CN109554741A - A kind of titanium surface treatment method integrated with plastic cement and its composite article - Google Patents
A kind of titanium surface treatment method integrated with plastic cement and its composite article Download PDFInfo
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- CN109554741A CN109554741A CN201910056606.XA CN201910056606A CN109554741A CN 109554741 A CN109554741 A CN 109554741A CN 201910056606 A CN201910056606 A CN 201910056606A CN 109554741 A CN109554741 A CN 109554741A
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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
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/1418—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the inserts being deformed or preformed, e.g. by the injection pressure
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Abstract
A kind of titanium surface treatment method integrated with plastic cement, includes the following steps: degreasing；Acid corrosion；Ash disposal；Activation delays the generation of secondary oxidation before removing while the oxide film layer of process titanium workpiece surface generation, the binding force of binder course and titanium substrate that after guarantee prepared by process；It is put into titanium workpiece as anode in electrolysis working solution, electrolysis working solution includes: phosphoric acid and electrolysis adjustment liquid, and be powered electrolysis, can be well combined in the acquisition of titanium workpiece surface with substrate, the binder course with diameter 30-60nm microcellular structure；It embathes for the first time；It embathes for the second time, forms one layer of absorption filling film in binder course micropore；Drying.The strong oxidizable disadvantage of surface-active that the present invention overcomes titaniums in preceding processing, and ideal porous binder course is formd in surface of metal titanium by special electrolytic oxidation and post-processing, the integral requirement of hot-fluid plastic cement and binder course when not only ensure that the bond strength of binder course and titanium substrate, but also having met injection molding.
Description
Technical field
The invention belongs to the process of surface treatment of titanium, are related to titanium or titanium alloy material and are formed with plastic cement integrated final
Titanium moulds a kind of innovative surface treatment method of composite article, and this method makes the knot that close and firm is realized between titanium and plastic cement
It closes.
Background technique
Application of the metal combination technology integrated with plastic cement in aluminium, copper, iron and stainless steel and other metal materials is relatively
Maturation is widely used on the components of automobile, household electrical appliance, electronic product.Titanium is since with high specific strength, height is anti-corrosion
Property and lightweight characteristic, and become high-end product preferred material, however at present for titanium or titanium alloy material still without maturation
Treatment process be able to achieve it is integrated with plastic cement combine, therefore significantly limit its industrial application.
The key of metal and plastic cement combination technology is two o'clock:
(1) metal surface it is microcosmic on specific structure:
I.e. by certain method make metal formed have bearing strength nano-micrometre grade is porous or gully surface, this
Superficial layer is referred to as the active binder course (hereinafter referred to as binder course) of metal, and binder course can pass through physical method or chemical attack
Be formed in metal surface, or the metal conversion film formed by certain chemistry or electrochemical reaction, this conversion film must and base
There is good bond strength between material metal.
(2) chemical activity of binder course:
It can be formed by strong characterization of adsorption comprising the surface by binder course microstructure, and pass through chemical bonding or physics
Fill the bonding performance formed between the nonmetallic or organo-functional group and hot-fluid plastic cement generated.
Above-mentioned two o'clock is not can be implemented simultaneously for the surface treatment method of titanium or titanium alloy material routine, so being difficult reality
Now with plastic cement integrated molding, the practical application of satisfactory titanium plastic composite structure there is no at present.
Have for the process of surface treatment of titanium or titanium alloy material relatively:
(1) titanium alloy conversion film (zinc system or manganese systems): feature is to form microcosmic gully surface, be can be used as general thin
The carrying of membrane coat surface, and there is certain binding force, limitation is that the binding force between conversion film and substrate is poor, is not achieved and engineering
The intensity requirement of plastic cement formation integral structure.
(2) titanium alloy anode oxidation: feature is that the same generation nanoscale in anodic oxidation of no image of Buddha aluminium alloy is porous
Binder course, surface-active is very poor, and since surface of metal titanium chemical property is extremely active, the oxidisability binder course and titanium of generation
Metallic substrates combine loosely, so after moulding substantially without binding force between titanium modeling, it is easy to degumming separation.
Summary of the invention
The technical problem to be solved by the present invention is to overcome above-mentioned the deficiencies in the prior art, a kind of titanium and plastic cement are provided
Integrated surface treatment method and its composite article.
The present invention solve above-mentioned technical problem the technical solution adopted is that: titanium surface treatment side integrated with plastic cement
Method includes the following steps:
(1) pre-treatment:
1, degreasing removes the greasy dirt of titanium workpiece surface；
2, acid corrosion removes the oxide skin and pollutant of titanium workpiece surface, obtains uniform surface；
3, ash disposal removes remaining one layer of titanium workpiece surface floating ash；
4, it activates, before removing while the oxide film layer of process titanium workpiece surface generation, delays the generation of secondary oxidation,
The binding force of binder course and titanium substrate that after guarantee prepared by process；
(2) electrolytic oxidation:
5, it is put into titanium workpiece as anode in electrolysis working solution, electrolysis working solution includes: phosphatase 11 50-200g/L and electricity
Solution adjustment liquid 100-150ml/L, electrolysis adjustment liquid includes: oxidizing species, and be powered electrolysis, can be obtained in titanium workpiece surface
It is well combined with substrate, the binder course with diameter 30-60nm microcellular structure；
(3) it post-processes:
6, it embathes for the first time, the residue of titanium workpiece binder course is cleaned out；
7, it embathes for the second time, forms one layer of absorption filling film in binder course micropore；
8, it dries, titanium workpiece is put into dustless hot-blast oven and is dried.
In step 4, activation working solution includes: phosphoric acid 20-40ml/L, sodium fluoride 3-8g/L and activation protection liquid 120-
180ml/L, treatment temperature room temperature handle time 30-60S.
The activation protection liquid includes: glycerine, sodium xylene sulfonate and water.
In step 7, embathing working solution for the second time includes: dehydrated alcohol, EDTA, couplant and water, dosage 180-
250ml/L, treatment temperature room temperature handle time 2-3min.
In step 5,25 DEG C for the treatment of temperature, voltage 10-15V, be powered electrolysis 10min, and cathode material uses SUS316 not
Become rusty steel plate or the active carbon slab of compacting.
In step 6, embathing working solution for the first time includes: triethanolamine, natrium carbonicum calcinatum, EDTA and water, and dosage is
180-250ml/L, treatment temperature room temperature handle time 2-3min.
In step 3, ash disposal working solution includes: that hydrofluoric acid 30-50ml/L and nitric acid 60-100ml/L, treatment temperature are normal
Temperature handles time 1-2min.
In step 2, acid corrosion working solution includes: hydrofluoric acid 60-100ml/L, phosphoric acid 250-350ml/L and ethylene glycol
10-20ml/L, treatment temperature room temperature handle time 30s.
Washing process is carried out between each step.
Composite article made from a kind of titanium surface treatment method integrated with plastic cement, comprising: titanium workpiece and integration
It is molded over the plastic cement of titanium workpiece surface, the titanium workpiece is prepared using above-mentioned surface treatment method.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is a kind of innovative electrolytic oxidation process of surface treatment of titanium or titanium alloy material, is different from general sun
Pole oxidation technology, this method meet titanium in the porous binder course that surface of metal titanium is formed and substrate is well combined, activity is strong
With the integrated molding requirement of plastic cement, it is finally made the composite article of titanium or titanium alloy and plastic cement.
The strong oxidizable disadvantage of surface-active that the present invention overcomes titaniums in preceding processing, and pass through special electrolysis oxygen
Change and post-process and form ideal porous binder course in surface of metal titanium, both ensure that the combination of binder course and titanium substrate was strong
The integral requirement of hot-fluid plastic cement and binder course when spending, and meeting injection molding.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, in which:
Fig. 1 is titanium micropore 3W times of enlarged drawing of binder course of the invention；
Fig. 2 is titanium micropore 10W times of enlarged drawing of binder course of the invention；
Fig. 3 is titanium micropore 20W times of enlarged drawing of binder course of the invention；
Fig. 4 is the titanium of the embodiment of the present invention 2 and the composite article structure chart of plastic cement；
Fig. 5 is the titanium of the embodiment of the present invention 3 and the composite article structure chart of plastic cement.
Specific embodiment
Below in conjunction with attached drawing and specific embodiment, the present invention is described further.Drawn in preferred embodiment
Such as "upper", "lower", "left", "right", " centre " and " one " term, only being illustrated convenient for narration, rather than to limit
The enforceable range of the present invention, relativeness are altered or modified, under the content of no substantial changes in technology, when being also considered as this hair
Bright enforceable scope.
Embodiment 1
A kind of titanium that the present invention designs surface treatment method integrated with plastic cement mainly includes following technique stream
Journey: degreasing --- --- washing --- --- acid corrosion --- --- washing --- --- ash disposal --- --- washing --- --- activation --- --- water
Wash --- --- electrolytic oxidation --- --- washing --- --- embathe for the first time --- --- washing --- --- embathe --- --- water for the second time
--- --- drying is washed, degreasing, acid corrosion, ash disposal and activation are pretreatment procedure, embathe for the first time, embathe and dry for the second time
For postprocessing working procedures, the operating process of each process step is detailed below.
(1) pre-treatment:
1, degreasing removes the greasy dirt of titanium workpiece surface.Due to surface of metal titanium one layer of very thin dense oxidation film easily generated,
Acid, alkali, there is in air and all high stability in saline solution, so it is clear to be applied basically for all machinery
The treatment process such as reason, solvent cleaning and chemical degreasing.The present invention does not make emphasis elaboration, only provides a kind of more conventional alkalinity
Degreasing process, degreasing agent include: sodium hydroxide 80g/L, sodium carbonate 30g/L, sodium phosphate 40g/L, sodium metasilicate 10g/L and 0P-
102g/L, handles time 5-10min by 60-70 DEG C for the treatment of temperature, can carry out auxiliary cleaning using ultrasonic wave.
2, acid corrosion, titanium workpiece are substantially by the techniques machine-shapings such as forging and stamping, CNC processing or heat treatment, this meeting
Titanium workpiece is set to generate oxide skin that is thicker and being securely adsorbed on surface and remaining metal pollutant, so that surface layer complex
And it is uneven, the oxide skin and pollutant of titanium workpiece surface can be effectively removed by sour corrosion, can not only obtain uniform one
The surface of cause, moreover it is possible to so that surface is formed certain roughness, the specific surface area combined when increasing subsequent titanium modeling integrated molding,
Be conducive to the adhesive strength that titanium modeling combines.
Acid corrosion working solution includes: the phosphoric acid 250-350ml/L of the hydrofluoric acid 60-100ml/L of concentration 40%, concentration 85%
And ethylene glycol 10-20ml/L, treatment temperature room temperature, time 30s is handled, titanium workpiece carries out slight oscillatory simultaneously.Acid corrosion work
What is reacted in skill to titanium is hydrofluoric acid, can also generally be substituted with acid ammonium fluoride；Phosphoric acid can promote the viscous of working solution
The evolution speed of reaction gas is effectively reduced in consistency, and hydrogen can not only be made to stay on titanium surface and play corrosion inhibition, moreover it is possible to be subtracted
The volatilization of few hydrogen fluoride, keeps working solution more stable, and weaken the penetrating odor generated when processing；Ethylene glycol plays certain
Booster action can enhance the interface dispersibility inside working solution, make the corrosion on titanium surface more evenly, at the same it also have promoted it is sticky
The effect of degree.
3, ash disposal, in addition to the pure titanium of metal, general industry titanium article is all alloy material, containing a small amount of other metals and
Non-metallic components, after above-mentioned acid corrosion processing, titanium workpiece surface often remains the floating ash of one layer of grey black, it is necessary into
The further removal of row.
Ash disposal working solution includes: the hydrofluoric acid 30-50ml/L of the concentration 40% and nitric acid 60-100ml/L of concentration 65%,
Treatment temperature room temperature, handles time 1-2min, and titanium workpiece carries out slight oscillatory simultaneously.After ash disposal is handled, titanium workpiece be can get
Silvery white surface clean and that there is certain mute degree.
4, activate, since titanium chemical activity itself is extremely strong, although after ash disposal is handled surface seem very
Cleaning, no matter but in water or in air or be easy to occur instantaneous oxidation, therefore in order to after ensureing process generate
The binding force of binder course and titanium substrate surface needs to carry out special activation processing.
Activation working solution includes: phosphoric acid 20-40ml/L, the sodium fluoride 3-8g/L and activation protection liquid 120- of concentration 85%
180ml/L, treatment temperature room temperature handle time 30-60S, and titanium workpiece carries out slight oscillatory simultaneously, wherein activation protection liquid packet
Include: mass percent is that 30% glycerine (i.e. glycerol), 10% sodium xylene sulfonate and balance of water form.Work
While the liquid oxide film layer that process surface of metal titanium generates before removal, effectively delay the generation of secondary oxidation, to protect
The binding force of binder course and titanium substrate that after card prepared by process.
Ensure the binding force of the micropore binder course that next step electrolytic oxidation generates and titanium substrate, it is necessary to assure enter electrolysis
The chemical activity of surface of metal titanium, that is, avoid premature oxidation when oxidation.In previous step ash disposal, due to the work of titanium itself
Property, in addition except oxidizing very strong nitric acid is contained in lixivium, so surface of metal titanium is extremely after the completion of ash disposal and when washing
It is oxidized easily.The purpose of activation is exactly the activity in order to guarantee surface of metal titanium before electrolytic oxidation, and wherein mechanism is, phosphorus
Acid can remove the oxide film layer of titanium workpiece surface with hydrogen ion provided by sodium fluoride and fluorine ion, so that active titanium substrate is naked
Exposing, plays main activation, titanyl compound form and comparison of ingredients are complicated, only by taking titanium dioxide as an example, reaction equation are as follows:
TiO2+ 6HF==H2TiF6+2H2O
And activating protection liquid is to delay it that secondary oxidation occurs to protect the titanium-based bottom surface after activation, mechanism is,
A small amount of oxygen molten can be deposited in working solution, glycerol dispersion has certain buffer action in surface of metal titanium, weakens oxygen
With the touch opportunity of surface of metal titanium, and titanium workpiece, when leaving working solution and air contacts, glycerine can also remain on titanium
Liquid film is formed on metal surface, this liquid film is thicker relative to common moisture film, and hang brokenly dissipate speed it is slower, effectively stop and
Delayed with the contact of oxygen in air, sodium xylene sulfonate is a kind of surfactant with solubilising, can help to liquid
Film is in the evenly dispersed of surface of metal titanium.
(2) electrolytic oxidation:
5, it is put into the titanium workpiece Jing Guo pre-treatment as anode in electrolysis working solution, electrolysis working solution includes: concentration
85% phosphatase 11 50-200g/L and electrolysis adjustment liquid 100-150ml/L, 25 DEG C of set temperature, voltage 10-15V, be powered electricity
Washing is taken out after solving 10min, can be obtained in surface of metal titanium and be well combined with substrate, there is diameter 30-60nm micropore
The binder course of structure can not visually be seen, be observed by high magnification numbe electron microscope, be obtained under Fig. 1 to 3 different multiples
Micrograph.Wherein cathode material using SUS316 stainless steel plate or suppresses active carbon slab.Electrolysis adjustment liquid is to promote titanium
The key of surface formation micropore.
Similar with aluminium alloy anode oxide, anodic oxidation of the titanium in acid medium is that extremely complex electrochemistry is anti-
Process is answered, mechanism can not also be interpreted at present by single chemical equation, but can be regarded as surface of metal titanium substantially
The balanced reaction process that anode reaction generates dense oxidation film (forward reaction) and oxidation film dissolution (back reaction) occurs.It is different
In aluminium alloy anode oxide, in single phosphoric acid, sulfuric acid or hydrochloric acid solution, the generation of titanium oxide film occupies absolute master
It leads, oxidation film dissolution can almost be ignored, i.e., forward reaction speed is far longer than back reaction speed, and anodic oxidation is very short
It completes in time and almost terminates.Why aluminium anode oxide film has microcellular structure, is the dissolution speed because of its oxidation film
Degree is only lower than oxidation film formation speed, but still forward reaction accounting is larger, and the balance of reaction continues and constantly becomes at any time
Change.Therefore in single acid solution, though surface of metal titanium can generate fine and close anode oxide film, similar aluminium can not be formed
The same porous structure of anode oxide film.
It is that the electrolysis adjustment liquid being related to can promote the reversed anti-of Ti anodic oxide film dissolution in place of original creation of the invention
Speed is answered, so that the corrosion of vertical direction occurs for oxidation film to form micropore.Electrolysis adjustment liquid is the molten of oxidizing species
Liquid, it is 30-35%, oxidizing species such as hydrogen peroxide, potassium permanganate, persulfuric acid that oxidizing species, which match mass concentration,
Ammonium, sodium perchlorate etc..Play the role of chemical attack to Ti anodic oxide film in acid condition.And the present invention select phosphoric acid as
Acid medium is because the formation of oxide-film micropore is accompanied by the gasification reaction on anode workpiece surface, and the microbubble of generation has
Barrier action, the selective dissolution of energy assisted oxidation film, is conducive to the formation of micropore, and compared to the media such as sulfuric acid, hydrochloric acid, phosphorus
Acid solution viscosity with higher is conducive to reaction and carries out so that microbubble is easy to stay in reaction interface.
(3) it post-processes:
6, it embathes for the first time, the surface of metal titanium after electrolytic oxidation forms micropore binder course, and acid is had in micropore
Liquid, electrolysis adjustment liquid and other metal residues need to wash out residue in such a way that acid-base neutralization penetrates into displacement
Come.
For the first time embathe working solution include: mass percent be 5% triethanolamine, 15% natrium carbonicum calcinatum, 15%
EDTA and excess water, dosage 180-250ml/L, treatment temperature room temperature, handle time 2-3min.It is soaked by first time
It washes, the micropore of binder course is cleaned out, increases specific surface area substantially, surface can significantly improve, therefore have living well
Property suction-operated.
7, it embathes for the second time, after the preliminary cleaning embathed for the first time, the micropore binder course of surface of metal titanium, which is presented, lives
Property characterization of adsorption.Embathing for the second time makes while further being cleaned to binder course, can be formed in the micropore of binder course
Very thin absorption filling film, this filling film can not only play a protective role to the surface-active of binder course, moreover it is possible to be molded into
It crosslinks and reacts between hot-fluid plastic cement when type, to substantially increase the binding force of titanium and plastic cement.
Embathe for the second time working solution include: mass percent be 5% dehydrated alcohol, 10% EDTA, 10% coupling
Agent and excess water, dosage 180-250ml/L, treatment temperature room temperature handle time 2-3min.It is using wide at present
Silane coupling agent, such as 3- TSL 8330,3- isocyanate propyl trimethoxysilane.It is embathed for the second time
In, couplant will disperse into the microcellular structure of surface of metal titanium binder course, and be adsorbed in micropore inwall, connect in couplant
The alkoxy meeting partial hydrolysis for connecing silicon atom is silanol, still has part residual after washing wherein, the shape after drying dehydration
At couplant molecular film.In integrated injection moulding, on the one hand, the silanol formed after silane coupling agent hydrolysis can enhance with plastic cement
The hydroxyl on body glass fiber material surface carries out condensation reaction, generates stable silicon oxygen bond, in addition, the organic group of coupling agent again can be with
Plastic resin forms hydrogen bond or chemical bond, and therefore, couplant filling film can be between surface of metal titanium binder course and hot-fluid plastic cement
Play good connection function, the combination between enhancing titanium modeling.
8, it dries, the titanium workpiece cleaned after embathing for the second time through pure water, which is put into dustless hot-blast oven, dries, and dries
Roasting 80-100 DEG C of temperature, drying time 10-20min.
It requires to carry out washing process between each step, the abundant complete of every step treatment process is ensured with this.
Percentage used in the present embodiment is the common mass fraction percentage of chemicals, is general row
Industry standard.
Embodiment 2
Refer to Fig. 4, compound system made from a kind of titanium that the present invention designs surface treatment method integrated with plastic cement
Product comprising: the plastic layer 2 of titanium alloy testing piece 1 and integrated molding on testing piece surface.
The preparation process of composite article:
(2) industrial titanium alloy plate is processed into the testing piece of long 50mm, width 15mm, thickness 1mm, processing method can be
Any one of forging and stamping, punching press, wire cutting, CNC；
(1) preparation of testing piece surface micropore binder course fixes testing piece titanium silk or dedicated titanium hanger, passes through
After pre-treatment that the embodiment of the present invention 1 is included, electrolytic oxidation, postprocessing working procedures, so that testing piece surface forms micropore and combines
Layer；
(2) titanium moulds integrated injection molding, the testing piece handled well is put into the testing piece injection molding machine of customization, with hot-fluid
Plastic cement progress is in-molded, so that the composite article that integration combines be made.Injection molding machine is that nanometer is molded dedicated board, and plastic cement can
To be polybutylene terephthalate (PBT), polyphenylene sulfide (PPS), polyamide (PA) and aforementioned three kinds of materials
Any one in the fiberglass reinforced plastics of material.
For composite article, titanium can mould drawing when negative drawing separates with the bond strength of plastic cement by titanium
Pull out force numerical value embodies, and is tested using measurer for pulling force, and sensing device connects digital display, and testing piece and plastic layer are de-
From when shown data be pulling capacity numerical value.
The present embodiment prepares corresponding composite article with tri- kinds of engineering plastics of PBT, PPS, PA using testing piece, carries out respectively
Pulling capacity test, as a result as follows, it can be deduced that the two combination is very secured:
| Plastic cement type | PBT | PPS | PA |
| Pulling capacity numerical value (kgf) | 120-160 | 160-200 | 180-240 |
Illustrate: the present embodiment only lists three kinds and is usually used in the engineering plastic of nanometer injection molding, but is not only restricted to this；Separately
Outside, there is some difference due to the difference of plastic material composition and tensile strength itself for pulling capacity numerical value.
Embodiment 3
Composite article made from a kind of titanium that the present invention designs surface treatment method integrated with plastic cement comprising:
The plastic portions 4 of titanium alloy mobile phone center 3 and integrated molding on mobile phone center.
The preparation process of composite article:
(2) industrial titanium alloy plate is processed by forging and stamping, punching press or CNC, and carries out polishing deburring and cleaning, hand is made
The semi-finished product embryo material of machine center；
(1) preparation of titanium alloy mobile phone center surface micropore binder course fixes mobile phone center with dedicated titanium hanger,
After pre-treatment that the embodiment of the present invention 1 is included, electrolytic oxidation, postprocessing working procedures so that mobile phone center surface formed it is micro-
Hole binder course；
(2) titanium moulds integrated injection molding, the mobile phone center handled well is put into the mold customized in injection molding machine, with heat
It is in-molded to flow plastic cement progress, so that the composite article that integration combines be made.Injection molding machine is that nanometer is molded dedicated board, plastic cement
It can be polybutylene terephthalate (PBT), polyphenylene sulfide (PPS), polyamide (PA) and three kinds aforementioned
Any one in the fiberglass reinforced plastics of material.
It, will also be by multiple CNC processing removal titanium alloy mobile phone center and modeling after composite article is made in practical application
Redundance on glue part, and appearance is modified by processes such as sanding and polishings, back segment carries out relevant outer again
Combination with decorative surfaces processing is seen, needs to undergo being cleaned multiple times and high-temperature baking in whole process.According to product requirement, titanium and modeling
In conjunction with very securely titanium modeling separation must cannot occur after above-mentioned a series of processing and processing for glue.It is made according to the present invention
The composite article obtained can guarantee the bond strength between titanium modeling, meet the above performance requirement.
The above described is only a preferred embodiment of the present invention, being not intended to limit the present invention in any form, appoint
What those skilled in the art implements to above according to the technical essence of the invention without departing from the scope of the present invention
Any brief introduction modification, equivalent variations and modification made by example, all of which are still within the scope of the technical scheme of the invention.
Claims (10)
1. titanium surface treatment method integrated with plastic cement, which comprises the steps of:
(1) pre-treatment:
1, degreasing removes the greasy dirt of titanium workpiece surface；
2, acid corrosion removes the oxide skin and pollutant of titanium workpiece surface, obtains uniform surface；
3, ash disposal removes remaining one layer of titanium workpiece surface floating ash；
4, it activates, before removing while the oxide film layer of process titanium workpiece surface generation, delays the generation of secondary oxidation, guarantee
The binding force of the binder course of process preparation and substrate afterwards；
(2) electrolytic oxidation:
5, it is put into titanium workpiece as anode in electrolysis working solution, electrolysis working solution includes: phosphatase 11 50200g/L and electrolysis adjustment
Liquid 100-150ml/L, electrolysis adjustment liquid includes: the solution containing oxidizing species, and be powered electrolysis, can be obtained in titanium workpiece surface
It must be well combined with substrate, the binder course with microcellular structure；
(3) it post-processes:
6, it embathes for the first time, the residue of titanium workpiece binder course is cleaned out；
7, it embathes for the second time, forms one layer of absorption filling film in binder course micropore；
8, it dries, titanium workpiece is put into dustless hot-blast oven and is dried.
2. titanium according to claim 1 surface treatment method integrated with plastic cement, which is characterized in that living in step 4
Changing working solution includes: that phosphoric acid 20-40ml/L, sodium fluoride 3-8g/L and activation protection liquid 120-180ml/L, treatment temperature are normal
Temperature handles time 30-60S.
3. titanium according to claim 2 surface treatment method integrated with plastic cement, which is characterized in that the activation is protected
Protecting liquid includes: glycerine and sodium xylene sulfonate.
4. titanium according to claim 1 surface treatment method integrated with plastic cement, which is characterized in that in step 7, the
The secondary working solution that embathes includes: dehydrated alcohol, EDTA and couplant, and treatment temperature room temperature handles time 2-3min.
5. titanium according to claim 1 surface treatment method integrated with plastic cement, which is characterized in that in step 5, place
25 DEG C of temperature, voltage 10-15V of reason, be powered electrolysis 10min, and cathode material is using SUS316 stainless steel plate or compacting active carbon
Plate；The oxidizing species are hydrogen peroxide, potassium permanganate, ammonium persulfate or sodium perchlorate.
6. titanium according to claim 1 surface treatment method integrated with plastic cement, which is characterized in that in step 6, the
Once embathing working solution includes: triethanolamine, natrium carbonicum calcinatum and EDTA, and treatment temperature room temperature handles time 2-3min.
7. titanium according to claim 1 surface treatment method integrated with plastic cement, which is characterized in that in step 3, remove
Grey working solution includes: hydrofluoric acid 30-50ml/L and nitric acid 60-100ml/L, and treatment temperature room temperature handles time 1-2min.
8. titanium according to claim 1 surface treatment method integrated with plastic cement, which is characterized in that in step 2, acid
Anticorrosion work liquid includes: that hydrofluoric acid 60-100ml/L, phosphoric acid 250-350ml/L and ethylene glycol 10-20ml/L, treatment temperature are normal
Temperature handles time 30s.
9. titanium according to claim 1 surface treatment method integrated with plastic cement, which is characterized in that between every step
All carry out washing process.
10. composite article made from a kind of titanium surface treatment method integrated with plastic cement characterized by comprising titanium work
Part and integrated molding are in the plastic cement of titanium workpiece surface, and the titanium workpiece is using surface as described in any one of claim 1 to 9
Processing method preparation.
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| CN201910056606.XA CN109554741B (en) | 2019-01-21 | 2019-01-21 | Titanium metal and plastic integrated surface treatment method and composite product thereof |
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| CN201910056606.XA CN109554741B (en) | 2019-01-21 | 2019-01-21 | Titanium metal and plastic integrated surface treatment method and composite product thereof |
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