claim 1, wherein in the step 3, the ash removal working solution comprises: 30-50ml/L of hydrofluoric acid and 60-100ml/L of nitric acid, and the treatment temperature is normal temperature and the treatment time is 1-2 min.
8. The method for integrally treating the surface of the titanium metal and the plastic as claimed in claim 1, wherein in the step 2, the acid etching working solution comprises: 60-100ml/L of hydrofluoric acid, 350ml/L of phosphoric acid and 10-20ml/L of ethylene glycol, the treatment temperature is normal temperature, and the treatment time is 30 s.
9. The method for integrally treating the surface of plastic and metal titanium as recited in claim 1, wherein a water washing treatment is performed between each step.
10. A composite product prepared by a titanium metal and plastic integrated surface treatment method is characterized by comprising the following steps: a titanium workpiece and plastic integrally molded on the surface of the titanium workpiece, the titanium workpiece being prepared by the surface treatment method according to any one of claims 1 to 9.
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| JPS5511756B2 (en) * | 1972-06-20 | 1980-03-27 | ||
| CN102051653A (en) * | 2009-11-03 | 2011-05-11 | 北京有色金属研究总院 | Anodic oxidation solution for titanium and titanium alloy and surface oxidation and coloring method |
| CN103556202A (en) * | 2013-11-20 | 2014-02-05 | 沈阳工业大学 | Implementation method of anodic oxidation employing titanium alloy contact method |
| CN103993340B (en) * | 2014-05-20 | 2017-05-17 | 广东长盈精密技术有限公司 | Metal sheet as well as metal resin composite and preparation method thereof |
| CN104479152B (en) * | 2014-11-25 | 2018-12-11 | 李强 | A kind of gold modeling complex and its manufacturing method |
| CN105128260B (en) * | 2015-09-30 | 2017-07-21 | 东莞市科泰汽车检夹具有限公司 | A kind of metal shell of electronic product and preparation method thereof |
| CN108327167A (en) * | 2018-03-07 | 2018-07-27 | 广州凯腾新材料科技有限公司 | The method that metal and plastic cement combine |
-
2019
- 2019-01-21 CN CN201910056606.XA patent/CN109554741B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4187001A1 (en) * | 2021-11-16 | 2023-05-31 | Dongguan DSP Technology Co., Ltd. | Titanium surface treatment method |
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