CN104772972A - Titanium alloy and engineering plastic integrated glue-free binding method - Google Patents
Titanium alloy and engineering plastic integrated glue-free binding method Download PDFInfo
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- CN104772972A CN104772972A CN201410013889.7A CN201410013889A CN104772972A CN 104772972 A CN104772972 A CN 104772972A CN 201410013889 A CN201410013889 A CN 201410013889A CN 104772972 A CN104772972 A CN 104772972A
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Abstract
The present invention relates to the technical field of surface treatments, particular to a titanium alloy and engineering plastic integrated glue-free binding method, which comprises ultrasonic wave acidification treatment, rinsing in a first water tank, fine etching with a fine etching liquid, rinsing in a second water tank, drying and injection. According to the present invention, the ultrasonic wave and acidification treatment combined manner is adopted, the micro-pore structure is rapidly etched on the titanium alloy surface through the acidification treatment, and the micro-pore structure formed by the acidification treatment is further expanded and deepened through the huge pressure produced by the micro-bubble formed during the acidification treatment process through ultrasonic wave cavitation and the local temperature adjusting; and the fine etching is further adopted to further slowly and meticulous expand and deepen the micro-pore structure on the basis of no damage on the original micro-pore structure, and the polymer chain segment of the engineering plastic can be deeply insert into the micro-pore structure when the engineering plastic is injected into the treated titanium alloy after the micro-pore structure is subjected to two expanding and deepening, such that the engineering plastic and the titanium alloy are firmly bound.
Description
Technical field
The present invention relates to technical field of surface, be specifically related to the method for titanium alloy glue-free combination integrated with engineering plastics.
Background technology
Usually, together with needing titanium alloy to be compound to engineering plastics in parts manufacture field such as automobile, domestic electrification goods, industrial equipments, usual is bonding technology, namely titanium alloy and engineering plastics is bonded together by adhesive.Adhesive technology has developed to obtain comparative maturity, the Chinese invention patent application being 201210321030.3 as application number provides epoxy resin adhesive, comprise following composition: epoxy resin 35-45 weight portion, diethylenetriamines 4-6 weight portion, dibutyl phthalate 6-8 weight portion; Application number be 201210426791.5 Chinese invention patent application disclose Epoxy adhesive, it is made up of the first and second two kinds of combinations: first component is made up of following raw material: 711 epoxy resin, modified epoxy, flexibilizer liquid polysulphide rubber JLY-124, silica flour; Described second component is made up of following raw material: 701 epoxy hardeners, coupling agent KH-550, altax P-30; Mixing, stirs, obtains described Epoxy adhesive.
Although the adhesive property of above-mentioned adhesive is very excellent, still employing dielectric layer---adhesive, not yet finds the method not using adhesive just titanium alloy and engineering plastics firmly can be combined at present.
Summary of the invention
The object of the invention is the deficiency overcoming prior art existence, the method for titanium alloy glue-free combination integrated with engineering plastics is provided.
Object of the present invention is achieved through the following technical solutions: the method for titanium alloy glue-free combination integrated with engineering plastics, comprises the steps:
A: titanium alloy is carried out be processed into titanium alloy shape thing, titanium alloy shape thing is carried out acidification under Ultrasonic Conditions;
B: the titanium alloy after steps A pickling is rinsed through the first pond;
C: the titanium alloy after being rinsed by step B is put into the groove that Micro etching liquid is housed and carried out Micro etching;
D: the titanium alloy after step C Micro etching is put into the second pond and rinse;
E: the titanium alloy after being rinsed by step D carries out drying;
F: engineering plastics are expelled on the titanium alloy of step e process.
Described hyperacoustic FREQUENCY CONTROL is at 35-40kHz, and the acidification time under Ultrasonic Conditions is 5-10min.
Wherein, by weight percentage, in described steps A, the acidifying solution of acidification comprises following component:
Phosphoric acid 5-15%
Potassium peroxydisulfate 0.1-1%
Diammonium hydrogen phosphate 1-5%
Hexamethylenetetramine 0.01-0.03%.
The acidifying solution etch effect of above-mentioned composition is good, etching speed fast and stablize, and can form microcellular structure fast at titanium alloy surface.
Wherein, in described step B and step D, the pH in the first pond and the second pond controls at 5-7.
Wherein, by weight percentage, the Micro etching liquid in described step C comprises following component:
Acetic acid 2-6%
Benzoic acid 0.1-1%
2-benzothiazolyl mercaptan 0.5-1%.
The organic acid that Micro etching liquid of the present invention selects acid more weak acetic acid and benzoic acid to be formed, slowly to corrode, Micro etching liquid of the present invention also adds corrosion inhibiter 2-benzothiazolyl mercaptan simultaneously, 2-benzothiazolyl mercaptan can make titanium alloy surface form oxide-film, after oxide-film reaches certain thickness, the speed of oxidation reaction slows down, corrosion rate reduces greatly, prevent original microcellular structure from too being corroded, to sum up, adopt above-mentioned Micro etching liquid, can on the basis not destroying original microcellular structure, slow and careful further expands microcellular structure and deepens.
Wherein, in described step C, Micro etching temperature is 35-45 DEG C, and the Micro etching time is 1-3min.
Wherein, by weight percentage, in described step F, engineering plastics comprise the raw material of lower weight portion:
Polyphenylene sulfide 25-60 part
Glass fibre 5-10 part
Nano-calcium carbonate 1-4 part
Carbon black pellet 3-6 part
Preferably, in described step F, engineering plastics also include:
Ethylene-butyl acrylate 3-10 part
Pentaerythritol stearate 0.2-1 part
Dilauryl thiodipropionate 0.2-1 part.
The engineering plastics good fluidity of above-mentioned composition, mechanical property is good, is convenient to be deep in the microcellular structure of titanium alloy, makes engineering plastics and titanium alloy strong bonded, is not easy to depart from from the surface of titanium alloy.
Compared with prior art, tool has the following advantages and beneficial effect in the present invention:
The method of titanium alloy provided by the invention glue-free combination integrated with engineering plastics, comprise ultrasonic wave acidification, first pond is rinsed, Micro etching liquid Micro etching, second pond is rinsed, drying and injecting step, the mode that the present invention adopts ultrasonic wave to combine with acidification, acidification goes out microcellular structure at titanium alloy surface fast-etching, the microbubble formed in acidification process vibrates under the effect of sound wave, when acoustic pressure or the sound intensity reach certain value, bubble increases rapidly, then close suddenly, produce shock wave in the moment that bubble is closed to make around bubble, to produce immense pressure and local temperature adjustment, the immense pressure that this ultrasonic cavitation produces and the microcellular structure that local temperature adjustment makes acidification be formed expand further and deepen, the Micro etching that the present invention also adopts Micro etching liquid to carry out, on the basis not destroying original microcellular structure, can on slow and careful basis, microcellular structure further be expanded and deepen, microcellular structure is through twice expansion with after deepening, when engineering plastics being expelled to the titanium alloy through above-mentioned process, the polymer segment of engineering plastics just deeply can slip in microcellular structure, and then makes together with engineering plastics are firmly bonded to titanium alloy.
Detailed description of the invention
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1.
The method of titanium alloy glue-free combination integrated with engineering plastics, comprises the steps:
A: titanium alloy is carried out be processed into titanium alloy shape thing, titanium alloy shape thing is carried out acidification under Ultrasonic Conditions;
B: the titanium alloy after steps A pickling is rinsed through the first pond;
C: the titanium alloy after being rinsed by step B is put into the groove that Micro etching liquid is housed and carried out Micro etching;
D: the titanium alloy after step C Micro etching is put into the second pond and rinse;
E: the titanium alloy after being rinsed by step D carries out drying;
F: engineering plastics are expelled on the titanium alloy of step e process.
Described hyperacoustic FREQUENCY CONTROL is at 35kHz, and the acidification time under Ultrasonic Conditions is 5min.
Wherein, by weight percentage, in described steps A, the acidifying solution of acidification comprises following component:
Phosphoric acid 5%
Potassium peroxydisulfate 1%
Diammonium hydrogen phosphate 5%
Hexamethylenetetramine 0.01%
Water surplus.
Wherein, in described step B and step D, the pH in the first pond and the second pond controls 5.
Wherein, by weight percentage, the Micro etching liquid in described step C is made up of following component:
Acetic acid 2%
Benzoic acid 1%
2-benzothiazolyl mercaptan 1%
Water surplus.
Wherein, in described step C, Micro etching temperature is 35 DEG C, and the Micro etching time is 1min.
Wherein, by weight percentage, in described step F, engineering plastics are made up of the raw material of following weight portion:
Polyphenylene sulfide 25 parts
5 parts, glass fibre
Nano-calcium carbonate 1 part
Carbon black pellet 3 parts
Ethylene-butyl acrylate 3 parts
Pentaerythritol stearate 0.2 part
Dilauryl thiodipropionate 0.2 part.
By the method for the present embodiment, engineering plastics and titanium alloy are carried out glue-free combination, recording its shear fracture power is 24.6MPa.
Embodiment 2.
The method of titanium alloy glue-free combination integrated with engineering plastics, comprises the steps:
A: titanium alloy is carried out be processed into titanium alloy shape thing, titanium alloy shape thing is carried out acidification under Ultrasonic Conditions;
B: the titanium alloy after steps A pickling is rinsed through the first pond;
C: the titanium alloy after being rinsed by step B is put into the groove that Micro etching liquid is housed and carried out Micro etching;
D: the titanium alloy after step C Micro etching is put into the second pond and rinse;
E: the titanium alloy after being rinsed by step D carries out drying;
F: engineering plastics are expelled on the titanium alloy of step e process.
Described hyperacoustic FREQUENCY CONTROL is at 38kHz, and the acidification time under Ultrasonic Conditions is 8min.
Wherein, by weight percentage, in described steps A, the acidifying solution of acidification comprises following component:
Phosphatase 11 5%
Potassium peroxydisulfate 0.1%
Diammonium hydrogen phosphate 1%
Hexamethylenetetramine 0.03%
Water surplus.
Wherein, in described step B and step D, the pH in the first pond and the second pond controls 6.
Wherein, by weight percentage, the Micro etching liquid in described step C is made up of following component:
Acetic acid 3%
Benzoic acid 0.5%
2-benzothiazolyl mercaptan 0.8%
Water surplus.
Wherein, in described step C, Micro etching temperature is 38 DEG C, and the Micro etching time is 2min.
Wherein, by weight percentage, in described step F, engineering plastics are made up of the raw material of following weight portion:
Polyphenylene sulfide 40 parts
8 parts, glass fibre
Nano-calcium carbonate 3 parts
Carbon black pellet 4 parts
Ethylene-butyl acrylate 6 parts
Pentaerythritol stearate 0.6 part
Dilauryl thiodipropionate 0.6 part.
By the method for the present embodiment, engineering plastics and titanium alloy are carried out glue-free combination, recording its shear fracture power is 24.1MPa.
Embodiment 3.
The method of titanium alloy glue-free combination integrated with engineering plastics, comprises the steps:
A: titanium alloy is carried out be processed into titanium alloy shape thing, titanium alloy shape thing is carried out acidification under Ultrasonic Conditions;
B: the titanium alloy after steps A pickling is rinsed through the first pond;
C: the titanium alloy after being rinsed by step B is put into the groove that Micro etching liquid is housed and carried out Micro etching;
D: the titanium alloy after step C Micro etching is put into the second pond and rinse;
E: the titanium alloy after being rinsed by step D carries out drying;
F: engineering plastics are expelled on the titanium alloy of step e process.
Described hyperacoustic FREQUENCY CONTROL is at 40kHz, and the acidification time under Ultrasonic Conditions is 10min.
Wherein, by weight percentage, in described steps A, the acidifying solution of acidification comprises following component:
Phosphatase 11 5%
Potassium peroxydisulfate 1%
Diammonium hydrogen phosphate 5%
Hexamethylenetetramine 0.03%
Water surplus.
Wherein, in described step B and step D, the pH in the first pond and the second pond controls 7.
Wherein, by weight percentage, the Micro etching liquid in described step C is made up of following component:
Acetic acid 6%
Benzoic acid 0.1%
2-benzothiazolyl mercaptan 0.5%
Water surplus.
Wherein, in described step C, Micro etching temperature is 45 DEG C, and the Micro etching time is 3min.
Wherein, by weight percentage, in described step F, engineering plastics are made up of the raw material of following weight portion:
Polyphenylene sulfide 60 parts
10 parts, glass fibre
Nano-calcium carbonate 4 parts
Carbon black pellet 6 parts
Ethylene-butyl acrylate 10 parts
Pentaerythritol stearate 1 part
Dilauryl thiodipropionate 1 part.
By the method for the present embodiment, engineering plastics and titanium alloy are carried out glue-free combination, recording its shear fracture power is 23.9MPa.
Embodiment 4.
The method of titanium alloy glue-free combination integrated with engineering plastics, comprises the steps:
A: titanium alloy is carried out be processed into titanium alloy shape thing, titanium alloy shape thing is carried out acidification under Ultrasonic Conditions;
B: the titanium alloy after steps A pickling is rinsed through the first pond;
C: the titanium alloy after being rinsed by step B is put into the groove that Micro etching liquid is housed and carried out Micro etching;
D: the titanium alloy after step C Micro etching is put into the second pond and rinse;
E: the titanium alloy after being rinsed by step D carries out drying;
F: engineering plastics are expelled on the titanium alloy of step e process.
Described hyperacoustic FREQUENCY CONTROL is at 35kHz, and the acidification time under Ultrasonic Conditions is 5min.
Wherein, by weight percentage, in described steps A, the acidifying solution of acidification comprises following component:
Phosphatase 11 2%
Potassium peroxydisulfate 0.2%
Diammonium hydrogen phosphate 2%
Hexamethylenetetramine 0.02%
Water surplus.
Wherein, in described step B and step D, the pH in the first pond and the second pond controls 5.
Wherein, by weight percentage, the Micro etching liquid in described step C is made up of following component:
Acetic acid 5%
Benzoic acid 0.7%
2-benzothiazolyl mercaptan 0.6%
Water surplus.
Wherein, in described step C, Micro etching temperature is 42 DEG C, and the Micro etching time is 2min.
Wherein, by weight percentage, in described step F, engineering plastics are made up of the raw material of following weight portion:
Polyphenylene sulfide 55 parts
6 parts, glass fibre
Nano-calcium carbonate 3 parts
Carbon black pellet 5 parts
Ethylene-butyl acrylate 9 parts
Pentaerythritol stearate 0.7 part
Dilauryl thiodipropionate 0.6 part.
By the method for the present embodiment, engineering plastics and titanium alloy are carried out glue-free combination, recording its shear fracture power is 23.6MPa.
Embodiment 5.
The method of titanium alloy glue-free combination integrated with engineering plastics, comprises the steps:
A: titanium alloy is carried out be processed into titanium alloy shape thing, titanium alloy shape thing is carried out acidification under Ultrasonic Conditions;
B: the titanium alloy after steps A pickling is rinsed through the first pond;
C: the titanium alloy after being rinsed by step B is put into the groove that Micro etching liquid is housed and carried out Micro etching;
D: the titanium alloy after step C Micro etching is put into the second pond and rinse;
E: the titanium alloy after being rinsed by step D carries out drying;
F: engineering plastics are expelled on the titanium alloy of step e process.
Described hyperacoustic FREQUENCY CONTROL is at 39kHz, and the acidification time under Ultrasonic Conditions is 9min.
Wherein, by weight percentage, in described steps A, the acidifying solution of acidification comprises following component:
Phosphoric acid 5%
Potassium peroxydisulfate 0.1%
Diammonium hydrogen phosphate 1%
Hexamethylenetetramine 0.01%
Water surplus.
Wherein, in described step B and step D, the pH in the first pond and the second pond controls 5.
Wherein, by weight percentage, the Micro etching liquid in described step C is made up of following component:
Acetic acid 4%
Benzoic acid 0.3%
2-benzothiazolyl mercaptan 0.9%
Water surplus.
Wherein, in described step C, Micro etching temperature is 43 DEG C, and the Micro etching time is 2min.
Wherein, by weight percentage, in described step F, engineering plastics are made up of the raw material of following weight portion:
Polyphenylene sulfide 25 parts
5 parts, glass fibre
Nano-calcium carbonate 1 part
Carbon black pellet 3 parts
Ethylene-butyl acrylate 3 parts
Pentaerythritol stearate 0.2 part
Dilauryl thiodipropionate 0.2 part.
By the method for the present embodiment, engineering plastics and titanium alloy are carried out glue-free combination, recording its shear fracture power is 24.2MPa.
Embodiment 6.
The method of titanium alloy glue-free combination integrated with engineering plastics, comprises the steps:
A: titanium alloy is carried out be processed into titanium alloy shape thing, titanium alloy shape thing is carried out acidification under Ultrasonic Conditions;
B: the titanium alloy after steps A pickling is rinsed through the first pond;
C: the titanium alloy after being rinsed by step B is put into the groove that Micro etching liquid is housed and carried out Micro etching;
D: the titanium alloy after step C Micro etching is put into the second pond and rinse;
E: the titanium alloy after being rinsed by step D carries out drying;
F: engineering plastics are expelled on the titanium alloy of step e process.
Described hyperacoustic FREQUENCY CONTROL is at 40kHz, and the acidification time under Ultrasonic Conditions is 10min.
Wherein, by weight percentage, in described steps A, the acidifying solution of acidification comprises following component:
Phosphatase 11 5%
Potassium peroxydisulfate 1%
Diammonium hydrogen phosphate 5%
Hexamethylenetetramine 0.03%
Water surplus.
Wherein, in described step B and step D, the pH in the first pond and the second pond controls 7.
Wherein, by weight percentage, the Micro etching liquid in described step C is made up of following component:
Acetic acid 6%
Benzoic acid 0.1%
2-benzothiazolyl mercaptan 0.8%
Water surplus.
Wherein, in described step C, Micro etching temperature is 39 DEG C, and the Micro etching time is 2min.
Wherein, by weight percentage, in described step F, engineering plastics are made up of the raw material of following weight portion:
Polyphenylene sulfide 60 parts
10 parts, glass fibre
Nano-calcium carbonate 4 parts
Carbon black pellet 6 parts
Ethylene-butyl acrylate 10 parts
Pentaerythritol stearate 1 part
Dilauryl thiodipropionate 1 part.
By the method for the present embodiment, engineering plastics and titanium alloy are carried out glue-free combination, recording its shear fracture power is 24.5MPa.
Above-described embodiment is the present invention's preferably embodiment, but embodiments of the present invention are not restricted to the described embodiments, and therefore according to the equivalent variations that the present patent application the scope of the claims is done, is included within protection scope of the present invention.
Claims (8)
1. the method for titanium alloy glue-free combination integrated with engineering plastics, is characterized in that: comprise the steps:
A: titanium alloy is carried out be processed into titanium alloy shape thing, titanium alloy shape thing is carried out acidification under Ultrasonic Conditions;
B: the titanium alloy after steps A pickling is rinsed through the first pond;
C: the titanium alloy after being rinsed by step B is put into the groove that Micro etching liquid is housed and carried out Micro etching;
D: the titanium alloy after step C Micro etching is put into the second pond and rinse;
E: the titanium alloy after being rinsed by step D carries out drying;
F: engineering plastics are expelled on the titanium alloy of step e process.
2. the method for titanium alloy according to claim 1 glue-free combination integrated with engineering plastics, is characterized in that: described hyperacoustic FREQUENCY CONTROL is at 35-40kHz, and the acidification time under Ultrasonic Conditions is 5-10min.
3. the method for titanium alloy according to claim 1 glue-free combination integrated with engineering plastics, it is characterized in that: by weight percentage, in described steps A, the acidifying solution of acidification comprises following component:
Phosphoric acid 5-15%
Potassium peroxydisulfate 0.1-1%
Diammonium hydrogen phosphate 1-5%
Hexamethylenetetramine 0.01-0.03%.
4. the method for titanium alloy according to claim 1 glue-free combination integrated with engineering plastics, it is characterized in that: in described step B and step D, the pH in the first pond and the second pond controls at 5-7.
5. the method for titanium alloy according to claim 1 glue-free combination integrated with engineering plastics, is characterized in that: by weight percentage, and the Micro etching liquid in described step C comprises following component:
Acetic acid 2-6%
Benzoic acid 0.1-1%
2-benzothiazolyl mercaptan 0.5-1%.
6. the method for titanium alloy according to claim 1 glue-free combination integrated with engineering plastics, is characterized in that: in described step C, and Micro etching temperature is 35-45 DEG C, and the Micro etching time is 1-3min.
7. the method for titanium alloy according to claim 1 glue-free combination integrated with engineering plastics, it is characterized in that: by weight percentage, in described step F, engineering plastics comprise the raw material of lower weight portion:
Polyphenylene sulfide 25-60 part
Glass fibre 5-10 part
Nano-calcium carbonate 1-4 part
Carbon black pellet 3-6 part.
8. the method for titanium alloy according to claim 7 glue-free combination integrated with engineering plastics, is characterized in that: in described step F, engineering plastics also include:
Ethylene-butyl acrylate 3-10 part
Pentaerythritol stearate 0.2-1 part
Dilauryl thiodipropionate 0.2-1 part.
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| CN109355659A (en) * | 2018-09-21 | 2019-02-19 | 广东长盈精密技术有限公司 | The surface treatment method and titanium alloy product of titanium alloy, titanium alloy-Plastic composite body and preparation method thereof |
| CN112828291A (en) * | 2020-12-31 | 2021-05-25 | 宁波通导电子有限公司 | Manufacturing method of high-temperature operation robot |
| CN114606499A (en) * | 2022-04-07 | 2022-06-10 | 燕山大学 | Metal with microporous structure on surface and preparation method and application thereof |
| JP7272704B1 (en) | 2021-11-16 | 2023-05-12 | ドングァン ディーエスピー テクノロジー カンパニー リミテッド | Titanium surface treatment method for polymer titanium joints |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109355659A (en) * | 2018-09-21 | 2019-02-19 | 广东长盈精密技术有限公司 | The surface treatment method and titanium alloy product of titanium alloy, titanium alloy-Plastic composite body and preparation method thereof |
| CN112828291A (en) * | 2020-12-31 | 2021-05-25 | 宁波通导电子有限公司 | Manufacturing method of high-temperature operation robot |
| JP7272704B1 (en) | 2021-11-16 | 2023-05-12 | ドングァン ディーエスピー テクノロジー カンパニー リミテッド | Titanium surface treatment method for polymer titanium joints |
| CN116136023A (en) * | 2021-11-16 | 2023-05-19 | 东莞市德施普技术有限公司 | Titanium surface treatment method |
| JP2023073924A (en) * | 2021-11-16 | 2023-05-26 | ドングァン ディーエスピー テクノロジー カンパニー リミテッド | Titanium surface treatment method for polymer-titanium joint structure |
| EP4187001A1 (en) * | 2021-11-16 | 2023-05-31 | Dongguan DSP Technology Co., Ltd. | Titanium surface treatment method |
| CN114606499A (en) * | 2022-04-07 | 2022-06-10 | 燕山大学 | Metal with microporous structure on surface and preparation method and application thereof |
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Application publication date: 20150715 |